research article spectroscopic characteristics of...

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Research Article Spectroscopic Characteristics of Dissolved Organic Matter in Afforestation Forest Soil of Miyun District, Beijing Shi-Jie Gao, 1,2 Chen Zhao, 2 Zong-Hai Shi, 3 Jun Zhong, 2 Jian-Guo Liu, 2 and Jun-Qing Li 1 1 College of Forestry, Beijing Forestry University, Beijing 100083, China 2 Key Laboratory of Urban Stormwater System, Beijing University of Civil Engineering and Architecture, Beijing 100044, China 3 Beijing Industrial Technician College, Beijing 100023, China Correspondence should be addressed to Shi-Jie Gao; [email protected] Received 6 April 2016; Accepted 30 May 2016 Academic Editor: Miguel de la Guardia Copyright © 2016 Shi-Jie Gao et al. is is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. In this study, soil samples collected from different plain afforestation time (1 year, 4 years, 10 years, 15 years, and 20 years) in Miyun were characterized, including total organic carbon (TOC), total nitrogen (TN), total phosphorus (TP), available K (K + ), microbial biomass carbon (MBC), and dissolved organic carbon (DOC). e DOM in the soil samples with different afforestation time was further characterized via DOC, UV-Visible spectroscopy, excitation-emission matrix (EEM) fluorescence spectroscopy, and 1 H NMR spectroscopy. e results suggested that the texture of soil sample was sandy. e extracted DOM from soil consisted mainly of aliphatic chains and only a minor aromatic component. It can be included that afforestation can improve the soil quality to some extent, which can be partly reflected from the indexes like TOC, TN, TP, K + , MBC, and DOC. And the characterization of DOM implied that UV humic-like substances were the major fluorophores components in the DOM of the soil samples, which consisted of aliphatic chains and aromatic components with carbonyl, carboxyl, and hydroxyl groups. 1. Introduction Urban forestry is oſten regarded as a key ecological asset of a city, which can significantly improve the ecoenvironment by lowering urban temperature by reducing heat island effect, improving air quality by absorbing pollutants, mitigat- ing urban waterlogging by quick infiltration of stormwater runoff, and enhancing biodiversity by provision of habitat for living things. Each year, many efforts are put into urban afforestation in China, which led to the increase of the total forest area and the amount of forest reserves, further to make the cities more attractive and livable [1]. In case of Beijing, the capital of China, a large-scale plain reforestation project was launched, in which 133,000 hm 2 afforestation forest was planned to increase each year from 2012 to 2015 [2]. Up to now, numerous studies have been carried out to investigate the characters of forest soil [3–5] and the dissolv- ing organic matter in farmland soil [6], but few attentions were put to study the soil status of urban afforestation area. In order to assess the soil quality of urban afforestation, the dissolved organic matter (DOM), as the part of organic matter, was deemed to play a significant role in soil biological activity [7, 8]. And DOM can be regarded as a measure of soil quality and an integral part in a forest ecosystem, as its presence can increase the forest production by reducing erosion, increasing the elasticity, porosity, and water retention [9]. It is the most active and labile fraction with different molecular sizes, structures, and functional properties [8, 10] and exhibits heterogeneous nature as it is composed of the diverse and complicated compounds with different func- tional groups like aliphatic/phenolic hydroxy, amino, and carbohydrates [11, 12]. Generally, DOM plays an important role in the growth of plants due to its molecular structure. And it helps to break up clay and compacted soils, assists in transferring nutrients from the soil to the plant, and enhances water retention. Hence, to understand the dynamics of plant growth, it is nec- essary to know how DOM is distributed throughout the soil. In this paper, Miyun District, which was a typical afforesta- tion area in Beijing, was chosen as sampling area. And the Hindawi Publishing Corporation Journal of Analytical Methods in Chemistry Volume 2016, Article ID 1480857, 10 pages http://dx.doi.org/10.1155/2016/1480857

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Page 1: Research Article Spectroscopic Characteristics of ...downloads.hindawi.com/journals/jamc/2016/1480857.pdf · Microbial biomass carbon (MBC) analysis was determined by the chloroform

Research ArticleSpectroscopic Characteristics of Dissolved Organic Matter inAfforestation Forest Soil of Miyun District Beijing

Shi-Jie Gao12 Chen Zhao2 Zong-Hai Shi3 Jun Zhong2 Jian-Guo Liu2 and Jun-Qing Li1

1College of Forestry Beijing Forestry University Beijing 100083 China2Key Laboratory of Urban Stormwater System Beijing University of Civil Engineering and Architecture Beijing 100044 China3Beijing Industrial Technician College Beijing 100023 China

Correspondence should be addressed to Shi-Jie Gao gaoshijie2006163com

Received 6 April 2016 Accepted 30 May 2016

Academic Editor Miguel de la Guardia

Copyright copy 2016 Shi-Jie Gao et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

In this study soil samples collected from different plain afforestation time (1 year 4 years 10 years 15 years and 20 years) in Miyunwere characterized including total organic carbon (TOC) total nitrogen (TN) total phosphorus (TP) available K (K+) microbialbiomass carbon (MBC) and dissolved organic carbon (DOC) The DOM in the soil samples with different afforestation time wasfurther characterized via DOC UV-Visible spectroscopy excitation-emission matrix (EEM) fluorescence spectroscopy and 1HNMR spectroscopyThe results suggested that the texture of soil sample was sandyThe extracted DOM from soil consisted mainlyof aliphatic chains and only a minor aromatic component It can be included that afforestation can improve the soil quality to someextent which can be partly reflected from the indexes like TOC TN TP K+ MBC and DOC And the characterization of DOMimplied that UV humic-like substances were the major fluorophores components in the DOM of the soil samples which consistedof aliphatic chains and aromatic components with carbonyl carboxyl and hydroxyl groups

1 Introduction

Urban forestry is often regarded as a key ecological asset ofa city which can significantly improve the ecoenvironmentby lowering urban temperature by reducing heat islandeffect improving air quality by absorbing pollutants mitigat-ing urban waterlogging by quick infiltration of stormwaterrunoff and enhancing biodiversity by provision of habitatfor living things Each year many efforts are put into urbanafforestation in China which led to the increase of the totalforest area and the amount of forest reserves further to makethe cities more attractive and livable [1] In case of Beijingthe capital of China a large-scale plain reforestation projectwas launched in which 133000 hm2 afforestation forest wasplanned to increase each year from 2012 to 2015 [2]

Up to now numerous studies have been carried out toinvestigate the characters of forest soil [3ndash5] and the dissolv-ing organic matter in farmland soil [6] but few attentionswere put to study the soil status of urban afforestation areaIn order to assess the soil quality of urban afforestation

the dissolved organic matter (DOM) as the part of organicmatter was deemed to play a significant role in soil biologicalactivity [7 8] And DOM can be regarded as a measure ofsoil quality and an integral part in a forest ecosystem asits presence can increase the forest production by reducingerosion increasing the elasticity porosity andwater retention[9] It is the most active and labile fraction with differentmolecular sizes structures and functional properties [8 10]and exhibits heterogeneous nature as it is composed of thediverse and complicated compounds with different func-tional groups like aliphaticphenolic hydroxy amino andcarbohydrates [11 12]

Generally DOM plays an important role in the growth ofplants due to its molecular structure And it helps to breakup clay and compacted soils assists in transferring nutrientsfrom the soil to the plant and enhances water retentionHence to understand the dynamics of plant growth it is nec-essary to know how DOM is distributed throughout the soilIn this paper Miyun District which was a typical afforesta-tion area in Beijing was chosen as sampling area And the

Hindawi Publishing CorporationJournal of Analytical Methods in ChemistryVolume 2016 Article ID 1480857 10 pageshttpdxdoiorg10115520161480857

2 Journal of Analytical Methods in Chemistry

Miyun District

Xi Tian Ge Zhuang ZhenBeijing

Miyun

(m)(m)

(m)

0 5000025000 0 2500012500

0 50002500

NE

SW

NE

SW

NE

SW

Xi Tian Ge Zhuang Zhen

Miyun Zhen

Y-1

Y-4

Y-10Y-15

Y-20

Figure 1 Schematic map of the selected area and the sampling sites

total organic carbon (TOC) total nitrogen (TN) total phos-phorus (TP) available potassium (K+) microbial biomasscarbon (MBC) and dissolved organic carbon (DOC) weredetermined The DOM in the soil samples with differentafforestation timewas extracted and further characterized viadissolved organic carbon (DOC) UV-Visible spectroscopyEEM fluorescence spectroscopy and 1H NMR spectroscopySome valuable information on the soil quality of afforestationarea can be provided whichwill guide the future afforestationand corresponding management plan in Beijing

2 Materials and Experimental

21 Sampling Sites Description As a typical afforestation areaXi Tian Ge Zhuang town of Miyun District was selected assampling region as illustrated in Figure 1 The mean annualrainfall and average temperature of this area is 6613mm and108∘C respectively Five sampling regionswith different plain

afforestation time (1 year 4 years 10 years 15 years and20 years) were selected in this study and the samples werecollected on June 27th 2015 (Table 1) At each sampling area5 samples were collected with columns of 20 times 5 cm (long timesdiameter) via Soil Core Samplers (AMS samplers AmericanFalls Idaho) [9 13]

22 Pretreatment of the Soil Samples In laboratory after thevisible roots plant fragments grass and tones were removedthe soil samples were dried in the open air passed througha 2mm sieve and stored at room temperature in airtightglassware containers [5]

23 The Determination of Some Soil Parameters Soil bulkdensity wasmeasured according toMA Rab using bulk den-sity soil sampling kit (AMS samplers American Falls Idaho)[14] The distribution of soil particle was analyzed with Mas-tersizer 3000 (Malvern Instrument Ltd UK) to determine

Journal of Analytical Methods in Chemistry 3

Table 1 Locations and afforestation information of the samples

Abbreviation Tree species Growing period CoordinatesY-1 Pagoda tree 1 yr N40∘24101584059610158401015840 E116∘45101584043710158401015840

Y-4 Pagoda tree 4 yrs N40∘24101584030810158401015840 E116∘45101584000010158401015840

Y-10 Populus tomentosa 10 yrs N40∘23101584058410158401015840 E116∘43101584041610158401015840

Y-15 Populus tomentosa 15 yrs N40∘24101584000710158401015840 E116∘43101584037110158401015840

Y-20 Shrub and locust 20 yrs N40∘20101584052210158401015840 E116∘49101584022010158401015840

the content of clay silt and sand in the soil samples [15]The pH values of the soil were measured in a suspension(waterdry soil 25 1) using a PB-10 pH meter (SartoriusGermany) [16] Microbial biomass carbon (MBC) analysiswas determined by the chloroform fumigation-extractionmethod [17] Total organic carbon (TOC) was calculatedby subtracting inorganic carbon (calculated from CaCO

3

content) from total carbon by a Jena multi NC 3100 analyzer[18] The total N P and available P of the soil sample weremeasured using a AA3 continuous-flow analyzer (Seal Ana-lytical Corporation Germany)The available Kwasmeasuredby flame atomic absorption spectrometric method via PerkinElmer 9100 Atomic Absorption Spectrometry

24 DOM Extraction and Analytical Methods 100 g soilsample was mixed with 500mL distilled water in 1000mLcentrifuge tube whichwas shaken at 200 rmin in a reciprocalshaker for 16 h under room temperature (25∘C) and thencentrifuged at 12000 rmin for 20min The supernatant wasmoved out of centrifuge tube with a hydrophilic PVDFMillipore membrane filter (045 120583m) to carry out the follow-ing characterizations like dissolved organic carbon (DOC)UV-Visible spectroscopy excitation-emission matrix (EEM)fluorescence spectroscopy and even 1H NMR spectroscopy

25 UV-Visible Spectroscopy UV-Visible spectra of the DOMin filtered supernatant were recorded from 200 to 600 nmon a PerkinElmer Lambda 650S spectrophotometer using a10 cmquartz cell [19]The absorbance at 300 nmwas adjustedto 002 to avoid inner filter effects [20] Ultrapure water(Milli-Q 18MΩsdotcm) was selected as the blank

26 Excitation-Emission Matrix (EEM) Fluorescence Spec-troscopy The excitation and emission spectra of the DOMin filtered supernatant were measured on a Hitachi F-7000fluorescence spectrophotometer using a 150W xenon arclamp as the light source Both excitation and emission slitsare 10 nmwith a scan range from 200 nm to 550 nmThe scanrate was 1200 nmmin and the photomultiplier tube voltagewas 700V The standard quinine sulfate units (QSU) wereintroduced to determine the samplesrsquo relative fluorescentintensities that is 4221 intensity unit is equivalent to oneQSU (1 QSU = 1 120583g Lminus1 = 1 ppb quinine sulfate in 005mol Lminus1H2SO4) [21 22] The Rayleigh scatter effects were eliminated

from the data set by adding zero to the EEMs in the twotriangle regions (Em le Ex + 20 nm and Em ge 2Ex minus10 nm) [23] along with Raman scatter that was avoided bysubtracting the background value of the ultrapure water asblank [23 24] to highlight the useful fluorescent information

27 1H NMR Spectroscopy Agilent VacElut SPS 24 solidphase extraction (SPE) equipment with Bond Elut C-18 assorbent was selected to isolate the DOM from the samplesin which 100mL leaching liquor extracted from soil samplewas pumped through the SPE column with the speed of10mLmin Two 50mL ultrapure water solvents were usedto pass through the SPE column to wash off the residual saltsTheDOMheld in the C-18 packing of SPE columnwas elutedoffwith 6mL solutionmatrix of water andmethanol with vol-ume ratio of 1 9The reduced pressure was stained for 30minto remove the residual solvent [21] Finally the extractedDOM was dried under N

2gas with Termovap Sample

Concentrator (YGC-1217 Bao Jing Company) [22] In orderto conduct 1H NMR spectroscopy analysis the obtainedsolid DOM extracts were dissolved in D

2O (Jin Ouxiang

Company) to avoid water peaks Measurements of 1H NMRspectra of theDOMwere performed on aBruker 400MNMRspectrometerThe pulse conditions of 1HNMRwere listed asthe following operating frequency = 499898MHz acquisi-tion time= 2045 s recycle delay = 10 s and line broadening =10Hz The standard s2pul pulse sequence and baselinecorrection was applied The functional groups in the 1HNMR spectra were identified on their corresponding chemi-cal shifts (120575H) relative to that of the water (47 ppm) [25]

3 Results and Discussion

31 Soil Texture and Soil Quality Indicators The basic phys-ical and chemical properties of the soil samples are assessedAs listed in Table 2 it can be seen that all of the soil samplesselected in this study are sandy texture with a siltsand ratioranging from 7389 to 9264 and the bulk densities werein the range of 145ndash157 gsdotcmminus3 which matched well thepreviously reported values [26] As shown in Table 3 thebasic indexes of soil fertility total organic carbon (TOC)total nitrogen (TN) total phosphorus (TP) and availablepotassium (K) are ranging from 264 to 452 gsdotkgminus1 003to 005 gsdotkgminus1 005 to 048 gsdotkgminus1 and 021 to 061 gsdotkgminus1respectively The TOC increases with the increasing of theafforestation time when the afforestation time is less than tenyear and then remains nearly constant when the time is up toten year The microbial biomass carbon analysis (MBC) andwater extracted dissolved organic carbon (DOC) are in therange of 1628 to 9270mgsdotkgminus1 and 5608 to 8110mgsdotkgminus1respectively The highest MBC (9270mgsdotkgminus1) is observed atsample Y-20 All of the basic physical and chemical propertiesof the samples are shown that the afforestation can improvebiomass in soil

4 Journal of Analytical Methods in Chemistry

Table 2 Basic physical properties of the soil samples

Sample point Clay () Silt () Sand () Bulk density(gsdotcmminus3)

Y-1 021 715 9123 157Y-4 094 2075 7830 149Y-10 082 2324 7594 145Y-15 025 1004 8971 151Y-20 114 2497 7189 151

Abso

rban

ce

200

300

400

500

600 Wav

eleng

ths (

nm)

Y-1Y-4

Y-10Y-15

Y-20

12

10

08

06

04

02

00

Figure 2 UV-Visible spectra of the soil samples

32 Spectroscopic Characteristics of DOM in Soil Samples

321 UV-Visible Spectroscopy As an efficient tool the UV-Visible spectroscopy is employed to evaluate the compositionand structure of DOM [27 28] As illustrated in Figure 2all the UV-Visible spectrum absorbance of the five samplesdecreased with the wavelength which can be found inother studies [5 24 29 30] Some small shoulder peakscan be found in the region of 250ndash300 nm which might becontributed by phenolic aromatic carboxylic and polycyclicaromatic compounds (120587 rarr 120587lowast transition) [31]

The spectral slope coefficients (119878) calculated from theUV-Visible spectra data exhibited the light absorption efficiencyof DOM as a function of the wavelength which negativelyrelates to molecular weight of DOM [32 33] Jamieson et alcalculated 119878 values within the spectra region of 275ndash295 nmto characterize the biochar-derived DOM isolated from soil[32] and Stedmon et al calculated 119878 values in the region from300 to 650 nm to investigate themolecular weight of DOM inDanish coastal water bodies [34] To avoid the use of spectraldata near the detection limit of the instruments the ratioof the slope of the shorter wavelength region (275ndash295 nm119878275ndash295) to that of the longerwavelength region (350ndash400 nm119878350ndash400) was calculated and this dimensionless parametercan be called 119878

119877[33]

The 119878 and 119878119877values were calculated as follows

119886 (120582) = 119886 (1205820) 119890119878(1205820minus120582)

+ 119870

119886 (120582) =

2303119860 (120582)

119897

119878119877=

119878275ndash295119878350ndash400

(1)

in which 119886(120582) and 119886(1205820) represent absorption coefficients

and absorption coefficients at reference wavelength respec-tively 120582 and 120582

0are the reference wavelength (300 nm was

selected in this study) and the selected wavelength (rangingfrom 240 nm to 400 nm) respectively 119860(120582) represents theabsorbance at wavelength 120582 (nm) 119897 (m) is the optical pathlength (001m in this study) and 119870 is a background 119889parameter to improve the goodness of fitting

The median of 119878119877

values determined for the DOMsamples of the five sits (Y-1 Y-4 Y-10 Y-15 and Y-20) was064 107 092 095 and 077 respectively suggesting that themolecular weight of DOM in the soil samples is Y-1 gt Y-20 gtY-10 gt Y-15 gt Y-4

In order to explore the aromaticity of the DOM samplesSUVA

254was introduced as follows

SUVA254=

119886254

DOC (2)

where 119886254

(mminus1) is the absorbance coefficient measured at254 nm The median values of SUVA

254were 539 590 483

533 and 439 LmgCminus1mminus1 for Y-1 Y-4 Y-10 Y-15 and Y-20 respectively The previously reported SUVA

254values of

wetland soil [35] and the agricultural soil [27] were 351ndash441 and 032ndash465 respectively suggesting that the DOM inour study contained a greater amount of aromatic structuresAnd previous studies proposed that different landscapes werelikely to produce different types of DOM [36 37] thereforethe SUVA

254values in this study could roughly imply that

afforestation in suburban area can produce the aromaticsubstances The highest values of SUVA

254were observed at

Y-4 while the lowest values were observed at Y-20

322 Excitation-Emission Matrix (EEM) Fluorescence Spec-troscopy The excitation-emission matrix (EEM) fluores-cence technique is powerful to provide sufficient informa-tion on DOMrsquos molecular size chemical composition andaromaticity or aliphatic properties [5 27] EEM can identifyhumic-like (designated as A C and M) and protein-likefluorescence peaks (B and T) as listed in Table 4 EEMfluorescence spectra of the study areas samples were depictedin Figures 3(a)ndash3(e) suggesting that the UV humic-likesubstances were the primary fluorophores components inthe DOM extracted from afforestation land samples [38]The first identified peak (peak A) was located at ExEm of257 nm448 nm 256 nm440 nm 262 nm443 nm 260 nm425 nm and 260 nm435 nm for the Y-1 Y-4 Y-10 Y-15 andY-20 samples respectively suggesting the existence of UVhumic-like substances The second typical peak (peak T)was observed at ExEm of 271 nm347 nm 280 nm325 nm

Journal of Analytical Methods in Chemistry 5

Table 3 Basic chemical properties of the soil samples

Sample point pH TN (gsdotkgminus1) TP (gsdotkgminus1) Available K (mgsdotkgminus1) TOC (gsdotkgminus1) MBC (mgsdotkgminus1) DOC (mgsdotkgminus1)Y-1 634 003 009 051 264 1628 8110Y-4 633 005 019 030 277 4209 6845Y-10 657 002 021 025 445 1964 6125Y-15 665 002 048 021 452 5945 5608Y-20 705 003 005 061 445 9270 6943

Table 4 Peaks description and excitationemission maxima of fluorescent DOM

Peaks Description Excitation max (nm) Emission max (nm)A UV humic-like less aromatic lt260 380ndash460C Visible humic-like more aromatic 320ndash360 420ndash460M Marine-humic-like 290ndash310 370ndash410B Tyrosine-like substances 260 280T Protein-like tryptophan 250ndash300 305ndash355

275 nm338 nm 279 nm333 nm and 271 nm339 nm for thefive samples stated above respectively implying the pres-ence of tryptophan protein-like components [38] GenerallyDOM in soil is affected by some factors like local geologyland use and microbial and human activities [38] And itcan be believed that the presence of tryptophan protein-likesubstances could further confirm the larger molecular weightDOM presented in the soil [39 40]

Moreover the fluorescence intensities of the five sites (Y-1Y-4 Y-10 Y-15 andY-20) for peakAwere 24 60 78 63 and 81QSU respectively while the peak T fluorescence intensities ofthe five sites were 834 91 106 76 and 124 QSU respectively

Three typical fluorescence indices like the fluorescenceindex (FI) the humification index (HIX) and the biologicalindex (BIX) were selected to investigate the sources thedegree of maturation and the influence from autochthonousbiological activity of DOM as listed in the following

FI =119891450

119891500

HIX = 119867119871

BIX =119891380

119891430

(3)

where 119891450

and 119891500

are the intensities at the emission wave-length of 450 nm and 500 nm at the excitation wavelength370 nm respectively [41 42] while 119891

380and 119891

430are the

fluorescence intensity at the emission wavelength of 380 nmand 430 nm at the excitation wavelength 310 nm respectively[27 38] 119867 and 119871 represent the integral values from 435to 480 nm and 300 to 345 nm at the excitation wavelength254 nm respectively [27 43]

As listed in Table 5 themean FI values of the five sitesrsquo soilsamples were 154 161 146 152 and 151 for Y-1 Y-4 Y-10Y-15 and Y-20 respectively Considering that the terrestrialand microbial end-member values were reported as 14 and19 [41 42] the FI values in this study suggested that thesources of DOM in the soil samples were possibly assigned

Table 5 Results of UV-Visible spectroscopy and EEM fluorescencespectroscopy

Sample point SUVA254

(mgminus1sdotmminus1) SR FI BIX HIXY-1 539 064 154 056 147Y-4 590 107 161 048 1890Y-10 483 092 146 057 217Y-15 533 095 152 043 616Y-20 439 077 151 067 366

to both terrestrial and microbial sources which cannot beinfluenced by the afforestation time The mean HIX valuesin this study were 1470 1890 217 616 and 366 for Y-1Y-4 Y-10 Y-15 and Y-20 respectively It was believed thatthe high HIX values at the region of 10ndash16 are the indicatorof the strongly humic organic substances (terrestrial origin)whereas low values (lt4) imply the presence of autochthonousorganic components [38ndash40]

Compared to the samples of the Y-10 and Y-20 siteswhich mainly consisted of autochthonous organic matters(HIX valueslt 405) theDOMextracted from the soil samplesof the other three sites (Y-1 Y-4 and Y-15) was composed ofboth allochthonous and autochthonous organic substancesPrevious study reported that the allochthonous organic mat-ters originated from incomplete decomposition of plant andanimal residues while the autochthonous organic ones mayderive from the photosynthesis [40] High BIX values (gt1)correspond to autochthonous sources while low BIX values(lt1) imply low abundance of organic matter of biologicalorigin [38ndash40] The mean BIX values of the five sitesrsquo soilsamples were 056 048 057 043 and 067 for Y-1 Y-4 Y-10Y-15 and Y-20 respectively indicative of low abundance ofbiological origin organic components

323 1H NMR Spectroscopy Proton NMR spectroscopy (1HNMR) was often utilized to characterize the composition oftheDOM in soil samples which can provide semiquantitative

6 Journal of Analytical Methods in Chemistry

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

Y-1

0000

2500

5000

7500

1000

1250

1500

1750

2000

2250

200

250

300

350

400

450

500

550Em

issio

n w

avele

ngth

(nm

)

T

A

(a)

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

Y-4

200

250

300

350

400

450

500

550

Emiss

ion

wav

eleng

th (n

m)

0000

6000

1200

1800

2400

3000

3600

4200

4800

5400

T

A

(b)

200

250

300

350

400

450

500

550

Emiss

ion

wav

eleng

th (n

m)

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

0000

8000

1600

2400

3200

4000

4800

5600

6400

7200Y-10

T

A

(c)

200

250

300

350

400

450

500

550

Emiss

ion

wav

eleng

th (n

m)

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

0000

6500

1300

1950

2600

3250

3900

4550

5200

5850

6500Y-15

T

A

(d)

200

250

300

350

400

450

500

550

Emiss

ion

wav

eleng

th (n

m)

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

0000

9000

1800

2700

3600

4500

5400

6300

7200

8100Y-20

T

A

(e)

Figure 3 EEM fluorescence contour profiles of the five sitesrsquo DOM

information on aromatic aliphatic and carboxylic groups[27 44 45] Much different from UV-Visible spectroscopyand EEM 1H NMR can give us the content and structuralinformation via the corresponding integrated areas and thechemical shifts (120575H) [18 19] As illustrated in Figure 4 the1H NMR results of the five sites exhibit some distinct peaksoverlaying bands implying the existence of complicatedmixtures in theDOMDespite the large variety of overlapping

resonances each 1H NMR spectrum was analyzed based onthe chemical shift assignments following the methoddescribed in the previously reported literatures for soilDOM [27] The integrated regions in the 1H NMR spectrawere listed as follows 120575H = 05ndash29 ppm (aliphatic protonsH-C) 120575H = 30ndash42 ppm (carbohydrates H-C-C=) and120575H = 60ndash80 ppm (aromatic protons) [27] The spectra offive sites were depicted in Figure 5 The 1H NMR results of

Journal of Analytical Methods in Chemistry 7

0123456789

(ppm)

Y-1

0123456789

(ppm)

Y-4

0123456789

(ppm)

Y-10

0123456789

(ppm)

Y-15

0123456789

(ppm)

Y-20

Figure 4 1H NMR spectra of DOM in the extracted samples of the five sampling sites

the five sites exhibited similar patterns as to functional groupcomposition suggesting the presence of more aliphaticand carbohydrates structures and less quantity of aromaticorganic matters (Table 6)

The content of saturated aliphatic substances in site Y-1(42) was lower than other sites (681 645 367 and340 forY-4 Y-10 Y-15 andY-20 resp) while the content of

carbohydrates (922) was higher than other sites (335335 598 and 642 for Y-4 Y-10 Y-15 and Y-20 resp)The content of aromatic structures in the five sites was 3647 2 35 and 18 for Y-1 Y-4 Y-10 Y-15 and Y-20respectively The results implied that the saturated aliphaticchains and carbohydrates were the main structures inafforestation forest land

8 Journal of Analytical Methods in Chemistry

Table 6 Results of the 1H NMR analyses

Samplesites

aliphatics(05ndash300 ppm)

carbohydrates(300ndash42 ppm)

aromatics(600ndash800 ppm)

Y-1 42 922 36Y-4 618 335 47Y-10 645 335 2Y-15 367 598 35Y-20 34 642 18

H-C H-C-C= H-Ar0

20

40

60

80

100

Perc

enta

ge (

)

Y-1Y-4

Y-15Y-20

Y-10

Figure 5The relative abundance of each type of protons estimatedas the partial integrals of the spectra reported in Figure 4

4 Conclusions

With this study a preliminary soil quality evaluation werecarried out based on soil texture and some chemical indi-cators like TOC TN TP K+ MBC and DOC Particularlythe DOM in the soil samples with different afforestation timewas further characterized via DOC UV-Visible spectroscopyEEM fluorescence spectroscopy and 1H NMR spectroscopyThe results of EEM fluorescence spectroscopy demonstratedthat UV humic-like substances were the major fluorophorescomponents in the DOM of the soil samples The DOM inthe soil samples wasmainly composed of aliphatic chains andaromatic components with carbonyl carboxyl and hydroxylgroups DOM in soils plays a crucial role in soil physicalchemical and biological processes but little information isavailable on the formation and biodegradability of plant-derived DOM in afforestation forest soil With the develop-ment of afforestation forest in Beijing it is necessary to fur-ther investigate the DOMdistribution and the correspondinginfluence on soil quality plants growth and ecosystem

Competing Interests

The authors declare that there are no competing interestsregarding the publication of this paper

Acknowledgments

This study was supported by the Fund of 12th Five-Year National Science and Technology Support Program(2013BAJ02B0404)

References

[1] S Cao ldquoWhy large-scale afforestation efforts in China havefailed to solve the desertification problemrdquo EnvironmentalScience and Technology vol 42 no 6 pp 1826ndash1831 2008

[2] Y Qiao J Wang and J Li ldquoThe summary and reflection ofBeijingrsquos plain reforestation taking Qingyundian of Daxingdistrict as an examplerdquo Forestry Economics vol 4 article 0052014

[3] K Kaiser G Guggenberger and W Zech ldquoSorption of DOMand DOM fractions to forest soilsrdquo Geoderma vol 74 no 3-4pp 281ndash303 1996

[4] R G Qualls and B L Haines ldquoBiodegradability of dissolvedorganic matter in forest throughfall soil solution and streamwaterrdquo Soil Science Society of America Journal vol 56 no 2 pp578ndash586 1992

[5] R Bi Q Lu T Yuan S Zhou Y Yuan and Y Cai ldquoElectro-chemical and spectroscopic characteristics of dissolved organicmatter in a forest soil profilerdquo Journal of Environmental Sciencesvol 25 no 10 pp 2093ndash2101 2013

[6] X-J Guo N-M Zhu L Chen D-H Yuan and L-S HeldquoCharacterizing the fluorescent properties and copper complex-ation of dissolved organic matter in saline-alkali soils usingfluorescence excitation-emission matrix and parallel factoranalysisrdquo Journal of Soils and Sediments vol 15 no 7 pp 1473ndash1482 2015

[7] B Marschner and K Kalbitz ldquoControls of bioavailability andbiodegradability of dissolved organic matter in soilsrdquo Geo-derma vol 113 no 3-4 pp 211ndash235 2003

[8] K Kalbitz S Solinger J-H Park B Michalzik and E MatznerldquoControls on the dynamics dissolved organic matter in soils areviewrdquo Soil Science vol 165 no 4 pp 277ndash304 2000

[9] D L Jones P Simfukwe P W Hill R T E Mills and B AEmmett ldquoEvaluation of dissolved organic carbon as a soil qual-ity indicator in national monitoring schemesrdquo PLoS ONE vol9 no 3 Article ID e90882 2014

[10] T Yuan Y Yuan S Zhou F Li Z Liu and L Zhuang ldquoA rapidand simple electrochemical method for evaluating the electrontransfer capacities of dissolved organic matterrdquo Journal of Soilsand Sediments vol 11 no 3 pp 467ndash473 2011

[11] T Ohno I J Fernandez S Hiradate and J F Sherman ldquoEffectsof soil acidification and forest type on water soluble soil organicmatter propertiesrdquoGeoderma vol 140 no 1-2 pp 176ndash187 2007

[12] G F Vance and M B David ldquoChemical characteristics andacidity of soluble organic substances from a northern hardwoodforest floor central Maine USArdquo Geochimica et CosmochimicaActa vol 55 no 12 pp 3611ndash3625 1991

[13] Q-Y Wang Y Wang Q-C Wang et al ldquoEffects of land usechanges on the spectroscopic characterization of hot-waterextractable organic matter along a chronosequence correla-tionswith soil enzyme activityrdquoEuropean Journal of Soil Biologyvol 58 pp 8ndash12 2013

[14] M A Rab ldquoSoil physical and hydrological properties followinglogging and slash burning in the Eucalyptus regnans forest ofsoutheastern Australiardquo Forest Ecology and Management vol84 no 1ndash3 pp 159ndash176 1996

Journal of Analytical Methods in Chemistry 9

[15] M Han G Ji and J Ni ldquoWashing of field weathered crude oilcontaminated soil with an environmentally compatible surfac-tant alkyl polyglucosiderdquo Chemosphere vol 76 no 5 pp 579ndash586 2009

[16] X Bi L Ren M Gong Y He L Wang and Z Ma ldquoTransfer ofcadmium and lead from soil to mangoes in an uncontaminatedarea Hainan Island ChinardquoGeoderma vol 155 no 1-2 pp 115ndash120 2010

[17] J Akagi A Zsolnay and F Bastida ldquoQuantity and spectroscopicproperties of soil dissolved organic matter (DOM) as a func-tion of soil sample treatments air-drying and pre-incubationrdquoChemosphere vol 69 no 7 pp 1040ndash1046 2007

[18] N Roig J Sierra E Martı M Nadal M Schuhmacher and J LDomingo ldquoLong-term amendment of Spanish soils with sewagesludge effects on soil functioningrdquo Agriculture Ecosystems andEnvironment vol 158 pp 41ndash48 2012

[19] J L Weishaar G R Aiken B A Bergamaschi M S FramR Fujii and K Mopper ldquoEvaluation of specific ultravioletabsorbance as an indicator of the chemical composition andreactivity of dissolved organic carbonrdquo Environmental Scienceand Technology vol 37 no 20 pp 4702ndash4708 2003

[20] S A Green and N V Blough ldquoOptical absorption and fluores-cence properties of chromophoric dissolved organic matter innatural watersrdquo Limnology and Oceanography vol 39 no 8 pp1903ndash1916 1994

[21] P J Seaton R J Kieber J DWilley G B Avery and J L DixonldquoSeasonal and temporal characterization of dissolved organicmatter in rainwater by proton nuclear magnetic resonancespectroscopyrdquo Atmospheric Environment vol 65 pp 52ndash602013

[22] J Amador P J Milne C A Moore and R G Zika ldquoExtractionof chromophoric humic substances from seawaterrdquo MarineChemistry vol 29 pp 1ndash17 1990

[23] C A Stedmon and R Bro ldquoCharacterizing dissolved organicmatter fluorescence with parallel factor analysis a tutorialrdquoLimnology and Oceanography Methods vol 6 no 11 pp 572ndash579 2008

[24] P S M Santos M Otero R M B O Duarte and A C DuarteldquoSpectroscopic characterization of dissolved organicmatter iso-lated from rainwaterrdquoChemosphere vol 74 no 8 pp 1053ndash10612009

[25] C ZhaoC-CWang J-Q Li C-YWang PWang andZ-J PeildquoDissolved organic matter in urban stormwater runoff at threetypical regions in Beijing chemical composition structuralcharacterization and source identificationrdquo RSC Advances vol5 no 90 pp 73490ndash73500 2015

[26] Z Wang and Q Wang ldquoThe spatial heterogeneity of soilphysical properties in forestsrdquoActa Ecologica Sinica vol 20 no6 pp 945ndash950 1999

[27] M L Fernandez-Romero J M Clark C D Collins L Parras-Alcantara and B Lozano-Garcıa ldquoEvaluation of optical tech-niques for characterising soil organic matter quality in agricul-tural soilsrdquo Soil and Tillage Research vol 155 pp 450ndash460 2016

[28] K Kalbitz J Schmerwitz D Schwesig and E MatznerldquoBiodegradation of soil-derived dissolved organic matter asrelated to its propertiesrdquo Geoderma vol 113 no 3-4 pp 273ndash291 2003

[29] R M B O Duarte and A C Duarte ldquoApplication of non-ionic solid sorbents (XADResins) for the isolation and fraction-ation of water-soluble organic compounds from atmosphericaerosolsrdquo Journal of Atmospheric Chemistry vol 51 no 1 pp79ndash93 2005

[30] N Senesi T M Miano M R Provenzano and G BrunettildquoSpectroscopic and compositional comparative characteriza-tion of IHSS reference and standard fulvic and humic acidsof various originrdquo Science of the Total Environment vol 81-82pp 143ndash156 1989

[31] X-S He B-D Xi Y-H Jiang et al ldquoStructural transformationstudy of water-extractable organic matter during the industrialcomposting of cattle manurerdquo Microchemical Journal vol 106pp 160ndash166 2013

[32] T Jamieson E Sager and C Gueguen ldquoCharacterizationof biochar-derived dissolved organic matter using UV-visibleabsorption and excitation-emission fluorescence spectrosco-piesrdquo Chemosphere vol 103 pp 197ndash204 2014

[33] J R Helms A Stubbins J D Ritchie E C Minor D J Kieberand K Mopper ldquoAbsorption spectral slopes and slope ratiosas indicators of molecular weight source and photobleachingof chromophoric dissolved organic matterrdquo Limnology andOceanography vol 53 no 3 pp 955ndash969 2008

[34] C A Stedmon S Markager and H Kaas ldquoOptical proper-ties and signatures of chromophoric dissolved organic matter(CDOM) in Danish coastal watersrdquo Estuarine Coastal and ShelfScience vol 51 no 2 pp 267ndash278 2000

[35] J B Fellman D V DrsquoAmore E Hood and R D BooneldquoFluorescence characteristics and biodegradability of dissolvedorganic matter in forest and wetland soils from coastal temper-atewatersheds in southeastAlaskardquoBiogeochemistry vol 88 no2 pp 169ndash184 2008

[36] J Sanderman J A Baldock and R Amundson ldquoDissolvedorganic carbon chemistry and dynamics in contrasting forestand grassland soilsrdquo Biogeochemistry vol 89 no 2 pp 181ndash1982008

[37] K Fujii M Uemura C Hayakawa et al ldquoFluxes of dissolvedorganic carbon in two tropical forest ecosystems of East Kali-mantan Indonesiardquo Geoderma vol 152 no 1-2 pp 127ndash1362009

[38] A Huguet L Vacher S Relexans S Saubusse J M Froidefondand E Parlanti ldquoProperties of fluorescent dissolved organicmatter in the Gironde Estuaryrdquo Organic Geochemistry vol 40no 6 pp 706ndash719 2009

[39] A Huguet L Vacher S Saubusse et al ldquoNew insights intothe size distribution of fluorescent dissolved organic matter inestuarine watersrdquo Organic Geochemistry vol 41 no 6 pp 595ndash610 2010

[40] P R Salve H Lohkare T Gobre et al ldquoCharacterization ofchromophoric dissolved organic matter (CDOM) in rainwaterusing fluorescence spectrophotometryrdquoBulletin of Environmen-tal Contamination and Toxicology vol 88 no 2 pp 215ndash2182012

[41] D M McKnight E W Boyer P K Westerhoff P T DoranT Kulbe and D T Andersen ldquoSpectrofluorometric characteri-zation of dissolved organic matter for indication of precursororganic material and aromaticityrdquo Limnology and Oceanogra-phy vol 46 no 1 pp 38ndash48 2001

[42] R Jaffe J N Boyer X Lu et al ldquoSource characterization ofdissolved organic matter in a subtropical mangrove-dominatedestuary by fluorescence analysisrdquoMarine Chemistry vol 84 no3-4 pp 195ndash210 2004

[43] T Ohno ldquoFluorescence inner-filtering correction for deter-mining the humification index of dissolved organic matterrdquoEnvironmental Science amp Technology vol 36 no 4 pp 742ndash7462002

10 Journal of Analytical Methods in Chemistry

[44] L A Cardoza A K Korir W H Otto C J Wurrey and C KLarive ldquoApplications of NMR spectroscopy in environmentalsciencerdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 45 no 3-4 pp 209ndash238 2004

[45] C M Preston ldquoApplications of NMR to soil organic matteranalysis history and prospectsrdquo Soil Science vol 161 no 3 pp144ndash166 1996

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

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CatalystsJournal of

Page 2: Research Article Spectroscopic Characteristics of ...downloads.hindawi.com/journals/jamc/2016/1480857.pdf · Microbial biomass carbon (MBC) analysis was determined by the chloroform

2 Journal of Analytical Methods in Chemistry

Miyun District

Xi Tian Ge Zhuang ZhenBeijing

Miyun

(m)(m)

(m)

0 5000025000 0 2500012500

0 50002500

NE

SW

NE

SW

NE

SW

Xi Tian Ge Zhuang Zhen

Miyun Zhen

Y-1

Y-4

Y-10Y-15

Y-20

Figure 1 Schematic map of the selected area and the sampling sites

total organic carbon (TOC) total nitrogen (TN) total phos-phorus (TP) available potassium (K+) microbial biomasscarbon (MBC) and dissolved organic carbon (DOC) weredetermined The DOM in the soil samples with differentafforestation timewas extracted and further characterized viadissolved organic carbon (DOC) UV-Visible spectroscopyEEM fluorescence spectroscopy and 1H NMR spectroscopySome valuable information on the soil quality of afforestationarea can be provided whichwill guide the future afforestationand corresponding management plan in Beijing

2 Materials and Experimental

21 Sampling Sites Description As a typical afforestation areaXi Tian Ge Zhuang town of Miyun District was selected assampling region as illustrated in Figure 1 The mean annualrainfall and average temperature of this area is 6613mm and108∘C respectively Five sampling regionswith different plain

afforestation time (1 year 4 years 10 years 15 years and20 years) were selected in this study and the samples werecollected on June 27th 2015 (Table 1) At each sampling area5 samples were collected with columns of 20 times 5 cm (long timesdiameter) via Soil Core Samplers (AMS samplers AmericanFalls Idaho) [9 13]

22 Pretreatment of the Soil Samples In laboratory after thevisible roots plant fragments grass and tones were removedthe soil samples were dried in the open air passed througha 2mm sieve and stored at room temperature in airtightglassware containers [5]

23 The Determination of Some Soil Parameters Soil bulkdensity wasmeasured according toMA Rab using bulk den-sity soil sampling kit (AMS samplers American Falls Idaho)[14] The distribution of soil particle was analyzed with Mas-tersizer 3000 (Malvern Instrument Ltd UK) to determine

Journal of Analytical Methods in Chemistry 3

Table 1 Locations and afforestation information of the samples

Abbreviation Tree species Growing period CoordinatesY-1 Pagoda tree 1 yr N40∘24101584059610158401015840 E116∘45101584043710158401015840

Y-4 Pagoda tree 4 yrs N40∘24101584030810158401015840 E116∘45101584000010158401015840

Y-10 Populus tomentosa 10 yrs N40∘23101584058410158401015840 E116∘43101584041610158401015840

Y-15 Populus tomentosa 15 yrs N40∘24101584000710158401015840 E116∘43101584037110158401015840

Y-20 Shrub and locust 20 yrs N40∘20101584052210158401015840 E116∘49101584022010158401015840

the content of clay silt and sand in the soil samples [15]The pH values of the soil were measured in a suspension(waterdry soil 25 1) using a PB-10 pH meter (SartoriusGermany) [16] Microbial biomass carbon (MBC) analysiswas determined by the chloroform fumigation-extractionmethod [17] Total organic carbon (TOC) was calculatedby subtracting inorganic carbon (calculated from CaCO

3

content) from total carbon by a Jena multi NC 3100 analyzer[18] The total N P and available P of the soil sample weremeasured using a AA3 continuous-flow analyzer (Seal Ana-lytical Corporation Germany)The available Kwasmeasuredby flame atomic absorption spectrometric method via PerkinElmer 9100 Atomic Absorption Spectrometry

24 DOM Extraction and Analytical Methods 100 g soilsample was mixed with 500mL distilled water in 1000mLcentrifuge tube whichwas shaken at 200 rmin in a reciprocalshaker for 16 h under room temperature (25∘C) and thencentrifuged at 12000 rmin for 20min The supernatant wasmoved out of centrifuge tube with a hydrophilic PVDFMillipore membrane filter (045 120583m) to carry out the follow-ing characterizations like dissolved organic carbon (DOC)UV-Visible spectroscopy excitation-emission matrix (EEM)fluorescence spectroscopy and even 1H NMR spectroscopy

25 UV-Visible Spectroscopy UV-Visible spectra of the DOMin filtered supernatant were recorded from 200 to 600 nmon a PerkinElmer Lambda 650S spectrophotometer using a10 cmquartz cell [19]The absorbance at 300 nmwas adjustedto 002 to avoid inner filter effects [20] Ultrapure water(Milli-Q 18MΩsdotcm) was selected as the blank

26 Excitation-Emission Matrix (EEM) Fluorescence Spec-troscopy The excitation and emission spectra of the DOMin filtered supernatant were measured on a Hitachi F-7000fluorescence spectrophotometer using a 150W xenon arclamp as the light source Both excitation and emission slitsare 10 nmwith a scan range from 200 nm to 550 nmThe scanrate was 1200 nmmin and the photomultiplier tube voltagewas 700V The standard quinine sulfate units (QSU) wereintroduced to determine the samplesrsquo relative fluorescentintensities that is 4221 intensity unit is equivalent to oneQSU (1 QSU = 1 120583g Lminus1 = 1 ppb quinine sulfate in 005mol Lminus1H2SO4) [21 22] The Rayleigh scatter effects were eliminated

from the data set by adding zero to the EEMs in the twotriangle regions (Em le Ex + 20 nm and Em ge 2Ex minus10 nm) [23] along with Raman scatter that was avoided bysubtracting the background value of the ultrapure water asblank [23 24] to highlight the useful fluorescent information

27 1H NMR Spectroscopy Agilent VacElut SPS 24 solidphase extraction (SPE) equipment with Bond Elut C-18 assorbent was selected to isolate the DOM from the samplesin which 100mL leaching liquor extracted from soil samplewas pumped through the SPE column with the speed of10mLmin Two 50mL ultrapure water solvents were usedto pass through the SPE column to wash off the residual saltsTheDOMheld in the C-18 packing of SPE columnwas elutedoffwith 6mL solutionmatrix of water andmethanol with vol-ume ratio of 1 9The reduced pressure was stained for 30minto remove the residual solvent [21] Finally the extractedDOM was dried under N

2gas with Termovap Sample

Concentrator (YGC-1217 Bao Jing Company) [22] In orderto conduct 1H NMR spectroscopy analysis the obtainedsolid DOM extracts were dissolved in D

2O (Jin Ouxiang

Company) to avoid water peaks Measurements of 1H NMRspectra of theDOMwere performed on aBruker 400MNMRspectrometerThe pulse conditions of 1HNMRwere listed asthe following operating frequency = 499898MHz acquisi-tion time= 2045 s recycle delay = 10 s and line broadening =10Hz The standard s2pul pulse sequence and baselinecorrection was applied The functional groups in the 1HNMR spectra were identified on their corresponding chemi-cal shifts (120575H) relative to that of the water (47 ppm) [25]

3 Results and Discussion

31 Soil Texture and Soil Quality Indicators The basic phys-ical and chemical properties of the soil samples are assessedAs listed in Table 2 it can be seen that all of the soil samplesselected in this study are sandy texture with a siltsand ratioranging from 7389 to 9264 and the bulk densities werein the range of 145ndash157 gsdotcmminus3 which matched well thepreviously reported values [26] As shown in Table 3 thebasic indexes of soil fertility total organic carbon (TOC)total nitrogen (TN) total phosphorus (TP) and availablepotassium (K) are ranging from 264 to 452 gsdotkgminus1 003to 005 gsdotkgminus1 005 to 048 gsdotkgminus1 and 021 to 061 gsdotkgminus1respectively The TOC increases with the increasing of theafforestation time when the afforestation time is less than tenyear and then remains nearly constant when the time is up toten year The microbial biomass carbon analysis (MBC) andwater extracted dissolved organic carbon (DOC) are in therange of 1628 to 9270mgsdotkgminus1 and 5608 to 8110mgsdotkgminus1respectively The highest MBC (9270mgsdotkgminus1) is observed atsample Y-20 All of the basic physical and chemical propertiesof the samples are shown that the afforestation can improvebiomass in soil

4 Journal of Analytical Methods in Chemistry

Table 2 Basic physical properties of the soil samples

Sample point Clay () Silt () Sand () Bulk density(gsdotcmminus3)

Y-1 021 715 9123 157Y-4 094 2075 7830 149Y-10 082 2324 7594 145Y-15 025 1004 8971 151Y-20 114 2497 7189 151

Abso

rban

ce

200

300

400

500

600 Wav

eleng

ths (

nm)

Y-1Y-4

Y-10Y-15

Y-20

12

10

08

06

04

02

00

Figure 2 UV-Visible spectra of the soil samples

32 Spectroscopic Characteristics of DOM in Soil Samples

321 UV-Visible Spectroscopy As an efficient tool the UV-Visible spectroscopy is employed to evaluate the compositionand structure of DOM [27 28] As illustrated in Figure 2all the UV-Visible spectrum absorbance of the five samplesdecreased with the wavelength which can be found inother studies [5 24 29 30] Some small shoulder peakscan be found in the region of 250ndash300 nm which might becontributed by phenolic aromatic carboxylic and polycyclicaromatic compounds (120587 rarr 120587lowast transition) [31]

The spectral slope coefficients (119878) calculated from theUV-Visible spectra data exhibited the light absorption efficiencyof DOM as a function of the wavelength which negativelyrelates to molecular weight of DOM [32 33] Jamieson et alcalculated 119878 values within the spectra region of 275ndash295 nmto characterize the biochar-derived DOM isolated from soil[32] and Stedmon et al calculated 119878 values in the region from300 to 650 nm to investigate themolecular weight of DOM inDanish coastal water bodies [34] To avoid the use of spectraldata near the detection limit of the instruments the ratioof the slope of the shorter wavelength region (275ndash295 nm119878275ndash295) to that of the longerwavelength region (350ndash400 nm119878350ndash400) was calculated and this dimensionless parametercan be called 119878

119877[33]

The 119878 and 119878119877values were calculated as follows

119886 (120582) = 119886 (1205820) 119890119878(1205820minus120582)

+ 119870

119886 (120582) =

2303119860 (120582)

119897

119878119877=

119878275ndash295119878350ndash400

(1)

in which 119886(120582) and 119886(1205820) represent absorption coefficients

and absorption coefficients at reference wavelength respec-tively 120582 and 120582

0are the reference wavelength (300 nm was

selected in this study) and the selected wavelength (rangingfrom 240 nm to 400 nm) respectively 119860(120582) represents theabsorbance at wavelength 120582 (nm) 119897 (m) is the optical pathlength (001m in this study) and 119870 is a background 119889parameter to improve the goodness of fitting

The median of 119878119877

values determined for the DOMsamples of the five sits (Y-1 Y-4 Y-10 Y-15 and Y-20) was064 107 092 095 and 077 respectively suggesting that themolecular weight of DOM in the soil samples is Y-1 gt Y-20 gtY-10 gt Y-15 gt Y-4

In order to explore the aromaticity of the DOM samplesSUVA

254was introduced as follows

SUVA254=

119886254

DOC (2)

where 119886254

(mminus1) is the absorbance coefficient measured at254 nm The median values of SUVA

254were 539 590 483

533 and 439 LmgCminus1mminus1 for Y-1 Y-4 Y-10 Y-15 and Y-20 respectively The previously reported SUVA

254values of

wetland soil [35] and the agricultural soil [27] were 351ndash441 and 032ndash465 respectively suggesting that the DOM inour study contained a greater amount of aromatic structuresAnd previous studies proposed that different landscapes werelikely to produce different types of DOM [36 37] thereforethe SUVA

254values in this study could roughly imply that

afforestation in suburban area can produce the aromaticsubstances The highest values of SUVA

254were observed at

Y-4 while the lowest values were observed at Y-20

322 Excitation-Emission Matrix (EEM) Fluorescence Spec-troscopy The excitation-emission matrix (EEM) fluores-cence technique is powerful to provide sufficient informa-tion on DOMrsquos molecular size chemical composition andaromaticity or aliphatic properties [5 27] EEM can identifyhumic-like (designated as A C and M) and protein-likefluorescence peaks (B and T) as listed in Table 4 EEMfluorescence spectra of the study areas samples were depictedin Figures 3(a)ndash3(e) suggesting that the UV humic-likesubstances were the primary fluorophores components inthe DOM extracted from afforestation land samples [38]The first identified peak (peak A) was located at ExEm of257 nm448 nm 256 nm440 nm 262 nm443 nm 260 nm425 nm and 260 nm435 nm for the Y-1 Y-4 Y-10 Y-15 andY-20 samples respectively suggesting the existence of UVhumic-like substances The second typical peak (peak T)was observed at ExEm of 271 nm347 nm 280 nm325 nm

Journal of Analytical Methods in Chemistry 5

Table 3 Basic chemical properties of the soil samples

Sample point pH TN (gsdotkgminus1) TP (gsdotkgminus1) Available K (mgsdotkgminus1) TOC (gsdotkgminus1) MBC (mgsdotkgminus1) DOC (mgsdotkgminus1)Y-1 634 003 009 051 264 1628 8110Y-4 633 005 019 030 277 4209 6845Y-10 657 002 021 025 445 1964 6125Y-15 665 002 048 021 452 5945 5608Y-20 705 003 005 061 445 9270 6943

Table 4 Peaks description and excitationemission maxima of fluorescent DOM

Peaks Description Excitation max (nm) Emission max (nm)A UV humic-like less aromatic lt260 380ndash460C Visible humic-like more aromatic 320ndash360 420ndash460M Marine-humic-like 290ndash310 370ndash410B Tyrosine-like substances 260 280T Protein-like tryptophan 250ndash300 305ndash355

275 nm338 nm 279 nm333 nm and 271 nm339 nm for thefive samples stated above respectively implying the pres-ence of tryptophan protein-like components [38] GenerallyDOM in soil is affected by some factors like local geologyland use and microbial and human activities [38] And itcan be believed that the presence of tryptophan protein-likesubstances could further confirm the larger molecular weightDOM presented in the soil [39 40]

Moreover the fluorescence intensities of the five sites (Y-1Y-4 Y-10 Y-15 andY-20) for peakAwere 24 60 78 63 and 81QSU respectively while the peak T fluorescence intensities ofthe five sites were 834 91 106 76 and 124 QSU respectively

Three typical fluorescence indices like the fluorescenceindex (FI) the humification index (HIX) and the biologicalindex (BIX) were selected to investigate the sources thedegree of maturation and the influence from autochthonousbiological activity of DOM as listed in the following

FI =119891450

119891500

HIX = 119867119871

BIX =119891380

119891430

(3)

where 119891450

and 119891500

are the intensities at the emission wave-length of 450 nm and 500 nm at the excitation wavelength370 nm respectively [41 42] while 119891

380and 119891

430are the

fluorescence intensity at the emission wavelength of 380 nmand 430 nm at the excitation wavelength 310 nm respectively[27 38] 119867 and 119871 represent the integral values from 435to 480 nm and 300 to 345 nm at the excitation wavelength254 nm respectively [27 43]

As listed in Table 5 themean FI values of the five sitesrsquo soilsamples were 154 161 146 152 and 151 for Y-1 Y-4 Y-10Y-15 and Y-20 respectively Considering that the terrestrialand microbial end-member values were reported as 14 and19 [41 42] the FI values in this study suggested that thesources of DOM in the soil samples were possibly assigned

Table 5 Results of UV-Visible spectroscopy and EEM fluorescencespectroscopy

Sample point SUVA254

(mgminus1sdotmminus1) SR FI BIX HIXY-1 539 064 154 056 147Y-4 590 107 161 048 1890Y-10 483 092 146 057 217Y-15 533 095 152 043 616Y-20 439 077 151 067 366

to both terrestrial and microbial sources which cannot beinfluenced by the afforestation time The mean HIX valuesin this study were 1470 1890 217 616 and 366 for Y-1Y-4 Y-10 Y-15 and Y-20 respectively It was believed thatthe high HIX values at the region of 10ndash16 are the indicatorof the strongly humic organic substances (terrestrial origin)whereas low values (lt4) imply the presence of autochthonousorganic components [38ndash40]

Compared to the samples of the Y-10 and Y-20 siteswhich mainly consisted of autochthonous organic matters(HIX valueslt 405) theDOMextracted from the soil samplesof the other three sites (Y-1 Y-4 and Y-15) was composed ofboth allochthonous and autochthonous organic substancesPrevious study reported that the allochthonous organic mat-ters originated from incomplete decomposition of plant andanimal residues while the autochthonous organic ones mayderive from the photosynthesis [40] High BIX values (gt1)correspond to autochthonous sources while low BIX values(lt1) imply low abundance of organic matter of biologicalorigin [38ndash40] The mean BIX values of the five sitesrsquo soilsamples were 056 048 057 043 and 067 for Y-1 Y-4 Y-10Y-15 and Y-20 respectively indicative of low abundance ofbiological origin organic components

323 1H NMR Spectroscopy Proton NMR spectroscopy (1HNMR) was often utilized to characterize the composition oftheDOM in soil samples which can provide semiquantitative

6 Journal of Analytical Methods in Chemistry

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

Y-1

0000

2500

5000

7500

1000

1250

1500

1750

2000

2250

200

250

300

350

400

450

500

550Em

issio

n w

avele

ngth

(nm

)

T

A

(a)

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

Y-4

200

250

300

350

400

450

500

550

Emiss

ion

wav

eleng

th (n

m)

0000

6000

1200

1800

2400

3000

3600

4200

4800

5400

T

A

(b)

200

250

300

350

400

450

500

550

Emiss

ion

wav

eleng

th (n

m)

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

0000

8000

1600

2400

3200

4000

4800

5600

6400

7200Y-10

T

A

(c)

200

250

300

350

400

450

500

550

Emiss

ion

wav

eleng

th (n

m)

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

0000

6500

1300

1950

2600

3250

3900

4550

5200

5850

6500Y-15

T

A

(d)

200

250

300

350

400

450

500

550

Emiss

ion

wav

eleng

th (n

m)

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

0000

9000

1800

2700

3600

4500

5400

6300

7200

8100Y-20

T

A

(e)

Figure 3 EEM fluorescence contour profiles of the five sitesrsquo DOM

information on aromatic aliphatic and carboxylic groups[27 44 45] Much different from UV-Visible spectroscopyand EEM 1H NMR can give us the content and structuralinformation via the corresponding integrated areas and thechemical shifts (120575H) [18 19] As illustrated in Figure 4 the1H NMR results of the five sites exhibit some distinct peaksoverlaying bands implying the existence of complicatedmixtures in theDOMDespite the large variety of overlapping

resonances each 1H NMR spectrum was analyzed based onthe chemical shift assignments following the methoddescribed in the previously reported literatures for soilDOM [27] The integrated regions in the 1H NMR spectrawere listed as follows 120575H = 05ndash29 ppm (aliphatic protonsH-C) 120575H = 30ndash42 ppm (carbohydrates H-C-C=) and120575H = 60ndash80 ppm (aromatic protons) [27] The spectra offive sites were depicted in Figure 5 The 1H NMR results of

Journal of Analytical Methods in Chemistry 7

0123456789

(ppm)

Y-1

0123456789

(ppm)

Y-4

0123456789

(ppm)

Y-10

0123456789

(ppm)

Y-15

0123456789

(ppm)

Y-20

Figure 4 1H NMR spectra of DOM in the extracted samples of the five sampling sites

the five sites exhibited similar patterns as to functional groupcomposition suggesting the presence of more aliphaticand carbohydrates structures and less quantity of aromaticorganic matters (Table 6)

The content of saturated aliphatic substances in site Y-1(42) was lower than other sites (681 645 367 and340 forY-4 Y-10 Y-15 andY-20 resp) while the content of

carbohydrates (922) was higher than other sites (335335 598 and 642 for Y-4 Y-10 Y-15 and Y-20 resp)The content of aromatic structures in the five sites was 3647 2 35 and 18 for Y-1 Y-4 Y-10 Y-15 and Y-20respectively The results implied that the saturated aliphaticchains and carbohydrates were the main structures inafforestation forest land

8 Journal of Analytical Methods in Chemistry

Table 6 Results of the 1H NMR analyses

Samplesites

aliphatics(05ndash300 ppm)

carbohydrates(300ndash42 ppm)

aromatics(600ndash800 ppm)

Y-1 42 922 36Y-4 618 335 47Y-10 645 335 2Y-15 367 598 35Y-20 34 642 18

H-C H-C-C= H-Ar0

20

40

60

80

100

Perc

enta

ge (

)

Y-1Y-4

Y-15Y-20

Y-10

Figure 5The relative abundance of each type of protons estimatedas the partial integrals of the spectra reported in Figure 4

4 Conclusions

With this study a preliminary soil quality evaluation werecarried out based on soil texture and some chemical indi-cators like TOC TN TP K+ MBC and DOC Particularlythe DOM in the soil samples with different afforestation timewas further characterized via DOC UV-Visible spectroscopyEEM fluorescence spectroscopy and 1H NMR spectroscopyThe results of EEM fluorescence spectroscopy demonstratedthat UV humic-like substances were the major fluorophorescomponents in the DOM of the soil samples The DOM inthe soil samples wasmainly composed of aliphatic chains andaromatic components with carbonyl carboxyl and hydroxylgroups DOM in soils plays a crucial role in soil physicalchemical and biological processes but little information isavailable on the formation and biodegradability of plant-derived DOM in afforestation forest soil With the develop-ment of afforestation forest in Beijing it is necessary to fur-ther investigate the DOMdistribution and the correspondinginfluence on soil quality plants growth and ecosystem

Competing Interests

The authors declare that there are no competing interestsregarding the publication of this paper

Acknowledgments

This study was supported by the Fund of 12th Five-Year National Science and Technology Support Program(2013BAJ02B0404)

References

[1] S Cao ldquoWhy large-scale afforestation efforts in China havefailed to solve the desertification problemrdquo EnvironmentalScience and Technology vol 42 no 6 pp 1826ndash1831 2008

[2] Y Qiao J Wang and J Li ldquoThe summary and reflection ofBeijingrsquos plain reforestation taking Qingyundian of Daxingdistrict as an examplerdquo Forestry Economics vol 4 article 0052014

[3] K Kaiser G Guggenberger and W Zech ldquoSorption of DOMand DOM fractions to forest soilsrdquo Geoderma vol 74 no 3-4pp 281ndash303 1996

[4] R G Qualls and B L Haines ldquoBiodegradability of dissolvedorganic matter in forest throughfall soil solution and streamwaterrdquo Soil Science Society of America Journal vol 56 no 2 pp578ndash586 1992

[5] R Bi Q Lu T Yuan S Zhou Y Yuan and Y Cai ldquoElectro-chemical and spectroscopic characteristics of dissolved organicmatter in a forest soil profilerdquo Journal of Environmental Sciencesvol 25 no 10 pp 2093ndash2101 2013

[6] X-J Guo N-M Zhu L Chen D-H Yuan and L-S HeldquoCharacterizing the fluorescent properties and copper complex-ation of dissolved organic matter in saline-alkali soils usingfluorescence excitation-emission matrix and parallel factoranalysisrdquo Journal of Soils and Sediments vol 15 no 7 pp 1473ndash1482 2015

[7] B Marschner and K Kalbitz ldquoControls of bioavailability andbiodegradability of dissolved organic matter in soilsrdquo Geo-derma vol 113 no 3-4 pp 211ndash235 2003

[8] K Kalbitz S Solinger J-H Park B Michalzik and E MatznerldquoControls on the dynamics dissolved organic matter in soils areviewrdquo Soil Science vol 165 no 4 pp 277ndash304 2000

[9] D L Jones P Simfukwe P W Hill R T E Mills and B AEmmett ldquoEvaluation of dissolved organic carbon as a soil qual-ity indicator in national monitoring schemesrdquo PLoS ONE vol9 no 3 Article ID e90882 2014

[10] T Yuan Y Yuan S Zhou F Li Z Liu and L Zhuang ldquoA rapidand simple electrochemical method for evaluating the electrontransfer capacities of dissolved organic matterrdquo Journal of Soilsand Sediments vol 11 no 3 pp 467ndash473 2011

[11] T Ohno I J Fernandez S Hiradate and J F Sherman ldquoEffectsof soil acidification and forest type on water soluble soil organicmatter propertiesrdquoGeoderma vol 140 no 1-2 pp 176ndash187 2007

[12] G F Vance and M B David ldquoChemical characteristics andacidity of soluble organic substances from a northern hardwoodforest floor central Maine USArdquo Geochimica et CosmochimicaActa vol 55 no 12 pp 3611ndash3625 1991

[13] Q-Y Wang Y Wang Q-C Wang et al ldquoEffects of land usechanges on the spectroscopic characterization of hot-waterextractable organic matter along a chronosequence correla-tionswith soil enzyme activityrdquoEuropean Journal of Soil Biologyvol 58 pp 8ndash12 2013

[14] M A Rab ldquoSoil physical and hydrological properties followinglogging and slash burning in the Eucalyptus regnans forest ofsoutheastern Australiardquo Forest Ecology and Management vol84 no 1ndash3 pp 159ndash176 1996

Journal of Analytical Methods in Chemistry 9

[15] M Han G Ji and J Ni ldquoWashing of field weathered crude oilcontaminated soil with an environmentally compatible surfac-tant alkyl polyglucosiderdquo Chemosphere vol 76 no 5 pp 579ndash586 2009

[16] X Bi L Ren M Gong Y He L Wang and Z Ma ldquoTransfer ofcadmium and lead from soil to mangoes in an uncontaminatedarea Hainan Island ChinardquoGeoderma vol 155 no 1-2 pp 115ndash120 2010

[17] J Akagi A Zsolnay and F Bastida ldquoQuantity and spectroscopicproperties of soil dissolved organic matter (DOM) as a func-tion of soil sample treatments air-drying and pre-incubationrdquoChemosphere vol 69 no 7 pp 1040ndash1046 2007

[18] N Roig J Sierra E Martı M Nadal M Schuhmacher and J LDomingo ldquoLong-term amendment of Spanish soils with sewagesludge effects on soil functioningrdquo Agriculture Ecosystems andEnvironment vol 158 pp 41ndash48 2012

[19] J L Weishaar G R Aiken B A Bergamaschi M S FramR Fujii and K Mopper ldquoEvaluation of specific ultravioletabsorbance as an indicator of the chemical composition andreactivity of dissolved organic carbonrdquo Environmental Scienceand Technology vol 37 no 20 pp 4702ndash4708 2003

[20] S A Green and N V Blough ldquoOptical absorption and fluores-cence properties of chromophoric dissolved organic matter innatural watersrdquo Limnology and Oceanography vol 39 no 8 pp1903ndash1916 1994

[21] P J Seaton R J Kieber J DWilley G B Avery and J L DixonldquoSeasonal and temporal characterization of dissolved organicmatter in rainwater by proton nuclear magnetic resonancespectroscopyrdquo Atmospheric Environment vol 65 pp 52ndash602013

[22] J Amador P J Milne C A Moore and R G Zika ldquoExtractionof chromophoric humic substances from seawaterrdquo MarineChemistry vol 29 pp 1ndash17 1990

[23] C A Stedmon and R Bro ldquoCharacterizing dissolved organicmatter fluorescence with parallel factor analysis a tutorialrdquoLimnology and Oceanography Methods vol 6 no 11 pp 572ndash579 2008

[24] P S M Santos M Otero R M B O Duarte and A C DuarteldquoSpectroscopic characterization of dissolved organicmatter iso-lated from rainwaterrdquoChemosphere vol 74 no 8 pp 1053ndash10612009

[25] C ZhaoC-CWang J-Q Li C-YWang PWang andZ-J PeildquoDissolved organic matter in urban stormwater runoff at threetypical regions in Beijing chemical composition structuralcharacterization and source identificationrdquo RSC Advances vol5 no 90 pp 73490ndash73500 2015

[26] Z Wang and Q Wang ldquoThe spatial heterogeneity of soilphysical properties in forestsrdquoActa Ecologica Sinica vol 20 no6 pp 945ndash950 1999

[27] M L Fernandez-Romero J M Clark C D Collins L Parras-Alcantara and B Lozano-Garcıa ldquoEvaluation of optical tech-niques for characterising soil organic matter quality in agricul-tural soilsrdquo Soil and Tillage Research vol 155 pp 450ndash460 2016

[28] K Kalbitz J Schmerwitz D Schwesig and E MatznerldquoBiodegradation of soil-derived dissolved organic matter asrelated to its propertiesrdquo Geoderma vol 113 no 3-4 pp 273ndash291 2003

[29] R M B O Duarte and A C Duarte ldquoApplication of non-ionic solid sorbents (XADResins) for the isolation and fraction-ation of water-soluble organic compounds from atmosphericaerosolsrdquo Journal of Atmospheric Chemistry vol 51 no 1 pp79ndash93 2005

[30] N Senesi T M Miano M R Provenzano and G BrunettildquoSpectroscopic and compositional comparative characteriza-tion of IHSS reference and standard fulvic and humic acidsof various originrdquo Science of the Total Environment vol 81-82pp 143ndash156 1989

[31] X-S He B-D Xi Y-H Jiang et al ldquoStructural transformationstudy of water-extractable organic matter during the industrialcomposting of cattle manurerdquo Microchemical Journal vol 106pp 160ndash166 2013

[32] T Jamieson E Sager and C Gueguen ldquoCharacterizationof biochar-derived dissolved organic matter using UV-visibleabsorption and excitation-emission fluorescence spectrosco-piesrdquo Chemosphere vol 103 pp 197ndash204 2014

[33] J R Helms A Stubbins J D Ritchie E C Minor D J Kieberand K Mopper ldquoAbsorption spectral slopes and slope ratiosas indicators of molecular weight source and photobleachingof chromophoric dissolved organic matterrdquo Limnology andOceanography vol 53 no 3 pp 955ndash969 2008

[34] C A Stedmon S Markager and H Kaas ldquoOptical proper-ties and signatures of chromophoric dissolved organic matter(CDOM) in Danish coastal watersrdquo Estuarine Coastal and ShelfScience vol 51 no 2 pp 267ndash278 2000

[35] J B Fellman D V DrsquoAmore E Hood and R D BooneldquoFluorescence characteristics and biodegradability of dissolvedorganic matter in forest and wetland soils from coastal temper-atewatersheds in southeastAlaskardquoBiogeochemistry vol 88 no2 pp 169ndash184 2008

[36] J Sanderman J A Baldock and R Amundson ldquoDissolvedorganic carbon chemistry and dynamics in contrasting forestand grassland soilsrdquo Biogeochemistry vol 89 no 2 pp 181ndash1982008

[37] K Fujii M Uemura C Hayakawa et al ldquoFluxes of dissolvedorganic carbon in two tropical forest ecosystems of East Kali-mantan Indonesiardquo Geoderma vol 152 no 1-2 pp 127ndash1362009

[38] A Huguet L Vacher S Relexans S Saubusse J M Froidefondand E Parlanti ldquoProperties of fluorescent dissolved organicmatter in the Gironde Estuaryrdquo Organic Geochemistry vol 40no 6 pp 706ndash719 2009

[39] A Huguet L Vacher S Saubusse et al ldquoNew insights intothe size distribution of fluorescent dissolved organic matter inestuarine watersrdquo Organic Geochemistry vol 41 no 6 pp 595ndash610 2010

[40] P R Salve H Lohkare T Gobre et al ldquoCharacterization ofchromophoric dissolved organic matter (CDOM) in rainwaterusing fluorescence spectrophotometryrdquoBulletin of Environmen-tal Contamination and Toxicology vol 88 no 2 pp 215ndash2182012

[41] D M McKnight E W Boyer P K Westerhoff P T DoranT Kulbe and D T Andersen ldquoSpectrofluorometric characteri-zation of dissolved organic matter for indication of precursororganic material and aromaticityrdquo Limnology and Oceanogra-phy vol 46 no 1 pp 38ndash48 2001

[42] R Jaffe J N Boyer X Lu et al ldquoSource characterization ofdissolved organic matter in a subtropical mangrove-dominatedestuary by fluorescence analysisrdquoMarine Chemistry vol 84 no3-4 pp 195ndash210 2004

[43] T Ohno ldquoFluorescence inner-filtering correction for deter-mining the humification index of dissolved organic matterrdquoEnvironmental Science amp Technology vol 36 no 4 pp 742ndash7462002

10 Journal of Analytical Methods in Chemistry

[44] L A Cardoza A K Korir W H Otto C J Wurrey and C KLarive ldquoApplications of NMR spectroscopy in environmentalsciencerdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 45 no 3-4 pp 209ndash238 2004

[45] C M Preston ldquoApplications of NMR to soil organic matteranalysis history and prospectsrdquo Soil Science vol 161 no 3 pp144ndash166 1996

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

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Quantum Chemistry

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CatalystsJournal of

Page 3: Research Article Spectroscopic Characteristics of ...downloads.hindawi.com/journals/jamc/2016/1480857.pdf · Microbial biomass carbon (MBC) analysis was determined by the chloroform

Journal of Analytical Methods in Chemistry 3

Table 1 Locations and afforestation information of the samples

Abbreviation Tree species Growing period CoordinatesY-1 Pagoda tree 1 yr N40∘24101584059610158401015840 E116∘45101584043710158401015840

Y-4 Pagoda tree 4 yrs N40∘24101584030810158401015840 E116∘45101584000010158401015840

Y-10 Populus tomentosa 10 yrs N40∘23101584058410158401015840 E116∘43101584041610158401015840

Y-15 Populus tomentosa 15 yrs N40∘24101584000710158401015840 E116∘43101584037110158401015840

Y-20 Shrub and locust 20 yrs N40∘20101584052210158401015840 E116∘49101584022010158401015840

the content of clay silt and sand in the soil samples [15]The pH values of the soil were measured in a suspension(waterdry soil 25 1) using a PB-10 pH meter (SartoriusGermany) [16] Microbial biomass carbon (MBC) analysiswas determined by the chloroform fumigation-extractionmethod [17] Total organic carbon (TOC) was calculatedby subtracting inorganic carbon (calculated from CaCO

3

content) from total carbon by a Jena multi NC 3100 analyzer[18] The total N P and available P of the soil sample weremeasured using a AA3 continuous-flow analyzer (Seal Ana-lytical Corporation Germany)The available Kwasmeasuredby flame atomic absorption spectrometric method via PerkinElmer 9100 Atomic Absorption Spectrometry

24 DOM Extraction and Analytical Methods 100 g soilsample was mixed with 500mL distilled water in 1000mLcentrifuge tube whichwas shaken at 200 rmin in a reciprocalshaker for 16 h under room temperature (25∘C) and thencentrifuged at 12000 rmin for 20min The supernatant wasmoved out of centrifuge tube with a hydrophilic PVDFMillipore membrane filter (045 120583m) to carry out the follow-ing characterizations like dissolved organic carbon (DOC)UV-Visible spectroscopy excitation-emission matrix (EEM)fluorescence spectroscopy and even 1H NMR spectroscopy

25 UV-Visible Spectroscopy UV-Visible spectra of the DOMin filtered supernatant were recorded from 200 to 600 nmon a PerkinElmer Lambda 650S spectrophotometer using a10 cmquartz cell [19]The absorbance at 300 nmwas adjustedto 002 to avoid inner filter effects [20] Ultrapure water(Milli-Q 18MΩsdotcm) was selected as the blank

26 Excitation-Emission Matrix (EEM) Fluorescence Spec-troscopy The excitation and emission spectra of the DOMin filtered supernatant were measured on a Hitachi F-7000fluorescence spectrophotometer using a 150W xenon arclamp as the light source Both excitation and emission slitsare 10 nmwith a scan range from 200 nm to 550 nmThe scanrate was 1200 nmmin and the photomultiplier tube voltagewas 700V The standard quinine sulfate units (QSU) wereintroduced to determine the samplesrsquo relative fluorescentintensities that is 4221 intensity unit is equivalent to oneQSU (1 QSU = 1 120583g Lminus1 = 1 ppb quinine sulfate in 005mol Lminus1H2SO4) [21 22] The Rayleigh scatter effects were eliminated

from the data set by adding zero to the EEMs in the twotriangle regions (Em le Ex + 20 nm and Em ge 2Ex minus10 nm) [23] along with Raman scatter that was avoided bysubtracting the background value of the ultrapure water asblank [23 24] to highlight the useful fluorescent information

27 1H NMR Spectroscopy Agilent VacElut SPS 24 solidphase extraction (SPE) equipment with Bond Elut C-18 assorbent was selected to isolate the DOM from the samplesin which 100mL leaching liquor extracted from soil samplewas pumped through the SPE column with the speed of10mLmin Two 50mL ultrapure water solvents were usedto pass through the SPE column to wash off the residual saltsTheDOMheld in the C-18 packing of SPE columnwas elutedoffwith 6mL solutionmatrix of water andmethanol with vol-ume ratio of 1 9The reduced pressure was stained for 30minto remove the residual solvent [21] Finally the extractedDOM was dried under N

2gas with Termovap Sample

Concentrator (YGC-1217 Bao Jing Company) [22] In orderto conduct 1H NMR spectroscopy analysis the obtainedsolid DOM extracts were dissolved in D

2O (Jin Ouxiang

Company) to avoid water peaks Measurements of 1H NMRspectra of theDOMwere performed on aBruker 400MNMRspectrometerThe pulse conditions of 1HNMRwere listed asthe following operating frequency = 499898MHz acquisi-tion time= 2045 s recycle delay = 10 s and line broadening =10Hz The standard s2pul pulse sequence and baselinecorrection was applied The functional groups in the 1HNMR spectra were identified on their corresponding chemi-cal shifts (120575H) relative to that of the water (47 ppm) [25]

3 Results and Discussion

31 Soil Texture and Soil Quality Indicators The basic phys-ical and chemical properties of the soil samples are assessedAs listed in Table 2 it can be seen that all of the soil samplesselected in this study are sandy texture with a siltsand ratioranging from 7389 to 9264 and the bulk densities werein the range of 145ndash157 gsdotcmminus3 which matched well thepreviously reported values [26] As shown in Table 3 thebasic indexes of soil fertility total organic carbon (TOC)total nitrogen (TN) total phosphorus (TP) and availablepotassium (K) are ranging from 264 to 452 gsdotkgminus1 003to 005 gsdotkgminus1 005 to 048 gsdotkgminus1 and 021 to 061 gsdotkgminus1respectively The TOC increases with the increasing of theafforestation time when the afforestation time is less than tenyear and then remains nearly constant when the time is up toten year The microbial biomass carbon analysis (MBC) andwater extracted dissolved organic carbon (DOC) are in therange of 1628 to 9270mgsdotkgminus1 and 5608 to 8110mgsdotkgminus1respectively The highest MBC (9270mgsdotkgminus1) is observed atsample Y-20 All of the basic physical and chemical propertiesof the samples are shown that the afforestation can improvebiomass in soil

4 Journal of Analytical Methods in Chemistry

Table 2 Basic physical properties of the soil samples

Sample point Clay () Silt () Sand () Bulk density(gsdotcmminus3)

Y-1 021 715 9123 157Y-4 094 2075 7830 149Y-10 082 2324 7594 145Y-15 025 1004 8971 151Y-20 114 2497 7189 151

Abso

rban

ce

200

300

400

500

600 Wav

eleng

ths (

nm)

Y-1Y-4

Y-10Y-15

Y-20

12

10

08

06

04

02

00

Figure 2 UV-Visible spectra of the soil samples

32 Spectroscopic Characteristics of DOM in Soil Samples

321 UV-Visible Spectroscopy As an efficient tool the UV-Visible spectroscopy is employed to evaluate the compositionand structure of DOM [27 28] As illustrated in Figure 2all the UV-Visible spectrum absorbance of the five samplesdecreased with the wavelength which can be found inother studies [5 24 29 30] Some small shoulder peakscan be found in the region of 250ndash300 nm which might becontributed by phenolic aromatic carboxylic and polycyclicaromatic compounds (120587 rarr 120587lowast transition) [31]

The spectral slope coefficients (119878) calculated from theUV-Visible spectra data exhibited the light absorption efficiencyof DOM as a function of the wavelength which negativelyrelates to molecular weight of DOM [32 33] Jamieson et alcalculated 119878 values within the spectra region of 275ndash295 nmto characterize the biochar-derived DOM isolated from soil[32] and Stedmon et al calculated 119878 values in the region from300 to 650 nm to investigate themolecular weight of DOM inDanish coastal water bodies [34] To avoid the use of spectraldata near the detection limit of the instruments the ratioof the slope of the shorter wavelength region (275ndash295 nm119878275ndash295) to that of the longerwavelength region (350ndash400 nm119878350ndash400) was calculated and this dimensionless parametercan be called 119878

119877[33]

The 119878 and 119878119877values were calculated as follows

119886 (120582) = 119886 (1205820) 119890119878(1205820minus120582)

+ 119870

119886 (120582) =

2303119860 (120582)

119897

119878119877=

119878275ndash295119878350ndash400

(1)

in which 119886(120582) and 119886(1205820) represent absorption coefficients

and absorption coefficients at reference wavelength respec-tively 120582 and 120582

0are the reference wavelength (300 nm was

selected in this study) and the selected wavelength (rangingfrom 240 nm to 400 nm) respectively 119860(120582) represents theabsorbance at wavelength 120582 (nm) 119897 (m) is the optical pathlength (001m in this study) and 119870 is a background 119889parameter to improve the goodness of fitting

The median of 119878119877

values determined for the DOMsamples of the five sits (Y-1 Y-4 Y-10 Y-15 and Y-20) was064 107 092 095 and 077 respectively suggesting that themolecular weight of DOM in the soil samples is Y-1 gt Y-20 gtY-10 gt Y-15 gt Y-4

In order to explore the aromaticity of the DOM samplesSUVA

254was introduced as follows

SUVA254=

119886254

DOC (2)

where 119886254

(mminus1) is the absorbance coefficient measured at254 nm The median values of SUVA

254were 539 590 483

533 and 439 LmgCminus1mminus1 for Y-1 Y-4 Y-10 Y-15 and Y-20 respectively The previously reported SUVA

254values of

wetland soil [35] and the agricultural soil [27] were 351ndash441 and 032ndash465 respectively suggesting that the DOM inour study contained a greater amount of aromatic structuresAnd previous studies proposed that different landscapes werelikely to produce different types of DOM [36 37] thereforethe SUVA

254values in this study could roughly imply that

afforestation in suburban area can produce the aromaticsubstances The highest values of SUVA

254were observed at

Y-4 while the lowest values were observed at Y-20

322 Excitation-Emission Matrix (EEM) Fluorescence Spec-troscopy The excitation-emission matrix (EEM) fluores-cence technique is powerful to provide sufficient informa-tion on DOMrsquos molecular size chemical composition andaromaticity or aliphatic properties [5 27] EEM can identifyhumic-like (designated as A C and M) and protein-likefluorescence peaks (B and T) as listed in Table 4 EEMfluorescence spectra of the study areas samples were depictedin Figures 3(a)ndash3(e) suggesting that the UV humic-likesubstances were the primary fluorophores components inthe DOM extracted from afforestation land samples [38]The first identified peak (peak A) was located at ExEm of257 nm448 nm 256 nm440 nm 262 nm443 nm 260 nm425 nm and 260 nm435 nm for the Y-1 Y-4 Y-10 Y-15 andY-20 samples respectively suggesting the existence of UVhumic-like substances The second typical peak (peak T)was observed at ExEm of 271 nm347 nm 280 nm325 nm

Journal of Analytical Methods in Chemistry 5

Table 3 Basic chemical properties of the soil samples

Sample point pH TN (gsdotkgminus1) TP (gsdotkgminus1) Available K (mgsdotkgminus1) TOC (gsdotkgminus1) MBC (mgsdotkgminus1) DOC (mgsdotkgminus1)Y-1 634 003 009 051 264 1628 8110Y-4 633 005 019 030 277 4209 6845Y-10 657 002 021 025 445 1964 6125Y-15 665 002 048 021 452 5945 5608Y-20 705 003 005 061 445 9270 6943

Table 4 Peaks description and excitationemission maxima of fluorescent DOM

Peaks Description Excitation max (nm) Emission max (nm)A UV humic-like less aromatic lt260 380ndash460C Visible humic-like more aromatic 320ndash360 420ndash460M Marine-humic-like 290ndash310 370ndash410B Tyrosine-like substances 260 280T Protein-like tryptophan 250ndash300 305ndash355

275 nm338 nm 279 nm333 nm and 271 nm339 nm for thefive samples stated above respectively implying the pres-ence of tryptophan protein-like components [38] GenerallyDOM in soil is affected by some factors like local geologyland use and microbial and human activities [38] And itcan be believed that the presence of tryptophan protein-likesubstances could further confirm the larger molecular weightDOM presented in the soil [39 40]

Moreover the fluorescence intensities of the five sites (Y-1Y-4 Y-10 Y-15 andY-20) for peakAwere 24 60 78 63 and 81QSU respectively while the peak T fluorescence intensities ofthe five sites were 834 91 106 76 and 124 QSU respectively

Three typical fluorescence indices like the fluorescenceindex (FI) the humification index (HIX) and the biologicalindex (BIX) were selected to investigate the sources thedegree of maturation and the influence from autochthonousbiological activity of DOM as listed in the following

FI =119891450

119891500

HIX = 119867119871

BIX =119891380

119891430

(3)

where 119891450

and 119891500

are the intensities at the emission wave-length of 450 nm and 500 nm at the excitation wavelength370 nm respectively [41 42] while 119891

380and 119891

430are the

fluorescence intensity at the emission wavelength of 380 nmand 430 nm at the excitation wavelength 310 nm respectively[27 38] 119867 and 119871 represent the integral values from 435to 480 nm and 300 to 345 nm at the excitation wavelength254 nm respectively [27 43]

As listed in Table 5 themean FI values of the five sitesrsquo soilsamples were 154 161 146 152 and 151 for Y-1 Y-4 Y-10Y-15 and Y-20 respectively Considering that the terrestrialand microbial end-member values were reported as 14 and19 [41 42] the FI values in this study suggested that thesources of DOM in the soil samples were possibly assigned

Table 5 Results of UV-Visible spectroscopy and EEM fluorescencespectroscopy

Sample point SUVA254

(mgminus1sdotmminus1) SR FI BIX HIXY-1 539 064 154 056 147Y-4 590 107 161 048 1890Y-10 483 092 146 057 217Y-15 533 095 152 043 616Y-20 439 077 151 067 366

to both terrestrial and microbial sources which cannot beinfluenced by the afforestation time The mean HIX valuesin this study were 1470 1890 217 616 and 366 for Y-1Y-4 Y-10 Y-15 and Y-20 respectively It was believed thatthe high HIX values at the region of 10ndash16 are the indicatorof the strongly humic organic substances (terrestrial origin)whereas low values (lt4) imply the presence of autochthonousorganic components [38ndash40]

Compared to the samples of the Y-10 and Y-20 siteswhich mainly consisted of autochthonous organic matters(HIX valueslt 405) theDOMextracted from the soil samplesof the other three sites (Y-1 Y-4 and Y-15) was composed ofboth allochthonous and autochthonous organic substancesPrevious study reported that the allochthonous organic mat-ters originated from incomplete decomposition of plant andanimal residues while the autochthonous organic ones mayderive from the photosynthesis [40] High BIX values (gt1)correspond to autochthonous sources while low BIX values(lt1) imply low abundance of organic matter of biologicalorigin [38ndash40] The mean BIX values of the five sitesrsquo soilsamples were 056 048 057 043 and 067 for Y-1 Y-4 Y-10Y-15 and Y-20 respectively indicative of low abundance ofbiological origin organic components

323 1H NMR Spectroscopy Proton NMR spectroscopy (1HNMR) was often utilized to characterize the composition oftheDOM in soil samples which can provide semiquantitative

6 Journal of Analytical Methods in Chemistry

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

Y-1

0000

2500

5000

7500

1000

1250

1500

1750

2000

2250

200

250

300

350

400

450

500

550Em

issio

n w

avele

ngth

(nm

)

T

A

(a)

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

Y-4

200

250

300

350

400

450

500

550

Emiss

ion

wav

eleng

th (n

m)

0000

6000

1200

1800

2400

3000

3600

4200

4800

5400

T

A

(b)

200

250

300

350

400

450

500

550

Emiss

ion

wav

eleng

th (n

m)

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

0000

8000

1600

2400

3200

4000

4800

5600

6400

7200Y-10

T

A

(c)

200

250

300

350

400

450

500

550

Emiss

ion

wav

eleng

th (n

m)

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

0000

6500

1300

1950

2600

3250

3900

4550

5200

5850

6500Y-15

T

A

(d)

200

250

300

350

400

450

500

550

Emiss

ion

wav

eleng

th (n

m)

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

0000

9000

1800

2700

3600

4500

5400

6300

7200

8100Y-20

T

A

(e)

Figure 3 EEM fluorescence contour profiles of the five sitesrsquo DOM

information on aromatic aliphatic and carboxylic groups[27 44 45] Much different from UV-Visible spectroscopyand EEM 1H NMR can give us the content and structuralinformation via the corresponding integrated areas and thechemical shifts (120575H) [18 19] As illustrated in Figure 4 the1H NMR results of the five sites exhibit some distinct peaksoverlaying bands implying the existence of complicatedmixtures in theDOMDespite the large variety of overlapping

resonances each 1H NMR spectrum was analyzed based onthe chemical shift assignments following the methoddescribed in the previously reported literatures for soilDOM [27] The integrated regions in the 1H NMR spectrawere listed as follows 120575H = 05ndash29 ppm (aliphatic protonsH-C) 120575H = 30ndash42 ppm (carbohydrates H-C-C=) and120575H = 60ndash80 ppm (aromatic protons) [27] The spectra offive sites were depicted in Figure 5 The 1H NMR results of

Journal of Analytical Methods in Chemistry 7

0123456789

(ppm)

Y-1

0123456789

(ppm)

Y-4

0123456789

(ppm)

Y-10

0123456789

(ppm)

Y-15

0123456789

(ppm)

Y-20

Figure 4 1H NMR spectra of DOM in the extracted samples of the five sampling sites

the five sites exhibited similar patterns as to functional groupcomposition suggesting the presence of more aliphaticand carbohydrates structures and less quantity of aromaticorganic matters (Table 6)

The content of saturated aliphatic substances in site Y-1(42) was lower than other sites (681 645 367 and340 forY-4 Y-10 Y-15 andY-20 resp) while the content of

carbohydrates (922) was higher than other sites (335335 598 and 642 for Y-4 Y-10 Y-15 and Y-20 resp)The content of aromatic structures in the five sites was 3647 2 35 and 18 for Y-1 Y-4 Y-10 Y-15 and Y-20respectively The results implied that the saturated aliphaticchains and carbohydrates were the main structures inafforestation forest land

8 Journal of Analytical Methods in Chemistry

Table 6 Results of the 1H NMR analyses

Samplesites

aliphatics(05ndash300 ppm)

carbohydrates(300ndash42 ppm)

aromatics(600ndash800 ppm)

Y-1 42 922 36Y-4 618 335 47Y-10 645 335 2Y-15 367 598 35Y-20 34 642 18

H-C H-C-C= H-Ar0

20

40

60

80

100

Perc

enta

ge (

)

Y-1Y-4

Y-15Y-20

Y-10

Figure 5The relative abundance of each type of protons estimatedas the partial integrals of the spectra reported in Figure 4

4 Conclusions

With this study a preliminary soil quality evaluation werecarried out based on soil texture and some chemical indi-cators like TOC TN TP K+ MBC and DOC Particularlythe DOM in the soil samples with different afforestation timewas further characterized via DOC UV-Visible spectroscopyEEM fluorescence spectroscopy and 1H NMR spectroscopyThe results of EEM fluorescence spectroscopy demonstratedthat UV humic-like substances were the major fluorophorescomponents in the DOM of the soil samples The DOM inthe soil samples wasmainly composed of aliphatic chains andaromatic components with carbonyl carboxyl and hydroxylgroups DOM in soils plays a crucial role in soil physicalchemical and biological processes but little information isavailable on the formation and biodegradability of plant-derived DOM in afforestation forest soil With the develop-ment of afforestation forest in Beijing it is necessary to fur-ther investigate the DOMdistribution and the correspondinginfluence on soil quality plants growth and ecosystem

Competing Interests

The authors declare that there are no competing interestsregarding the publication of this paper

Acknowledgments

This study was supported by the Fund of 12th Five-Year National Science and Technology Support Program(2013BAJ02B0404)

References

[1] S Cao ldquoWhy large-scale afforestation efforts in China havefailed to solve the desertification problemrdquo EnvironmentalScience and Technology vol 42 no 6 pp 1826ndash1831 2008

[2] Y Qiao J Wang and J Li ldquoThe summary and reflection ofBeijingrsquos plain reforestation taking Qingyundian of Daxingdistrict as an examplerdquo Forestry Economics vol 4 article 0052014

[3] K Kaiser G Guggenberger and W Zech ldquoSorption of DOMand DOM fractions to forest soilsrdquo Geoderma vol 74 no 3-4pp 281ndash303 1996

[4] R G Qualls and B L Haines ldquoBiodegradability of dissolvedorganic matter in forest throughfall soil solution and streamwaterrdquo Soil Science Society of America Journal vol 56 no 2 pp578ndash586 1992

[5] R Bi Q Lu T Yuan S Zhou Y Yuan and Y Cai ldquoElectro-chemical and spectroscopic characteristics of dissolved organicmatter in a forest soil profilerdquo Journal of Environmental Sciencesvol 25 no 10 pp 2093ndash2101 2013

[6] X-J Guo N-M Zhu L Chen D-H Yuan and L-S HeldquoCharacterizing the fluorescent properties and copper complex-ation of dissolved organic matter in saline-alkali soils usingfluorescence excitation-emission matrix and parallel factoranalysisrdquo Journal of Soils and Sediments vol 15 no 7 pp 1473ndash1482 2015

[7] B Marschner and K Kalbitz ldquoControls of bioavailability andbiodegradability of dissolved organic matter in soilsrdquo Geo-derma vol 113 no 3-4 pp 211ndash235 2003

[8] K Kalbitz S Solinger J-H Park B Michalzik and E MatznerldquoControls on the dynamics dissolved organic matter in soils areviewrdquo Soil Science vol 165 no 4 pp 277ndash304 2000

[9] D L Jones P Simfukwe P W Hill R T E Mills and B AEmmett ldquoEvaluation of dissolved organic carbon as a soil qual-ity indicator in national monitoring schemesrdquo PLoS ONE vol9 no 3 Article ID e90882 2014

[10] T Yuan Y Yuan S Zhou F Li Z Liu and L Zhuang ldquoA rapidand simple electrochemical method for evaluating the electrontransfer capacities of dissolved organic matterrdquo Journal of Soilsand Sediments vol 11 no 3 pp 467ndash473 2011

[11] T Ohno I J Fernandez S Hiradate and J F Sherman ldquoEffectsof soil acidification and forest type on water soluble soil organicmatter propertiesrdquoGeoderma vol 140 no 1-2 pp 176ndash187 2007

[12] G F Vance and M B David ldquoChemical characteristics andacidity of soluble organic substances from a northern hardwoodforest floor central Maine USArdquo Geochimica et CosmochimicaActa vol 55 no 12 pp 3611ndash3625 1991

[13] Q-Y Wang Y Wang Q-C Wang et al ldquoEffects of land usechanges on the spectroscopic characterization of hot-waterextractable organic matter along a chronosequence correla-tionswith soil enzyme activityrdquoEuropean Journal of Soil Biologyvol 58 pp 8ndash12 2013

[14] M A Rab ldquoSoil physical and hydrological properties followinglogging and slash burning in the Eucalyptus regnans forest ofsoutheastern Australiardquo Forest Ecology and Management vol84 no 1ndash3 pp 159ndash176 1996

Journal of Analytical Methods in Chemistry 9

[15] M Han G Ji and J Ni ldquoWashing of field weathered crude oilcontaminated soil with an environmentally compatible surfac-tant alkyl polyglucosiderdquo Chemosphere vol 76 no 5 pp 579ndash586 2009

[16] X Bi L Ren M Gong Y He L Wang and Z Ma ldquoTransfer ofcadmium and lead from soil to mangoes in an uncontaminatedarea Hainan Island ChinardquoGeoderma vol 155 no 1-2 pp 115ndash120 2010

[17] J Akagi A Zsolnay and F Bastida ldquoQuantity and spectroscopicproperties of soil dissolved organic matter (DOM) as a func-tion of soil sample treatments air-drying and pre-incubationrdquoChemosphere vol 69 no 7 pp 1040ndash1046 2007

[18] N Roig J Sierra E Martı M Nadal M Schuhmacher and J LDomingo ldquoLong-term amendment of Spanish soils with sewagesludge effects on soil functioningrdquo Agriculture Ecosystems andEnvironment vol 158 pp 41ndash48 2012

[19] J L Weishaar G R Aiken B A Bergamaschi M S FramR Fujii and K Mopper ldquoEvaluation of specific ultravioletabsorbance as an indicator of the chemical composition andreactivity of dissolved organic carbonrdquo Environmental Scienceand Technology vol 37 no 20 pp 4702ndash4708 2003

[20] S A Green and N V Blough ldquoOptical absorption and fluores-cence properties of chromophoric dissolved organic matter innatural watersrdquo Limnology and Oceanography vol 39 no 8 pp1903ndash1916 1994

[21] P J Seaton R J Kieber J DWilley G B Avery and J L DixonldquoSeasonal and temporal characterization of dissolved organicmatter in rainwater by proton nuclear magnetic resonancespectroscopyrdquo Atmospheric Environment vol 65 pp 52ndash602013

[22] J Amador P J Milne C A Moore and R G Zika ldquoExtractionof chromophoric humic substances from seawaterrdquo MarineChemistry vol 29 pp 1ndash17 1990

[23] C A Stedmon and R Bro ldquoCharacterizing dissolved organicmatter fluorescence with parallel factor analysis a tutorialrdquoLimnology and Oceanography Methods vol 6 no 11 pp 572ndash579 2008

[24] P S M Santos M Otero R M B O Duarte and A C DuarteldquoSpectroscopic characterization of dissolved organicmatter iso-lated from rainwaterrdquoChemosphere vol 74 no 8 pp 1053ndash10612009

[25] C ZhaoC-CWang J-Q Li C-YWang PWang andZ-J PeildquoDissolved organic matter in urban stormwater runoff at threetypical regions in Beijing chemical composition structuralcharacterization and source identificationrdquo RSC Advances vol5 no 90 pp 73490ndash73500 2015

[26] Z Wang and Q Wang ldquoThe spatial heterogeneity of soilphysical properties in forestsrdquoActa Ecologica Sinica vol 20 no6 pp 945ndash950 1999

[27] M L Fernandez-Romero J M Clark C D Collins L Parras-Alcantara and B Lozano-Garcıa ldquoEvaluation of optical tech-niques for characterising soil organic matter quality in agricul-tural soilsrdquo Soil and Tillage Research vol 155 pp 450ndash460 2016

[28] K Kalbitz J Schmerwitz D Schwesig and E MatznerldquoBiodegradation of soil-derived dissolved organic matter asrelated to its propertiesrdquo Geoderma vol 113 no 3-4 pp 273ndash291 2003

[29] R M B O Duarte and A C Duarte ldquoApplication of non-ionic solid sorbents (XADResins) for the isolation and fraction-ation of water-soluble organic compounds from atmosphericaerosolsrdquo Journal of Atmospheric Chemistry vol 51 no 1 pp79ndash93 2005

[30] N Senesi T M Miano M R Provenzano and G BrunettildquoSpectroscopic and compositional comparative characteriza-tion of IHSS reference and standard fulvic and humic acidsof various originrdquo Science of the Total Environment vol 81-82pp 143ndash156 1989

[31] X-S He B-D Xi Y-H Jiang et al ldquoStructural transformationstudy of water-extractable organic matter during the industrialcomposting of cattle manurerdquo Microchemical Journal vol 106pp 160ndash166 2013

[32] T Jamieson E Sager and C Gueguen ldquoCharacterizationof biochar-derived dissolved organic matter using UV-visibleabsorption and excitation-emission fluorescence spectrosco-piesrdquo Chemosphere vol 103 pp 197ndash204 2014

[33] J R Helms A Stubbins J D Ritchie E C Minor D J Kieberand K Mopper ldquoAbsorption spectral slopes and slope ratiosas indicators of molecular weight source and photobleachingof chromophoric dissolved organic matterrdquo Limnology andOceanography vol 53 no 3 pp 955ndash969 2008

[34] C A Stedmon S Markager and H Kaas ldquoOptical proper-ties and signatures of chromophoric dissolved organic matter(CDOM) in Danish coastal watersrdquo Estuarine Coastal and ShelfScience vol 51 no 2 pp 267ndash278 2000

[35] J B Fellman D V DrsquoAmore E Hood and R D BooneldquoFluorescence characteristics and biodegradability of dissolvedorganic matter in forest and wetland soils from coastal temper-atewatersheds in southeastAlaskardquoBiogeochemistry vol 88 no2 pp 169ndash184 2008

[36] J Sanderman J A Baldock and R Amundson ldquoDissolvedorganic carbon chemistry and dynamics in contrasting forestand grassland soilsrdquo Biogeochemistry vol 89 no 2 pp 181ndash1982008

[37] K Fujii M Uemura C Hayakawa et al ldquoFluxes of dissolvedorganic carbon in two tropical forest ecosystems of East Kali-mantan Indonesiardquo Geoderma vol 152 no 1-2 pp 127ndash1362009

[38] A Huguet L Vacher S Relexans S Saubusse J M Froidefondand E Parlanti ldquoProperties of fluorescent dissolved organicmatter in the Gironde Estuaryrdquo Organic Geochemistry vol 40no 6 pp 706ndash719 2009

[39] A Huguet L Vacher S Saubusse et al ldquoNew insights intothe size distribution of fluorescent dissolved organic matter inestuarine watersrdquo Organic Geochemistry vol 41 no 6 pp 595ndash610 2010

[40] P R Salve H Lohkare T Gobre et al ldquoCharacterization ofchromophoric dissolved organic matter (CDOM) in rainwaterusing fluorescence spectrophotometryrdquoBulletin of Environmen-tal Contamination and Toxicology vol 88 no 2 pp 215ndash2182012

[41] D M McKnight E W Boyer P K Westerhoff P T DoranT Kulbe and D T Andersen ldquoSpectrofluorometric characteri-zation of dissolved organic matter for indication of precursororganic material and aromaticityrdquo Limnology and Oceanogra-phy vol 46 no 1 pp 38ndash48 2001

[42] R Jaffe J N Boyer X Lu et al ldquoSource characterization ofdissolved organic matter in a subtropical mangrove-dominatedestuary by fluorescence analysisrdquoMarine Chemistry vol 84 no3-4 pp 195ndash210 2004

[43] T Ohno ldquoFluorescence inner-filtering correction for deter-mining the humification index of dissolved organic matterrdquoEnvironmental Science amp Technology vol 36 no 4 pp 742ndash7462002

10 Journal of Analytical Methods in Chemistry

[44] L A Cardoza A K Korir W H Otto C J Wurrey and C KLarive ldquoApplications of NMR spectroscopy in environmentalsciencerdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 45 no 3-4 pp 209ndash238 2004

[45] C M Preston ldquoApplications of NMR to soil organic matteranalysis history and prospectsrdquo Soil Science vol 161 no 3 pp144ndash166 1996

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

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Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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Analytical ChemistryInternational Journal of

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Journal of

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Quantum Chemistry

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Organic Chemistry International

ElectrochemistryInternational Journal of

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CatalystsJournal of

Page 4: Research Article Spectroscopic Characteristics of ...downloads.hindawi.com/journals/jamc/2016/1480857.pdf · Microbial biomass carbon (MBC) analysis was determined by the chloroform

4 Journal of Analytical Methods in Chemistry

Table 2 Basic physical properties of the soil samples

Sample point Clay () Silt () Sand () Bulk density(gsdotcmminus3)

Y-1 021 715 9123 157Y-4 094 2075 7830 149Y-10 082 2324 7594 145Y-15 025 1004 8971 151Y-20 114 2497 7189 151

Abso

rban

ce

200

300

400

500

600 Wav

eleng

ths (

nm)

Y-1Y-4

Y-10Y-15

Y-20

12

10

08

06

04

02

00

Figure 2 UV-Visible spectra of the soil samples

32 Spectroscopic Characteristics of DOM in Soil Samples

321 UV-Visible Spectroscopy As an efficient tool the UV-Visible spectroscopy is employed to evaluate the compositionand structure of DOM [27 28] As illustrated in Figure 2all the UV-Visible spectrum absorbance of the five samplesdecreased with the wavelength which can be found inother studies [5 24 29 30] Some small shoulder peakscan be found in the region of 250ndash300 nm which might becontributed by phenolic aromatic carboxylic and polycyclicaromatic compounds (120587 rarr 120587lowast transition) [31]

The spectral slope coefficients (119878) calculated from theUV-Visible spectra data exhibited the light absorption efficiencyof DOM as a function of the wavelength which negativelyrelates to molecular weight of DOM [32 33] Jamieson et alcalculated 119878 values within the spectra region of 275ndash295 nmto characterize the biochar-derived DOM isolated from soil[32] and Stedmon et al calculated 119878 values in the region from300 to 650 nm to investigate themolecular weight of DOM inDanish coastal water bodies [34] To avoid the use of spectraldata near the detection limit of the instruments the ratioof the slope of the shorter wavelength region (275ndash295 nm119878275ndash295) to that of the longerwavelength region (350ndash400 nm119878350ndash400) was calculated and this dimensionless parametercan be called 119878

119877[33]

The 119878 and 119878119877values were calculated as follows

119886 (120582) = 119886 (1205820) 119890119878(1205820minus120582)

+ 119870

119886 (120582) =

2303119860 (120582)

119897

119878119877=

119878275ndash295119878350ndash400

(1)

in which 119886(120582) and 119886(1205820) represent absorption coefficients

and absorption coefficients at reference wavelength respec-tively 120582 and 120582

0are the reference wavelength (300 nm was

selected in this study) and the selected wavelength (rangingfrom 240 nm to 400 nm) respectively 119860(120582) represents theabsorbance at wavelength 120582 (nm) 119897 (m) is the optical pathlength (001m in this study) and 119870 is a background 119889parameter to improve the goodness of fitting

The median of 119878119877

values determined for the DOMsamples of the five sits (Y-1 Y-4 Y-10 Y-15 and Y-20) was064 107 092 095 and 077 respectively suggesting that themolecular weight of DOM in the soil samples is Y-1 gt Y-20 gtY-10 gt Y-15 gt Y-4

In order to explore the aromaticity of the DOM samplesSUVA

254was introduced as follows

SUVA254=

119886254

DOC (2)

where 119886254

(mminus1) is the absorbance coefficient measured at254 nm The median values of SUVA

254were 539 590 483

533 and 439 LmgCminus1mminus1 for Y-1 Y-4 Y-10 Y-15 and Y-20 respectively The previously reported SUVA

254values of

wetland soil [35] and the agricultural soil [27] were 351ndash441 and 032ndash465 respectively suggesting that the DOM inour study contained a greater amount of aromatic structuresAnd previous studies proposed that different landscapes werelikely to produce different types of DOM [36 37] thereforethe SUVA

254values in this study could roughly imply that

afforestation in suburban area can produce the aromaticsubstances The highest values of SUVA

254were observed at

Y-4 while the lowest values were observed at Y-20

322 Excitation-Emission Matrix (EEM) Fluorescence Spec-troscopy The excitation-emission matrix (EEM) fluores-cence technique is powerful to provide sufficient informa-tion on DOMrsquos molecular size chemical composition andaromaticity or aliphatic properties [5 27] EEM can identifyhumic-like (designated as A C and M) and protein-likefluorescence peaks (B and T) as listed in Table 4 EEMfluorescence spectra of the study areas samples were depictedin Figures 3(a)ndash3(e) suggesting that the UV humic-likesubstances were the primary fluorophores components inthe DOM extracted from afforestation land samples [38]The first identified peak (peak A) was located at ExEm of257 nm448 nm 256 nm440 nm 262 nm443 nm 260 nm425 nm and 260 nm435 nm for the Y-1 Y-4 Y-10 Y-15 andY-20 samples respectively suggesting the existence of UVhumic-like substances The second typical peak (peak T)was observed at ExEm of 271 nm347 nm 280 nm325 nm

Journal of Analytical Methods in Chemistry 5

Table 3 Basic chemical properties of the soil samples

Sample point pH TN (gsdotkgminus1) TP (gsdotkgminus1) Available K (mgsdotkgminus1) TOC (gsdotkgminus1) MBC (mgsdotkgminus1) DOC (mgsdotkgminus1)Y-1 634 003 009 051 264 1628 8110Y-4 633 005 019 030 277 4209 6845Y-10 657 002 021 025 445 1964 6125Y-15 665 002 048 021 452 5945 5608Y-20 705 003 005 061 445 9270 6943

Table 4 Peaks description and excitationemission maxima of fluorescent DOM

Peaks Description Excitation max (nm) Emission max (nm)A UV humic-like less aromatic lt260 380ndash460C Visible humic-like more aromatic 320ndash360 420ndash460M Marine-humic-like 290ndash310 370ndash410B Tyrosine-like substances 260 280T Protein-like tryptophan 250ndash300 305ndash355

275 nm338 nm 279 nm333 nm and 271 nm339 nm for thefive samples stated above respectively implying the pres-ence of tryptophan protein-like components [38] GenerallyDOM in soil is affected by some factors like local geologyland use and microbial and human activities [38] And itcan be believed that the presence of tryptophan protein-likesubstances could further confirm the larger molecular weightDOM presented in the soil [39 40]

Moreover the fluorescence intensities of the five sites (Y-1Y-4 Y-10 Y-15 andY-20) for peakAwere 24 60 78 63 and 81QSU respectively while the peak T fluorescence intensities ofthe five sites were 834 91 106 76 and 124 QSU respectively

Three typical fluorescence indices like the fluorescenceindex (FI) the humification index (HIX) and the biologicalindex (BIX) were selected to investigate the sources thedegree of maturation and the influence from autochthonousbiological activity of DOM as listed in the following

FI =119891450

119891500

HIX = 119867119871

BIX =119891380

119891430

(3)

where 119891450

and 119891500

are the intensities at the emission wave-length of 450 nm and 500 nm at the excitation wavelength370 nm respectively [41 42] while 119891

380and 119891

430are the

fluorescence intensity at the emission wavelength of 380 nmand 430 nm at the excitation wavelength 310 nm respectively[27 38] 119867 and 119871 represent the integral values from 435to 480 nm and 300 to 345 nm at the excitation wavelength254 nm respectively [27 43]

As listed in Table 5 themean FI values of the five sitesrsquo soilsamples were 154 161 146 152 and 151 for Y-1 Y-4 Y-10Y-15 and Y-20 respectively Considering that the terrestrialand microbial end-member values were reported as 14 and19 [41 42] the FI values in this study suggested that thesources of DOM in the soil samples were possibly assigned

Table 5 Results of UV-Visible spectroscopy and EEM fluorescencespectroscopy

Sample point SUVA254

(mgminus1sdotmminus1) SR FI BIX HIXY-1 539 064 154 056 147Y-4 590 107 161 048 1890Y-10 483 092 146 057 217Y-15 533 095 152 043 616Y-20 439 077 151 067 366

to both terrestrial and microbial sources which cannot beinfluenced by the afforestation time The mean HIX valuesin this study were 1470 1890 217 616 and 366 for Y-1Y-4 Y-10 Y-15 and Y-20 respectively It was believed thatthe high HIX values at the region of 10ndash16 are the indicatorof the strongly humic organic substances (terrestrial origin)whereas low values (lt4) imply the presence of autochthonousorganic components [38ndash40]

Compared to the samples of the Y-10 and Y-20 siteswhich mainly consisted of autochthonous organic matters(HIX valueslt 405) theDOMextracted from the soil samplesof the other three sites (Y-1 Y-4 and Y-15) was composed ofboth allochthonous and autochthonous organic substancesPrevious study reported that the allochthonous organic mat-ters originated from incomplete decomposition of plant andanimal residues while the autochthonous organic ones mayderive from the photosynthesis [40] High BIX values (gt1)correspond to autochthonous sources while low BIX values(lt1) imply low abundance of organic matter of biologicalorigin [38ndash40] The mean BIX values of the five sitesrsquo soilsamples were 056 048 057 043 and 067 for Y-1 Y-4 Y-10Y-15 and Y-20 respectively indicative of low abundance ofbiological origin organic components

323 1H NMR Spectroscopy Proton NMR spectroscopy (1HNMR) was often utilized to characterize the composition oftheDOM in soil samples which can provide semiquantitative

6 Journal of Analytical Methods in Chemistry

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

Y-1

0000

2500

5000

7500

1000

1250

1500

1750

2000

2250

200

250

300

350

400

450

500

550Em

issio

n w

avele

ngth

(nm

)

T

A

(a)

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

Y-4

200

250

300

350

400

450

500

550

Emiss

ion

wav

eleng

th (n

m)

0000

6000

1200

1800

2400

3000

3600

4200

4800

5400

T

A

(b)

200

250

300

350

400

450

500

550

Emiss

ion

wav

eleng

th (n

m)

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

0000

8000

1600

2400

3200

4000

4800

5600

6400

7200Y-10

T

A

(c)

200

250

300

350

400

450

500

550

Emiss

ion

wav

eleng

th (n

m)

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

0000

6500

1300

1950

2600

3250

3900

4550

5200

5850

6500Y-15

T

A

(d)

200

250

300

350

400

450

500

550

Emiss

ion

wav

eleng

th (n

m)

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

0000

9000

1800

2700

3600

4500

5400

6300

7200

8100Y-20

T

A

(e)

Figure 3 EEM fluorescence contour profiles of the five sitesrsquo DOM

information on aromatic aliphatic and carboxylic groups[27 44 45] Much different from UV-Visible spectroscopyand EEM 1H NMR can give us the content and structuralinformation via the corresponding integrated areas and thechemical shifts (120575H) [18 19] As illustrated in Figure 4 the1H NMR results of the five sites exhibit some distinct peaksoverlaying bands implying the existence of complicatedmixtures in theDOMDespite the large variety of overlapping

resonances each 1H NMR spectrum was analyzed based onthe chemical shift assignments following the methoddescribed in the previously reported literatures for soilDOM [27] The integrated regions in the 1H NMR spectrawere listed as follows 120575H = 05ndash29 ppm (aliphatic protonsH-C) 120575H = 30ndash42 ppm (carbohydrates H-C-C=) and120575H = 60ndash80 ppm (aromatic protons) [27] The spectra offive sites were depicted in Figure 5 The 1H NMR results of

Journal of Analytical Methods in Chemistry 7

0123456789

(ppm)

Y-1

0123456789

(ppm)

Y-4

0123456789

(ppm)

Y-10

0123456789

(ppm)

Y-15

0123456789

(ppm)

Y-20

Figure 4 1H NMR spectra of DOM in the extracted samples of the five sampling sites

the five sites exhibited similar patterns as to functional groupcomposition suggesting the presence of more aliphaticand carbohydrates structures and less quantity of aromaticorganic matters (Table 6)

The content of saturated aliphatic substances in site Y-1(42) was lower than other sites (681 645 367 and340 forY-4 Y-10 Y-15 andY-20 resp) while the content of

carbohydrates (922) was higher than other sites (335335 598 and 642 for Y-4 Y-10 Y-15 and Y-20 resp)The content of aromatic structures in the five sites was 3647 2 35 and 18 for Y-1 Y-4 Y-10 Y-15 and Y-20respectively The results implied that the saturated aliphaticchains and carbohydrates were the main structures inafforestation forest land

8 Journal of Analytical Methods in Chemistry

Table 6 Results of the 1H NMR analyses

Samplesites

aliphatics(05ndash300 ppm)

carbohydrates(300ndash42 ppm)

aromatics(600ndash800 ppm)

Y-1 42 922 36Y-4 618 335 47Y-10 645 335 2Y-15 367 598 35Y-20 34 642 18

H-C H-C-C= H-Ar0

20

40

60

80

100

Perc

enta

ge (

)

Y-1Y-4

Y-15Y-20

Y-10

Figure 5The relative abundance of each type of protons estimatedas the partial integrals of the spectra reported in Figure 4

4 Conclusions

With this study a preliminary soil quality evaluation werecarried out based on soil texture and some chemical indi-cators like TOC TN TP K+ MBC and DOC Particularlythe DOM in the soil samples with different afforestation timewas further characterized via DOC UV-Visible spectroscopyEEM fluorescence spectroscopy and 1H NMR spectroscopyThe results of EEM fluorescence spectroscopy demonstratedthat UV humic-like substances were the major fluorophorescomponents in the DOM of the soil samples The DOM inthe soil samples wasmainly composed of aliphatic chains andaromatic components with carbonyl carboxyl and hydroxylgroups DOM in soils plays a crucial role in soil physicalchemical and biological processes but little information isavailable on the formation and biodegradability of plant-derived DOM in afforestation forest soil With the develop-ment of afforestation forest in Beijing it is necessary to fur-ther investigate the DOMdistribution and the correspondinginfluence on soil quality plants growth and ecosystem

Competing Interests

The authors declare that there are no competing interestsregarding the publication of this paper

Acknowledgments

This study was supported by the Fund of 12th Five-Year National Science and Technology Support Program(2013BAJ02B0404)

References

[1] S Cao ldquoWhy large-scale afforestation efforts in China havefailed to solve the desertification problemrdquo EnvironmentalScience and Technology vol 42 no 6 pp 1826ndash1831 2008

[2] Y Qiao J Wang and J Li ldquoThe summary and reflection ofBeijingrsquos plain reforestation taking Qingyundian of Daxingdistrict as an examplerdquo Forestry Economics vol 4 article 0052014

[3] K Kaiser G Guggenberger and W Zech ldquoSorption of DOMand DOM fractions to forest soilsrdquo Geoderma vol 74 no 3-4pp 281ndash303 1996

[4] R G Qualls and B L Haines ldquoBiodegradability of dissolvedorganic matter in forest throughfall soil solution and streamwaterrdquo Soil Science Society of America Journal vol 56 no 2 pp578ndash586 1992

[5] R Bi Q Lu T Yuan S Zhou Y Yuan and Y Cai ldquoElectro-chemical and spectroscopic characteristics of dissolved organicmatter in a forest soil profilerdquo Journal of Environmental Sciencesvol 25 no 10 pp 2093ndash2101 2013

[6] X-J Guo N-M Zhu L Chen D-H Yuan and L-S HeldquoCharacterizing the fluorescent properties and copper complex-ation of dissolved organic matter in saline-alkali soils usingfluorescence excitation-emission matrix and parallel factoranalysisrdquo Journal of Soils and Sediments vol 15 no 7 pp 1473ndash1482 2015

[7] B Marschner and K Kalbitz ldquoControls of bioavailability andbiodegradability of dissolved organic matter in soilsrdquo Geo-derma vol 113 no 3-4 pp 211ndash235 2003

[8] K Kalbitz S Solinger J-H Park B Michalzik and E MatznerldquoControls on the dynamics dissolved organic matter in soils areviewrdquo Soil Science vol 165 no 4 pp 277ndash304 2000

[9] D L Jones P Simfukwe P W Hill R T E Mills and B AEmmett ldquoEvaluation of dissolved organic carbon as a soil qual-ity indicator in national monitoring schemesrdquo PLoS ONE vol9 no 3 Article ID e90882 2014

[10] T Yuan Y Yuan S Zhou F Li Z Liu and L Zhuang ldquoA rapidand simple electrochemical method for evaluating the electrontransfer capacities of dissolved organic matterrdquo Journal of Soilsand Sediments vol 11 no 3 pp 467ndash473 2011

[11] T Ohno I J Fernandez S Hiradate and J F Sherman ldquoEffectsof soil acidification and forest type on water soluble soil organicmatter propertiesrdquoGeoderma vol 140 no 1-2 pp 176ndash187 2007

[12] G F Vance and M B David ldquoChemical characteristics andacidity of soluble organic substances from a northern hardwoodforest floor central Maine USArdquo Geochimica et CosmochimicaActa vol 55 no 12 pp 3611ndash3625 1991

[13] Q-Y Wang Y Wang Q-C Wang et al ldquoEffects of land usechanges on the spectroscopic characterization of hot-waterextractable organic matter along a chronosequence correla-tionswith soil enzyme activityrdquoEuropean Journal of Soil Biologyvol 58 pp 8ndash12 2013

[14] M A Rab ldquoSoil physical and hydrological properties followinglogging and slash burning in the Eucalyptus regnans forest ofsoutheastern Australiardquo Forest Ecology and Management vol84 no 1ndash3 pp 159ndash176 1996

Journal of Analytical Methods in Chemistry 9

[15] M Han G Ji and J Ni ldquoWashing of field weathered crude oilcontaminated soil with an environmentally compatible surfac-tant alkyl polyglucosiderdquo Chemosphere vol 76 no 5 pp 579ndash586 2009

[16] X Bi L Ren M Gong Y He L Wang and Z Ma ldquoTransfer ofcadmium and lead from soil to mangoes in an uncontaminatedarea Hainan Island ChinardquoGeoderma vol 155 no 1-2 pp 115ndash120 2010

[17] J Akagi A Zsolnay and F Bastida ldquoQuantity and spectroscopicproperties of soil dissolved organic matter (DOM) as a func-tion of soil sample treatments air-drying and pre-incubationrdquoChemosphere vol 69 no 7 pp 1040ndash1046 2007

[18] N Roig J Sierra E Martı M Nadal M Schuhmacher and J LDomingo ldquoLong-term amendment of Spanish soils with sewagesludge effects on soil functioningrdquo Agriculture Ecosystems andEnvironment vol 158 pp 41ndash48 2012

[19] J L Weishaar G R Aiken B A Bergamaschi M S FramR Fujii and K Mopper ldquoEvaluation of specific ultravioletabsorbance as an indicator of the chemical composition andreactivity of dissolved organic carbonrdquo Environmental Scienceand Technology vol 37 no 20 pp 4702ndash4708 2003

[20] S A Green and N V Blough ldquoOptical absorption and fluores-cence properties of chromophoric dissolved organic matter innatural watersrdquo Limnology and Oceanography vol 39 no 8 pp1903ndash1916 1994

[21] P J Seaton R J Kieber J DWilley G B Avery and J L DixonldquoSeasonal and temporal characterization of dissolved organicmatter in rainwater by proton nuclear magnetic resonancespectroscopyrdquo Atmospheric Environment vol 65 pp 52ndash602013

[22] J Amador P J Milne C A Moore and R G Zika ldquoExtractionof chromophoric humic substances from seawaterrdquo MarineChemistry vol 29 pp 1ndash17 1990

[23] C A Stedmon and R Bro ldquoCharacterizing dissolved organicmatter fluorescence with parallel factor analysis a tutorialrdquoLimnology and Oceanography Methods vol 6 no 11 pp 572ndash579 2008

[24] P S M Santos M Otero R M B O Duarte and A C DuarteldquoSpectroscopic characterization of dissolved organicmatter iso-lated from rainwaterrdquoChemosphere vol 74 no 8 pp 1053ndash10612009

[25] C ZhaoC-CWang J-Q Li C-YWang PWang andZ-J PeildquoDissolved organic matter in urban stormwater runoff at threetypical regions in Beijing chemical composition structuralcharacterization and source identificationrdquo RSC Advances vol5 no 90 pp 73490ndash73500 2015

[26] Z Wang and Q Wang ldquoThe spatial heterogeneity of soilphysical properties in forestsrdquoActa Ecologica Sinica vol 20 no6 pp 945ndash950 1999

[27] M L Fernandez-Romero J M Clark C D Collins L Parras-Alcantara and B Lozano-Garcıa ldquoEvaluation of optical tech-niques for characterising soil organic matter quality in agricul-tural soilsrdquo Soil and Tillage Research vol 155 pp 450ndash460 2016

[28] K Kalbitz J Schmerwitz D Schwesig and E MatznerldquoBiodegradation of soil-derived dissolved organic matter asrelated to its propertiesrdquo Geoderma vol 113 no 3-4 pp 273ndash291 2003

[29] R M B O Duarte and A C Duarte ldquoApplication of non-ionic solid sorbents (XADResins) for the isolation and fraction-ation of water-soluble organic compounds from atmosphericaerosolsrdquo Journal of Atmospheric Chemistry vol 51 no 1 pp79ndash93 2005

[30] N Senesi T M Miano M R Provenzano and G BrunettildquoSpectroscopic and compositional comparative characteriza-tion of IHSS reference and standard fulvic and humic acidsof various originrdquo Science of the Total Environment vol 81-82pp 143ndash156 1989

[31] X-S He B-D Xi Y-H Jiang et al ldquoStructural transformationstudy of water-extractable organic matter during the industrialcomposting of cattle manurerdquo Microchemical Journal vol 106pp 160ndash166 2013

[32] T Jamieson E Sager and C Gueguen ldquoCharacterizationof biochar-derived dissolved organic matter using UV-visibleabsorption and excitation-emission fluorescence spectrosco-piesrdquo Chemosphere vol 103 pp 197ndash204 2014

[33] J R Helms A Stubbins J D Ritchie E C Minor D J Kieberand K Mopper ldquoAbsorption spectral slopes and slope ratiosas indicators of molecular weight source and photobleachingof chromophoric dissolved organic matterrdquo Limnology andOceanography vol 53 no 3 pp 955ndash969 2008

[34] C A Stedmon S Markager and H Kaas ldquoOptical proper-ties and signatures of chromophoric dissolved organic matter(CDOM) in Danish coastal watersrdquo Estuarine Coastal and ShelfScience vol 51 no 2 pp 267ndash278 2000

[35] J B Fellman D V DrsquoAmore E Hood and R D BooneldquoFluorescence characteristics and biodegradability of dissolvedorganic matter in forest and wetland soils from coastal temper-atewatersheds in southeastAlaskardquoBiogeochemistry vol 88 no2 pp 169ndash184 2008

[36] J Sanderman J A Baldock and R Amundson ldquoDissolvedorganic carbon chemistry and dynamics in contrasting forestand grassland soilsrdquo Biogeochemistry vol 89 no 2 pp 181ndash1982008

[37] K Fujii M Uemura C Hayakawa et al ldquoFluxes of dissolvedorganic carbon in two tropical forest ecosystems of East Kali-mantan Indonesiardquo Geoderma vol 152 no 1-2 pp 127ndash1362009

[38] A Huguet L Vacher S Relexans S Saubusse J M Froidefondand E Parlanti ldquoProperties of fluorescent dissolved organicmatter in the Gironde Estuaryrdquo Organic Geochemistry vol 40no 6 pp 706ndash719 2009

[39] A Huguet L Vacher S Saubusse et al ldquoNew insights intothe size distribution of fluorescent dissolved organic matter inestuarine watersrdquo Organic Geochemistry vol 41 no 6 pp 595ndash610 2010

[40] P R Salve H Lohkare T Gobre et al ldquoCharacterization ofchromophoric dissolved organic matter (CDOM) in rainwaterusing fluorescence spectrophotometryrdquoBulletin of Environmen-tal Contamination and Toxicology vol 88 no 2 pp 215ndash2182012

[41] D M McKnight E W Boyer P K Westerhoff P T DoranT Kulbe and D T Andersen ldquoSpectrofluorometric characteri-zation of dissolved organic matter for indication of precursororganic material and aromaticityrdquo Limnology and Oceanogra-phy vol 46 no 1 pp 38ndash48 2001

[42] R Jaffe J N Boyer X Lu et al ldquoSource characterization ofdissolved organic matter in a subtropical mangrove-dominatedestuary by fluorescence analysisrdquoMarine Chemistry vol 84 no3-4 pp 195ndash210 2004

[43] T Ohno ldquoFluorescence inner-filtering correction for deter-mining the humification index of dissolved organic matterrdquoEnvironmental Science amp Technology vol 36 no 4 pp 742ndash7462002

10 Journal of Analytical Methods in Chemistry

[44] L A Cardoza A K Korir W H Otto C J Wurrey and C KLarive ldquoApplications of NMR spectroscopy in environmentalsciencerdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 45 no 3-4 pp 209ndash238 2004

[45] C M Preston ldquoApplications of NMR to soil organic matteranalysis history and prospectsrdquo Soil Science vol 161 no 3 pp144ndash166 1996

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

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Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 5: Research Article Spectroscopic Characteristics of ...downloads.hindawi.com/journals/jamc/2016/1480857.pdf · Microbial biomass carbon (MBC) analysis was determined by the chloroform

Journal of Analytical Methods in Chemistry 5

Table 3 Basic chemical properties of the soil samples

Sample point pH TN (gsdotkgminus1) TP (gsdotkgminus1) Available K (mgsdotkgminus1) TOC (gsdotkgminus1) MBC (mgsdotkgminus1) DOC (mgsdotkgminus1)Y-1 634 003 009 051 264 1628 8110Y-4 633 005 019 030 277 4209 6845Y-10 657 002 021 025 445 1964 6125Y-15 665 002 048 021 452 5945 5608Y-20 705 003 005 061 445 9270 6943

Table 4 Peaks description and excitationemission maxima of fluorescent DOM

Peaks Description Excitation max (nm) Emission max (nm)A UV humic-like less aromatic lt260 380ndash460C Visible humic-like more aromatic 320ndash360 420ndash460M Marine-humic-like 290ndash310 370ndash410B Tyrosine-like substances 260 280T Protein-like tryptophan 250ndash300 305ndash355

275 nm338 nm 279 nm333 nm and 271 nm339 nm for thefive samples stated above respectively implying the pres-ence of tryptophan protein-like components [38] GenerallyDOM in soil is affected by some factors like local geologyland use and microbial and human activities [38] And itcan be believed that the presence of tryptophan protein-likesubstances could further confirm the larger molecular weightDOM presented in the soil [39 40]

Moreover the fluorescence intensities of the five sites (Y-1Y-4 Y-10 Y-15 andY-20) for peakAwere 24 60 78 63 and 81QSU respectively while the peak T fluorescence intensities ofthe five sites were 834 91 106 76 and 124 QSU respectively

Three typical fluorescence indices like the fluorescenceindex (FI) the humification index (HIX) and the biologicalindex (BIX) were selected to investigate the sources thedegree of maturation and the influence from autochthonousbiological activity of DOM as listed in the following

FI =119891450

119891500

HIX = 119867119871

BIX =119891380

119891430

(3)

where 119891450

and 119891500

are the intensities at the emission wave-length of 450 nm and 500 nm at the excitation wavelength370 nm respectively [41 42] while 119891

380and 119891

430are the

fluorescence intensity at the emission wavelength of 380 nmand 430 nm at the excitation wavelength 310 nm respectively[27 38] 119867 and 119871 represent the integral values from 435to 480 nm and 300 to 345 nm at the excitation wavelength254 nm respectively [27 43]

As listed in Table 5 themean FI values of the five sitesrsquo soilsamples were 154 161 146 152 and 151 for Y-1 Y-4 Y-10Y-15 and Y-20 respectively Considering that the terrestrialand microbial end-member values were reported as 14 and19 [41 42] the FI values in this study suggested that thesources of DOM in the soil samples were possibly assigned

Table 5 Results of UV-Visible spectroscopy and EEM fluorescencespectroscopy

Sample point SUVA254

(mgminus1sdotmminus1) SR FI BIX HIXY-1 539 064 154 056 147Y-4 590 107 161 048 1890Y-10 483 092 146 057 217Y-15 533 095 152 043 616Y-20 439 077 151 067 366

to both terrestrial and microbial sources which cannot beinfluenced by the afforestation time The mean HIX valuesin this study were 1470 1890 217 616 and 366 for Y-1Y-4 Y-10 Y-15 and Y-20 respectively It was believed thatthe high HIX values at the region of 10ndash16 are the indicatorof the strongly humic organic substances (terrestrial origin)whereas low values (lt4) imply the presence of autochthonousorganic components [38ndash40]

Compared to the samples of the Y-10 and Y-20 siteswhich mainly consisted of autochthonous organic matters(HIX valueslt 405) theDOMextracted from the soil samplesof the other three sites (Y-1 Y-4 and Y-15) was composed ofboth allochthonous and autochthonous organic substancesPrevious study reported that the allochthonous organic mat-ters originated from incomplete decomposition of plant andanimal residues while the autochthonous organic ones mayderive from the photosynthesis [40] High BIX values (gt1)correspond to autochthonous sources while low BIX values(lt1) imply low abundance of organic matter of biologicalorigin [38ndash40] The mean BIX values of the five sitesrsquo soilsamples were 056 048 057 043 and 067 for Y-1 Y-4 Y-10Y-15 and Y-20 respectively indicative of low abundance ofbiological origin organic components

323 1H NMR Spectroscopy Proton NMR spectroscopy (1HNMR) was often utilized to characterize the composition oftheDOM in soil samples which can provide semiquantitative

6 Journal of Analytical Methods in Chemistry

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

Y-1

0000

2500

5000

7500

1000

1250

1500

1750

2000

2250

200

250

300

350

400

450

500

550Em

issio

n w

avele

ngth

(nm

)

T

A

(a)

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

Y-4

200

250

300

350

400

450

500

550

Emiss

ion

wav

eleng

th (n

m)

0000

6000

1200

1800

2400

3000

3600

4200

4800

5400

T

A

(b)

200

250

300

350

400

450

500

550

Emiss

ion

wav

eleng

th (n

m)

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

0000

8000

1600

2400

3200

4000

4800

5600

6400

7200Y-10

T

A

(c)

200

250

300

350

400

450

500

550

Emiss

ion

wav

eleng

th (n

m)

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

0000

6500

1300

1950

2600

3250

3900

4550

5200

5850

6500Y-15

T

A

(d)

200

250

300

350

400

450

500

550

Emiss

ion

wav

eleng

th (n

m)

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

0000

9000

1800

2700

3600

4500

5400

6300

7200

8100Y-20

T

A

(e)

Figure 3 EEM fluorescence contour profiles of the five sitesrsquo DOM

information on aromatic aliphatic and carboxylic groups[27 44 45] Much different from UV-Visible spectroscopyand EEM 1H NMR can give us the content and structuralinformation via the corresponding integrated areas and thechemical shifts (120575H) [18 19] As illustrated in Figure 4 the1H NMR results of the five sites exhibit some distinct peaksoverlaying bands implying the existence of complicatedmixtures in theDOMDespite the large variety of overlapping

resonances each 1H NMR spectrum was analyzed based onthe chemical shift assignments following the methoddescribed in the previously reported literatures for soilDOM [27] The integrated regions in the 1H NMR spectrawere listed as follows 120575H = 05ndash29 ppm (aliphatic protonsH-C) 120575H = 30ndash42 ppm (carbohydrates H-C-C=) and120575H = 60ndash80 ppm (aromatic protons) [27] The spectra offive sites were depicted in Figure 5 The 1H NMR results of

Journal of Analytical Methods in Chemistry 7

0123456789

(ppm)

Y-1

0123456789

(ppm)

Y-4

0123456789

(ppm)

Y-10

0123456789

(ppm)

Y-15

0123456789

(ppm)

Y-20

Figure 4 1H NMR spectra of DOM in the extracted samples of the five sampling sites

the five sites exhibited similar patterns as to functional groupcomposition suggesting the presence of more aliphaticand carbohydrates structures and less quantity of aromaticorganic matters (Table 6)

The content of saturated aliphatic substances in site Y-1(42) was lower than other sites (681 645 367 and340 forY-4 Y-10 Y-15 andY-20 resp) while the content of

carbohydrates (922) was higher than other sites (335335 598 and 642 for Y-4 Y-10 Y-15 and Y-20 resp)The content of aromatic structures in the five sites was 3647 2 35 and 18 for Y-1 Y-4 Y-10 Y-15 and Y-20respectively The results implied that the saturated aliphaticchains and carbohydrates were the main structures inafforestation forest land

8 Journal of Analytical Methods in Chemistry

Table 6 Results of the 1H NMR analyses

Samplesites

aliphatics(05ndash300 ppm)

carbohydrates(300ndash42 ppm)

aromatics(600ndash800 ppm)

Y-1 42 922 36Y-4 618 335 47Y-10 645 335 2Y-15 367 598 35Y-20 34 642 18

H-C H-C-C= H-Ar0

20

40

60

80

100

Perc

enta

ge (

)

Y-1Y-4

Y-15Y-20

Y-10

Figure 5The relative abundance of each type of protons estimatedas the partial integrals of the spectra reported in Figure 4

4 Conclusions

With this study a preliminary soil quality evaluation werecarried out based on soil texture and some chemical indi-cators like TOC TN TP K+ MBC and DOC Particularlythe DOM in the soil samples with different afforestation timewas further characterized via DOC UV-Visible spectroscopyEEM fluorescence spectroscopy and 1H NMR spectroscopyThe results of EEM fluorescence spectroscopy demonstratedthat UV humic-like substances were the major fluorophorescomponents in the DOM of the soil samples The DOM inthe soil samples wasmainly composed of aliphatic chains andaromatic components with carbonyl carboxyl and hydroxylgroups DOM in soils plays a crucial role in soil physicalchemical and biological processes but little information isavailable on the formation and biodegradability of plant-derived DOM in afforestation forest soil With the develop-ment of afforestation forest in Beijing it is necessary to fur-ther investigate the DOMdistribution and the correspondinginfluence on soil quality plants growth and ecosystem

Competing Interests

The authors declare that there are no competing interestsregarding the publication of this paper

Acknowledgments

This study was supported by the Fund of 12th Five-Year National Science and Technology Support Program(2013BAJ02B0404)

References

[1] S Cao ldquoWhy large-scale afforestation efforts in China havefailed to solve the desertification problemrdquo EnvironmentalScience and Technology vol 42 no 6 pp 1826ndash1831 2008

[2] Y Qiao J Wang and J Li ldquoThe summary and reflection ofBeijingrsquos plain reforestation taking Qingyundian of Daxingdistrict as an examplerdquo Forestry Economics vol 4 article 0052014

[3] K Kaiser G Guggenberger and W Zech ldquoSorption of DOMand DOM fractions to forest soilsrdquo Geoderma vol 74 no 3-4pp 281ndash303 1996

[4] R G Qualls and B L Haines ldquoBiodegradability of dissolvedorganic matter in forest throughfall soil solution and streamwaterrdquo Soil Science Society of America Journal vol 56 no 2 pp578ndash586 1992

[5] R Bi Q Lu T Yuan S Zhou Y Yuan and Y Cai ldquoElectro-chemical and spectroscopic characteristics of dissolved organicmatter in a forest soil profilerdquo Journal of Environmental Sciencesvol 25 no 10 pp 2093ndash2101 2013

[6] X-J Guo N-M Zhu L Chen D-H Yuan and L-S HeldquoCharacterizing the fluorescent properties and copper complex-ation of dissolved organic matter in saline-alkali soils usingfluorescence excitation-emission matrix and parallel factoranalysisrdquo Journal of Soils and Sediments vol 15 no 7 pp 1473ndash1482 2015

[7] B Marschner and K Kalbitz ldquoControls of bioavailability andbiodegradability of dissolved organic matter in soilsrdquo Geo-derma vol 113 no 3-4 pp 211ndash235 2003

[8] K Kalbitz S Solinger J-H Park B Michalzik and E MatznerldquoControls on the dynamics dissolved organic matter in soils areviewrdquo Soil Science vol 165 no 4 pp 277ndash304 2000

[9] D L Jones P Simfukwe P W Hill R T E Mills and B AEmmett ldquoEvaluation of dissolved organic carbon as a soil qual-ity indicator in national monitoring schemesrdquo PLoS ONE vol9 no 3 Article ID e90882 2014

[10] T Yuan Y Yuan S Zhou F Li Z Liu and L Zhuang ldquoA rapidand simple electrochemical method for evaluating the electrontransfer capacities of dissolved organic matterrdquo Journal of Soilsand Sediments vol 11 no 3 pp 467ndash473 2011

[11] T Ohno I J Fernandez S Hiradate and J F Sherman ldquoEffectsof soil acidification and forest type on water soluble soil organicmatter propertiesrdquoGeoderma vol 140 no 1-2 pp 176ndash187 2007

[12] G F Vance and M B David ldquoChemical characteristics andacidity of soluble organic substances from a northern hardwoodforest floor central Maine USArdquo Geochimica et CosmochimicaActa vol 55 no 12 pp 3611ndash3625 1991

[13] Q-Y Wang Y Wang Q-C Wang et al ldquoEffects of land usechanges on the spectroscopic characterization of hot-waterextractable organic matter along a chronosequence correla-tionswith soil enzyme activityrdquoEuropean Journal of Soil Biologyvol 58 pp 8ndash12 2013

[14] M A Rab ldquoSoil physical and hydrological properties followinglogging and slash burning in the Eucalyptus regnans forest ofsoutheastern Australiardquo Forest Ecology and Management vol84 no 1ndash3 pp 159ndash176 1996

Journal of Analytical Methods in Chemistry 9

[15] M Han G Ji and J Ni ldquoWashing of field weathered crude oilcontaminated soil with an environmentally compatible surfac-tant alkyl polyglucosiderdquo Chemosphere vol 76 no 5 pp 579ndash586 2009

[16] X Bi L Ren M Gong Y He L Wang and Z Ma ldquoTransfer ofcadmium and lead from soil to mangoes in an uncontaminatedarea Hainan Island ChinardquoGeoderma vol 155 no 1-2 pp 115ndash120 2010

[17] J Akagi A Zsolnay and F Bastida ldquoQuantity and spectroscopicproperties of soil dissolved organic matter (DOM) as a func-tion of soil sample treatments air-drying and pre-incubationrdquoChemosphere vol 69 no 7 pp 1040ndash1046 2007

[18] N Roig J Sierra E Martı M Nadal M Schuhmacher and J LDomingo ldquoLong-term amendment of Spanish soils with sewagesludge effects on soil functioningrdquo Agriculture Ecosystems andEnvironment vol 158 pp 41ndash48 2012

[19] J L Weishaar G R Aiken B A Bergamaschi M S FramR Fujii and K Mopper ldquoEvaluation of specific ultravioletabsorbance as an indicator of the chemical composition andreactivity of dissolved organic carbonrdquo Environmental Scienceand Technology vol 37 no 20 pp 4702ndash4708 2003

[20] S A Green and N V Blough ldquoOptical absorption and fluores-cence properties of chromophoric dissolved organic matter innatural watersrdquo Limnology and Oceanography vol 39 no 8 pp1903ndash1916 1994

[21] P J Seaton R J Kieber J DWilley G B Avery and J L DixonldquoSeasonal and temporal characterization of dissolved organicmatter in rainwater by proton nuclear magnetic resonancespectroscopyrdquo Atmospheric Environment vol 65 pp 52ndash602013

[22] J Amador P J Milne C A Moore and R G Zika ldquoExtractionof chromophoric humic substances from seawaterrdquo MarineChemistry vol 29 pp 1ndash17 1990

[23] C A Stedmon and R Bro ldquoCharacterizing dissolved organicmatter fluorescence with parallel factor analysis a tutorialrdquoLimnology and Oceanography Methods vol 6 no 11 pp 572ndash579 2008

[24] P S M Santos M Otero R M B O Duarte and A C DuarteldquoSpectroscopic characterization of dissolved organicmatter iso-lated from rainwaterrdquoChemosphere vol 74 no 8 pp 1053ndash10612009

[25] C ZhaoC-CWang J-Q Li C-YWang PWang andZ-J PeildquoDissolved organic matter in urban stormwater runoff at threetypical regions in Beijing chemical composition structuralcharacterization and source identificationrdquo RSC Advances vol5 no 90 pp 73490ndash73500 2015

[26] Z Wang and Q Wang ldquoThe spatial heterogeneity of soilphysical properties in forestsrdquoActa Ecologica Sinica vol 20 no6 pp 945ndash950 1999

[27] M L Fernandez-Romero J M Clark C D Collins L Parras-Alcantara and B Lozano-Garcıa ldquoEvaluation of optical tech-niques for characterising soil organic matter quality in agricul-tural soilsrdquo Soil and Tillage Research vol 155 pp 450ndash460 2016

[28] K Kalbitz J Schmerwitz D Schwesig and E MatznerldquoBiodegradation of soil-derived dissolved organic matter asrelated to its propertiesrdquo Geoderma vol 113 no 3-4 pp 273ndash291 2003

[29] R M B O Duarte and A C Duarte ldquoApplication of non-ionic solid sorbents (XADResins) for the isolation and fraction-ation of water-soluble organic compounds from atmosphericaerosolsrdquo Journal of Atmospheric Chemistry vol 51 no 1 pp79ndash93 2005

[30] N Senesi T M Miano M R Provenzano and G BrunettildquoSpectroscopic and compositional comparative characteriza-tion of IHSS reference and standard fulvic and humic acidsof various originrdquo Science of the Total Environment vol 81-82pp 143ndash156 1989

[31] X-S He B-D Xi Y-H Jiang et al ldquoStructural transformationstudy of water-extractable organic matter during the industrialcomposting of cattle manurerdquo Microchemical Journal vol 106pp 160ndash166 2013

[32] T Jamieson E Sager and C Gueguen ldquoCharacterizationof biochar-derived dissolved organic matter using UV-visibleabsorption and excitation-emission fluorescence spectrosco-piesrdquo Chemosphere vol 103 pp 197ndash204 2014

[33] J R Helms A Stubbins J D Ritchie E C Minor D J Kieberand K Mopper ldquoAbsorption spectral slopes and slope ratiosas indicators of molecular weight source and photobleachingof chromophoric dissolved organic matterrdquo Limnology andOceanography vol 53 no 3 pp 955ndash969 2008

[34] C A Stedmon S Markager and H Kaas ldquoOptical proper-ties and signatures of chromophoric dissolved organic matter(CDOM) in Danish coastal watersrdquo Estuarine Coastal and ShelfScience vol 51 no 2 pp 267ndash278 2000

[35] J B Fellman D V DrsquoAmore E Hood and R D BooneldquoFluorescence characteristics and biodegradability of dissolvedorganic matter in forest and wetland soils from coastal temper-atewatersheds in southeastAlaskardquoBiogeochemistry vol 88 no2 pp 169ndash184 2008

[36] J Sanderman J A Baldock and R Amundson ldquoDissolvedorganic carbon chemistry and dynamics in contrasting forestand grassland soilsrdquo Biogeochemistry vol 89 no 2 pp 181ndash1982008

[37] K Fujii M Uemura C Hayakawa et al ldquoFluxes of dissolvedorganic carbon in two tropical forest ecosystems of East Kali-mantan Indonesiardquo Geoderma vol 152 no 1-2 pp 127ndash1362009

[38] A Huguet L Vacher S Relexans S Saubusse J M Froidefondand E Parlanti ldquoProperties of fluorescent dissolved organicmatter in the Gironde Estuaryrdquo Organic Geochemistry vol 40no 6 pp 706ndash719 2009

[39] A Huguet L Vacher S Saubusse et al ldquoNew insights intothe size distribution of fluorescent dissolved organic matter inestuarine watersrdquo Organic Geochemistry vol 41 no 6 pp 595ndash610 2010

[40] P R Salve H Lohkare T Gobre et al ldquoCharacterization ofchromophoric dissolved organic matter (CDOM) in rainwaterusing fluorescence spectrophotometryrdquoBulletin of Environmen-tal Contamination and Toxicology vol 88 no 2 pp 215ndash2182012

[41] D M McKnight E W Boyer P K Westerhoff P T DoranT Kulbe and D T Andersen ldquoSpectrofluorometric characteri-zation of dissolved organic matter for indication of precursororganic material and aromaticityrdquo Limnology and Oceanogra-phy vol 46 no 1 pp 38ndash48 2001

[42] R Jaffe J N Boyer X Lu et al ldquoSource characterization ofdissolved organic matter in a subtropical mangrove-dominatedestuary by fluorescence analysisrdquoMarine Chemistry vol 84 no3-4 pp 195ndash210 2004

[43] T Ohno ldquoFluorescence inner-filtering correction for deter-mining the humification index of dissolved organic matterrdquoEnvironmental Science amp Technology vol 36 no 4 pp 742ndash7462002

10 Journal of Analytical Methods in Chemistry

[44] L A Cardoza A K Korir W H Otto C J Wurrey and C KLarive ldquoApplications of NMR spectroscopy in environmentalsciencerdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 45 no 3-4 pp 209ndash238 2004

[45] C M Preston ldquoApplications of NMR to soil organic matteranalysis history and prospectsrdquo Soil Science vol 161 no 3 pp144ndash166 1996

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 6: Research Article Spectroscopic Characteristics of ...downloads.hindawi.com/journals/jamc/2016/1480857.pdf · Microbial biomass carbon (MBC) analysis was determined by the chloroform

6 Journal of Analytical Methods in Chemistry

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

Y-1

0000

2500

5000

7500

1000

1250

1500

1750

2000

2250

200

250

300

350

400

450

500

550Em

issio

n w

avele

ngth

(nm

)

T

A

(a)

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

Y-4

200

250

300

350

400

450

500

550

Emiss

ion

wav

eleng

th (n

m)

0000

6000

1200

1800

2400

3000

3600

4200

4800

5400

T

A

(b)

200

250

300

350

400

450

500

550

Emiss

ion

wav

eleng

th (n

m)

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

0000

8000

1600

2400

3200

4000

4800

5600

6400

7200Y-10

T

A

(c)

200

250

300

350

400

450

500

550

Emiss

ion

wav

eleng

th (n

m)

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

0000

6500

1300

1950

2600

3250

3900

4550

5200

5850

6500Y-15

T

A

(d)

200

250

300

350

400

450

500

550

Emiss

ion

wav

eleng

th (n

m)

200 250 300 350 400 450 500 550

Excitation wavelength (nm)

0000

9000

1800

2700

3600

4500

5400

6300

7200

8100Y-20

T

A

(e)

Figure 3 EEM fluorescence contour profiles of the five sitesrsquo DOM

information on aromatic aliphatic and carboxylic groups[27 44 45] Much different from UV-Visible spectroscopyand EEM 1H NMR can give us the content and structuralinformation via the corresponding integrated areas and thechemical shifts (120575H) [18 19] As illustrated in Figure 4 the1H NMR results of the five sites exhibit some distinct peaksoverlaying bands implying the existence of complicatedmixtures in theDOMDespite the large variety of overlapping

resonances each 1H NMR spectrum was analyzed based onthe chemical shift assignments following the methoddescribed in the previously reported literatures for soilDOM [27] The integrated regions in the 1H NMR spectrawere listed as follows 120575H = 05ndash29 ppm (aliphatic protonsH-C) 120575H = 30ndash42 ppm (carbohydrates H-C-C=) and120575H = 60ndash80 ppm (aromatic protons) [27] The spectra offive sites were depicted in Figure 5 The 1H NMR results of

Journal of Analytical Methods in Chemistry 7

0123456789

(ppm)

Y-1

0123456789

(ppm)

Y-4

0123456789

(ppm)

Y-10

0123456789

(ppm)

Y-15

0123456789

(ppm)

Y-20

Figure 4 1H NMR spectra of DOM in the extracted samples of the five sampling sites

the five sites exhibited similar patterns as to functional groupcomposition suggesting the presence of more aliphaticand carbohydrates structures and less quantity of aromaticorganic matters (Table 6)

The content of saturated aliphatic substances in site Y-1(42) was lower than other sites (681 645 367 and340 forY-4 Y-10 Y-15 andY-20 resp) while the content of

carbohydrates (922) was higher than other sites (335335 598 and 642 for Y-4 Y-10 Y-15 and Y-20 resp)The content of aromatic structures in the five sites was 3647 2 35 and 18 for Y-1 Y-4 Y-10 Y-15 and Y-20respectively The results implied that the saturated aliphaticchains and carbohydrates were the main structures inafforestation forest land

8 Journal of Analytical Methods in Chemistry

Table 6 Results of the 1H NMR analyses

Samplesites

aliphatics(05ndash300 ppm)

carbohydrates(300ndash42 ppm)

aromatics(600ndash800 ppm)

Y-1 42 922 36Y-4 618 335 47Y-10 645 335 2Y-15 367 598 35Y-20 34 642 18

H-C H-C-C= H-Ar0

20

40

60

80

100

Perc

enta

ge (

)

Y-1Y-4

Y-15Y-20

Y-10

Figure 5The relative abundance of each type of protons estimatedas the partial integrals of the spectra reported in Figure 4

4 Conclusions

With this study a preliminary soil quality evaluation werecarried out based on soil texture and some chemical indi-cators like TOC TN TP K+ MBC and DOC Particularlythe DOM in the soil samples with different afforestation timewas further characterized via DOC UV-Visible spectroscopyEEM fluorescence spectroscopy and 1H NMR spectroscopyThe results of EEM fluorescence spectroscopy demonstratedthat UV humic-like substances were the major fluorophorescomponents in the DOM of the soil samples The DOM inthe soil samples wasmainly composed of aliphatic chains andaromatic components with carbonyl carboxyl and hydroxylgroups DOM in soils plays a crucial role in soil physicalchemical and biological processes but little information isavailable on the formation and biodegradability of plant-derived DOM in afforestation forest soil With the develop-ment of afforestation forest in Beijing it is necessary to fur-ther investigate the DOMdistribution and the correspondinginfluence on soil quality plants growth and ecosystem

Competing Interests

The authors declare that there are no competing interestsregarding the publication of this paper

Acknowledgments

This study was supported by the Fund of 12th Five-Year National Science and Technology Support Program(2013BAJ02B0404)

References

[1] S Cao ldquoWhy large-scale afforestation efforts in China havefailed to solve the desertification problemrdquo EnvironmentalScience and Technology vol 42 no 6 pp 1826ndash1831 2008

[2] Y Qiao J Wang and J Li ldquoThe summary and reflection ofBeijingrsquos plain reforestation taking Qingyundian of Daxingdistrict as an examplerdquo Forestry Economics vol 4 article 0052014

[3] K Kaiser G Guggenberger and W Zech ldquoSorption of DOMand DOM fractions to forest soilsrdquo Geoderma vol 74 no 3-4pp 281ndash303 1996

[4] R G Qualls and B L Haines ldquoBiodegradability of dissolvedorganic matter in forest throughfall soil solution and streamwaterrdquo Soil Science Society of America Journal vol 56 no 2 pp578ndash586 1992

[5] R Bi Q Lu T Yuan S Zhou Y Yuan and Y Cai ldquoElectro-chemical and spectroscopic characteristics of dissolved organicmatter in a forest soil profilerdquo Journal of Environmental Sciencesvol 25 no 10 pp 2093ndash2101 2013

[6] X-J Guo N-M Zhu L Chen D-H Yuan and L-S HeldquoCharacterizing the fluorescent properties and copper complex-ation of dissolved organic matter in saline-alkali soils usingfluorescence excitation-emission matrix and parallel factoranalysisrdquo Journal of Soils and Sediments vol 15 no 7 pp 1473ndash1482 2015

[7] B Marschner and K Kalbitz ldquoControls of bioavailability andbiodegradability of dissolved organic matter in soilsrdquo Geo-derma vol 113 no 3-4 pp 211ndash235 2003

[8] K Kalbitz S Solinger J-H Park B Michalzik and E MatznerldquoControls on the dynamics dissolved organic matter in soils areviewrdquo Soil Science vol 165 no 4 pp 277ndash304 2000

[9] D L Jones P Simfukwe P W Hill R T E Mills and B AEmmett ldquoEvaluation of dissolved organic carbon as a soil qual-ity indicator in national monitoring schemesrdquo PLoS ONE vol9 no 3 Article ID e90882 2014

[10] T Yuan Y Yuan S Zhou F Li Z Liu and L Zhuang ldquoA rapidand simple electrochemical method for evaluating the electrontransfer capacities of dissolved organic matterrdquo Journal of Soilsand Sediments vol 11 no 3 pp 467ndash473 2011

[11] T Ohno I J Fernandez S Hiradate and J F Sherman ldquoEffectsof soil acidification and forest type on water soluble soil organicmatter propertiesrdquoGeoderma vol 140 no 1-2 pp 176ndash187 2007

[12] G F Vance and M B David ldquoChemical characteristics andacidity of soluble organic substances from a northern hardwoodforest floor central Maine USArdquo Geochimica et CosmochimicaActa vol 55 no 12 pp 3611ndash3625 1991

[13] Q-Y Wang Y Wang Q-C Wang et al ldquoEffects of land usechanges on the spectroscopic characterization of hot-waterextractable organic matter along a chronosequence correla-tionswith soil enzyme activityrdquoEuropean Journal of Soil Biologyvol 58 pp 8ndash12 2013

[14] M A Rab ldquoSoil physical and hydrological properties followinglogging and slash burning in the Eucalyptus regnans forest ofsoutheastern Australiardquo Forest Ecology and Management vol84 no 1ndash3 pp 159ndash176 1996

Journal of Analytical Methods in Chemistry 9

[15] M Han G Ji and J Ni ldquoWashing of field weathered crude oilcontaminated soil with an environmentally compatible surfac-tant alkyl polyglucosiderdquo Chemosphere vol 76 no 5 pp 579ndash586 2009

[16] X Bi L Ren M Gong Y He L Wang and Z Ma ldquoTransfer ofcadmium and lead from soil to mangoes in an uncontaminatedarea Hainan Island ChinardquoGeoderma vol 155 no 1-2 pp 115ndash120 2010

[17] J Akagi A Zsolnay and F Bastida ldquoQuantity and spectroscopicproperties of soil dissolved organic matter (DOM) as a func-tion of soil sample treatments air-drying and pre-incubationrdquoChemosphere vol 69 no 7 pp 1040ndash1046 2007

[18] N Roig J Sierra E Martı M Nadal M Schuhmacher and J LDomingo ldquoLong-term amendment of Spanish soils with sewagesludge effects on soil functioningrdquo Agriculture Ecosystems andEnvironment vol 158 pp 41ndash48 2012

[19] J L Weishaar G R Aiken B A Bergamaschi M S FramR Fujii and K Mopper ldquoEvaluation of specific ultravioletabsorbance as an indicator of the chemical composition andreactivity of dissolved organic carbonrdquo Environmental Scienceand Technology vol 37 no 20 pp 4702ndash4708 2003

[20] S A Green and N V Blough ldquoOptical absorption and fluores-cence properties of chromophoric dissolved organic matter innatural watersrdquo Limnology and Oceanography vol 39 no 8 pp1903ndash1916 1994

[21] P J Seaton R J Kieber J DWilley G B Avery and J L DixonldquoSeasonal and temporal characterization of dissolved organicmatter in rainwater by proton nuclear magnetic resonancespectroscopyrdquo Atmospheric Environment vol 65 pp 52ndash602013

[22] J Amador P J Milne C A Moore and R G Zika ldquoExtractionof chromophoric humic substances from seawaterrdquo MarineChemistry vol 29 pp 1ndash17 1990

[23] C A Stedmon and R Bro ldquoCharacterizing dissolved organicmatter fluorescence with parallel factor analysis a tutorialrdquoLimnology and Oceanography Methods vol 6 no 11 pp 572ndash579 2008

[24] P S M Santos M Otero R M B O Duarte and A C DuarteldquoSpectroscopic characterization of dissolved organicmatter iso-lated from rainwaterrdquoChemosphere vol 74 no 8 pp 1053ndash10612009

[25] C ZhaoC-CWang J-Q Li C-YWang PWang andZ-J PeildquoDissolved organic matter in urban stormwater runoff at threetypical regions in Beijing chemical composition structuralcharacterization and source identificationrdquo RSC Advances vol5 no 90 pp 73490ndash73500 2015

[26] Z Wang and Q Wang ldquoThe spatial heterogeneity of soilphysical properties in forestsrdquoActa Ecologica Sinica vol 20 no6 pp 945ndash950 1999

[27] M L Fernandez-Romero J M Clark C D Collins L Parras-Alcantara and B Lozano-Garcıa ldquoEvaluation of optical tech-niques for characterising soil organic matter quality in agricul-tural soilsrdquo Soil and Tillage Research vol 155 pp 450ndash460 2016

[28] K Kalbitz J Schmerwitz D Schwesig and E MatznerldquoBiodegradation of soil-derived dissolved organic matter asrelated to its propertiesrdquo Geoderma vol 113 no 3-4 pp 273ndash291 2003

[29] R M B O Duarte and A C Duarte ldquoApplication of non-ionic solid sorbents (XADResins) for the isolation and fraction-ation of water-soluble organic compounds from atmosphericaerosolsrdquo Journal of Atmospheric Chemistry vol 51 no 1 pp79ndash93 2005

[30] N Senesi T M Miano M R Provenzano and G BrunettildquoSpectroscopic and compositional comparative characteriza-tion of IHSS reference and standard fulvic and humic acidsof various originrdquo Science of the Total Environment vol 81-82pp 143ndash156 1989

[31] X-S He B-D Xi Y-H Jiang et al ldquoStructural transformationstudy of water-extractable organic matter during the industrialcomposting of cattle manurerdquo Microchemical Journal vol 106pp 160ndash166 2013

[32] T Jamieson E Sager and C Gueguen ldquoCharacterizationof biochar-derived dissolved organic matter using UV-visibleabsorption and excitation-emission fluorescence spectrosco-piesrdquo Chemosphere vol 103 pp 197ndash204 2014

[33] J R Helms A Stubbins J D Ritchie E C Minor D J Kieberand K Mopper ldquoAbsorption spectral slopes and slope ratiosas indicators of molecular weight source and photobleachingof chromophoric dissolved organic matterrdquo Limnology andOceanography vol 53 no 3 pp 955ndash969 2008

[34] C A Stedmon S Markager and H Kaas ldquoOptical proper-ties and signatures of chromophoric dissolved organic matter(CDOM) in Danish coastal watersrdquo Estuarine Coastal and ShelfScience vol 51 no 2 pp 267ndash278 2000

[35] J B Fellman D V DrsquoAmore E Hood and R D BooneldquoFluorescence characteristics and biodegradability of dissolvedorganic matter in forest and wetland soils from coastal temper-atewatersheds in southeastAlaskardquoBiogeochemistry vol 88 no2 pp 169ndash184 2008

[36] J Sanderman J A Baldock and R Amundson ldquoDissolvedorganic carbon chemistry and dynamics in contrasting forestand grassland soilsrdquo Biogeochemistry vol 89 no 2 pp 181ndash1982008

[37] K Fujii M Uemura C Hayakawa et al ldquoFluxes of dissolvedorganic carbon in two tropical forest ecosystems of East Kali-mantan Indonesiardquo Geoderma vol 152 no 1-2 pp 127ndash1362009

[38] A Huguet L Vacher S Relexans S Saubusse J M Froidefondand E Parlanti ldquoProperties of fluorescent dissolved organicmatter in the Gironde Estuaryrdquo Organic Geochemistry vol 40no 6 pp 706ndash719 2009

[39] A Huguet L Vacher S Saubusse et al ldquoNew insights intothe size distribution of fluorescent dissolved organic matter inestuarine watersrdquo Organic Geochemistry vol 41 no 6 pp 595ndash610 2010

[40] P R Salve H Lohkare T Gobre et al ldquoCharacterization ofchromophoric dissolved organic matter (CDOM) in rainwaterusing fluorescence spectrophotometryrdquoBulletin of Environmen-tal Contamination and Toxicology vol 88 no 2 pp 215ndash2182012

[41] D M McKnight E W Boyer P K Westerhoff P T DoranT Kulbe and D T Andersen ldquoSpectrofluorometric characteri-zation of dissolved organic matter for indication of precursororganic material and aromaticityrdquo Limnology and Oceanogra-phy vol 46 no 1 pp 38ndash48 2001

[42] R Jaffe J N Boyer X Lu et al ldquoSource characterization ofdissolved organic matter in a subtropical mangrove-dominatedestuary by fluorescence analysisrdquoMarine Chemistry vol 84 no3-4 pp 195ndash210 2004

[43] T Ohno ldquoFluorescence inner-filtering correction for deter-mining the humification index of dissolved organic matterrdquoEnvironmental Science amp Technology vol 36 no 4 pp 742ndash7462002

10 Journal of Analytical Methods in Chemistry

[44] L A Cardoza A K Korir W H Otto C J Wurrey and C KLarive ldquoApplications of NMR spectroscopy in environmentalsciencerdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 45 no 3-4 pp 209ndash238 2004

[45] C M Preston ldquoApplications of NMR to soil organic matteranalysis history and prospectsrdquo Soil Science vol 161 no 3 pp144ndash166 1996

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 7: Research Article Spectroscopic Characteristics of ...downloads.hindawi.com/journals/jamc/2016/1480857.pdf · Microbial biomass carbon (MBC) analysis was determined by the chloroform

Journal of Analytical Methods in Chemistry 7

0123456789

(ppm)

Y-1

0123456789

(ppm)

Y-4

0123456789

(ppm)

Y-10

0123456789

(ppm)

Y-15

0123456789

(ppm)

Y-20

Figure 4 1H NMR spectra of DOM in the extracted samples of the five sampling sites

the five sites exhibited similar patterns as to functional groupcomposition suggesting the presence of more aliphaticand carbohydrates structures and less quantity of aromaticorganic matters (Table 6)

The content of saturated aliphatic substances in site Y-1(42) was lower than other sites (681 645 367 and340 forY-4 Y-10 Y-15 andY-20 resp) while the content of

carbohydrates (922) was higher than other sites (335335 598 and 642 for Y-4 Y-10 Y-15 and Y-20 resp)The content of aromatic structures in the five sites was 3647 2 35 and 18 for Y-1 Y-4 Y-10 Y-15 and Y-20respectively The results implied that the saturated aliphaticchains and carbohydrates were the main structures inafforestation forest land

8 Journal of Analytical Methods in Chemistry

Table 6 Results of the 1H NMR analyses

Samplesites

aliphatics(05ndash300 ppm)

carbohydrates(300ndash42 ppm)

aromatics(600ndash800 ppm)

Y-1 42 922 36Y-4 618 335 47Y-10 645 335 2Y-15 367 598 35Y-20 34 642 18

H-C H-C-C= H-Ar0

20

40

60

80

100

Perc

enta

ge (

)

Y-1Y-4

Y-15Y-20

Y-10

Figure 5The relative abundance of each type of protons estimatedas the partial integrals of the spectra reported in Figure 4

4 Conclusions

With this study a preliminary soil quality evaluation werecarried out based on soil texture and some chemical indi-cators like TOC TN TP K+ MBC and DOC Particularlythe DOM in the soil samples with different afforestation timewas further characterized via DOC UV-Visible spectroscopyEEM fluorescence spectroscopy and 1H NMR spectroscopyThe results of EEM fluorescence spectroscopy demonstratedthat UV humic-like substances were the major fluorophorescomponents in the DOM of the soil samples The DOM inthe soil samples wasmainly composed of aliphatic chains andaromatic components with carbonyl carboxyl and hydroxylgroups DOM in soils plays a crucial role in soil physicalchemical and biological processes but little information isavailable on the formation and biodegradability of plant-derived DOM in afforestation forest soil With the develop-ment of afforestation forest in Beijing it is necessary to fur-ther investigate the DOMdistribution and the correspondinginfluence on soil quality plants growth and ecosystem

Competing Interests

The authors declare that there are no competing interestsregarding the publication of this paper

Acknowledgments

This study was supported by the Fund of 12th Five-Year National Science and Technology Support Program(2013BAJ02B0404)

References

[1] S Cao ldquoWhy large-scale afforestation efforts in China havefailed to solve the desertification problemrdquo EnvironmentalScience and Technology vol 42 no 6 pp 1826ndash1831 2008

[2] Y Qiao J Wang and J Li ldquoThe summary and reflection ofBeijingrsquos plain reforestation taking Qingyundian of Daxingdistrict as an examplerdquo Forestry Economics vol 4 article 0052014

[3] K Kaiser G Guggenberger and W Zech ldquoSorption of DOMand DOM fractions to forest soilsrdquo Geoderma vol 74 no 3-4pp 281ndash303 1996

[4] R G Qualls and B L Haines ldquoBiodegradability of dissolvedorganic matter in forest throughfall soil solution and streamwaterrdquo Soil Science Society of America Journal vol 56 no 2 pp578ndash586 1992

[5] R Bi Q Lu T Yuan S Zhou Y Yuan and Y Cai ldquoElectro-chemical and spectroscopic characteristics of dissolved organicmatter in a forest soil profilerdquo Journal of Environmental Sciencesvol 25 no 10 pp 2093ndash2101 2013

[6] X-J Guo N-M Zhu L Chen D-H Yuan and L-S HeldquoCharacterizing the fluorescent properties and copper complex-ation of dissolved organic matter in saline-alkali soils usingfluorescence excitation-emission matrix and parallel factoranalysisrdquo Journal of Soils and Sediments vol 15 no 7 pp 1473ndash1482 2015

[7] B Marschner and K Kalbitz ldquoControls of bioavailability andbiodegradability of dissolved organic matter in soilsrdquo Geo-derma vol 113 no 3-4 pp 211ndash235 2003

[8] K Kalbitz S Solinger J-H Park B Michalzik and E MatznerldquoControls on the dynamics dissolved organic matter in soils areviewrdquo Soil Science vol 165 no 4 pp 277ndash304 2000

[9] D L Jones P Simfukwe P W Hill R T E Mills and B AEmmett ldquoEvaluation of dissolved organic carbon as a soil qual-ity indicator in national monitoring schemesrdquo PLoS ONE vol9 no 3 Article ID e90882 2014

[10] T Yuan Y Yuan S Zhou F Li Z Liu and L Zhuang ldquoA rapidand simple electrochemical method for evaluating the electrontransfer capacities of dissolved organic matterrdquo Journal of Soilsand Sediments vol 11 no 3 pp 467ndash473 2011

[11] T Ohno I J Fernandez S Hiradate and J F Sherman ldquoEffectsof soil acidification and forest type on water soluble soil organicmatter propertiesrdquoGeoderma vol 140 no 1-2 pp 176ndash187 2007

[12] G F Vance and M B David ldquoChemical characteristics andacidity of soluble organic substances from a northern hardwoodforest floor central Maine USArdquo Geochimica et CosmochimicaActa vol 55 no 12 pp 3611ndash3625 1991

[13] Q-Y Wang Y Wang Q-C Wang et al ldquoEffects of land usechanges on the spectroscopic characterization of hot-waterextractable organic matter along a chronosequence correla-tionswith soil enzyme activityrdquoEuropean Journal of Soil Biologyvol 58 pp 8ndash12 2013

[14] M A Rab ldquoSoil physical and hydrological properties followinglogging and slash burning in the Eucalyptus regnans forest ofsoutheastern Australiardquo Forest Ecology and Management vol84 no 1ndash3 pp 159ndash176 1996

Journal of Analytical Methods in Chemistry 9

[15] M Han G Ji and J Ni ldquoWashing of field weathered crude oilcontaminated soil with an environmentally compatible surfac-tant alkyl polyglucosiderdquo Chemosphere vol 76 no 5 pp 579ndash586 2009

[16] X Bi L Ren M Gong Y He L Wang and Z Ma ldquoTransfer ofcadmium and lead from soil to mangoes in an uncontaminatedarea Hainan Island ChinardquoGeoderma vol 155 no 1-2 pp 115ndash120 2010

[17] J Akagi A Zsolnay and F Bastida ldquoQuantity and spectroscopicproperties of soil dissolved organic matter (DOM) as a func-tion of soil sample treatments air-drying and pre-incubationrdquoChemosphere vol 69 no 7 pp 1040ndash1046 2007

[18] N Roig J Sierra E Martı M Nadal M Schuhmacher and J LDomingo ldquoLong-term amendment of Spanish soils with sewagesludge effects on soil functioningrdquo Agriculture Ecosystems andEnvironment vol 158 pp 41ndash48 2012

[19] J L Weishaar G R Aiken B A Bergamaschi M S FramR Fujii and K Mopper ldquoEvaluation of specific ultravioletabsorbance as an indicator of the chemical composition andreactivity of dissolved organic carbonrdquo Environmental Scienceand Technology vol 37 no 20 pp 4702ndash4708 2003

[20] S A Green and N V Blough ldquoOptical absorption and fluores-cence properties of chromophoric dissolved organic matter innatural watersrdquo Limnology and Oceanography vol 39 no 8 pp1903ndash1916 1994

[21] P J Seaton R J Kieber J DWilley G B Avery and J L DixonldquoSeasonal and temporal characterization of dissolved organicmatter in rainwater by proton nuclear magnetic resonancespectroscopyrdquo Atmospheric Environment vol 65 pp 52ndash602013

[22] J Amador P J Milne C A Moore and R G Zika ldquoExtractionof chromophoric humic substances from seawaterrdquo MarineChemistry vol 29 pp 1ndash17 1990

[23] C A Stedmon and R Bro ldquoCharacterizing dissolved organicmatter fluorescence with parallel factor analysis a tutorialrdquoLimnology and Oceanography Methods vol 6 no 11 pp 572ndash579 2008

[24] P S M Santos M Otero R M B O Duarte and A C DuarteldquoSpectroscopic characterization of dissolved organicmatter iso-lated from rainwaterrdquoChemosphere vol 74 no 8 pp 1053ndash10612009

[25] C ZhaoC-CWang J-Q Li C-YWang PWang andZ-J PeildquoDissolved organic matter in urban stormwater runoff at threetypical regions in Beijing chemical composition structuralcharacterization and source identificationrdquo RSC Advances vol5 no 90 pp 73490ndash73500 2015

[26] Z Wang and Q Wang ldquoThe spatial heterogeneity of soilphysical properties in forestsrdquoActa Ecologica Sinica vol 20 no6 pp 945ndash950 1999

[27] M L Fernandez-Romero J M Clark C D Collins L Parras-Alcantara and B Lozano-Garcıa ldquoEvaluation of optical tech-niques for characterising soil organic matter quality in agricul-tural soilsrdquo Soil and Tillage Research vol 155 pp 450ndash460 2016

[28] K Kalbitz J Schmerwitz D Schwesig and E MatznerldquoBiodegradation of soil-derived dissolved organic matter asrelated to its propertiesrdquo Geoderma vol 113 no 3-4 pp 273ndash291 2003

[29] R M B O Duarte and A C Duarte ldquoApplication of non-ionic solid sorbents (XADResins) for the isolation and fraction-ation of water-soluble organic compounds from atmosphericaerosolsrdquo Journal of Atmospheric Chemistry vol 51 no 1 pp79ndash93 2005

[30] N Senesi T M Miano M R Provenzano and G BrunettildquoSpectroscopic and compositional comparative characteriza-tion of IHSS reference and standard fulvic and humic acidsof various originrdquo Science of the Total Environment vol 81-82pp 143ndash156 1989

[31] X-S He B-D Xi Y-H Jiang et al ldquoStructural transformationstudy of water-extractable organic matter during the industrialcomposting of cattle manurerdquo Microchemical Journal vol 106pp 160ndash166 2013

[32] T Jamieson E Sager and C Gueguen ldquoCharacterizationof biochar-derived dissolved organic matter using UV-visibleabsorption and excitation-emission fluorescence spectrosco-piesrdquo Chemosphere vol 103 pp 197ndash204 2014

[33] J R Helms A Stubbins J D Ritchie E C Minor D J Kieberand K Mopper ldquoAbsorption spectral slopes and slope ratiosas indicators of molecular weight source and photobleachingof chromophoric dissolved organic matterrdquo Limnology andOceanography vol 53 no 3 pp 955ndash969 2008

[34] C A Stedmon S Markager and H Kaas ldquoOptical proper-ties and signatures of chromophoric dissolved organic matter(CDOM) in Danish coastal watersrdquo Estuarine Coastal and ShelfScience vol 51 no 2 pp 267ndash278 2000

[35] J B Fellman D V DrsquoAmore E Hood and R D BooneldquoFluorescence characteristics and biodegradability of dissolvedorganic matter in forest and wetland soils from coastal temper-atewatersheds in southeastAlaskardquoBiogeochemistry vol 88 no2 pp 169ndash184 2008

[36] J Sanderman J A Baldock and R Amundson ldquoDissolvedorganic carbon chemistry and dynamics in contrasting forestand grassland soilsrdquo Biogeochemistry vol 89 no 2 pp 181ndash1982008

[37] K Fujii M Uemura C Hayakawa et al ldquoFluxes of dissolvedorganic carbon in two tropical forest ecosystems of East Kali-mantan Indonesiardquo Geoderma vol 152 no 1-2 pp 127ndash1362009

[38] A Huguet L Vacher S Relexans S Saubusse J M Froidefondand E Parlanti ldquoProperties of fluorescent dissolved organicmatter in the Gironde Estuaryrdquo Organic Geochemistry vol 40no 6 pp 706ndash719 2009

[39] A Huguet L Vacher S Saubusse et al ldquoNew insights intothe size distribution of fluorescent dissolved organic matter inestuarine watersrdquo Organic Geochemistry vol 41 no 6 pp 595ndash610 2010

[40] P R Salve H Lohkare T Gobre et al ldquoCharacterization ofchromophoric dissolved organic matter (CDOM) in rainwaterusing fluorescence spectrophotometryrdquoBulletin of Environmen-tal Contamination and Toxicology vol 88 no 2 pp 215ndash2182012

[41] D M McKnight E W Boyer P K Westerhoff P T DoranT Kulbe and D T Andersen ldquoSpectrofluorometric characteri-zation of dissolved organic matter for indication of precursororganic material and aromaticityrdquo Limnology and Oceanogra-phy vol 46 no 1 pp 38ndash48 2001

[42] R Jaffe J N Boyer X Lu et al ldquoSource characterization ofdissolved organic matter in a subtropical mangrove-dominatedestuary by fluorescence analysisrdquoMarine Chemistry vol 84 no3-4 pp 195ndash210 2004

[43] T Ohno ldquoFluorescence inner-filtering correction for deter-mining the humification index of dissolved organic matterrdquoEnvironmental Science amp Technology vol 36 no 4 pp 742ndash7462002

10 Journal of Analytical Methods in Chemistry

[44] L A Cardoza A K Korir W H Otto C J Wurrey and C KLarive ldquoApplications of NMR spectroscopy in environmentalsciencerdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 45 no 3-4 pp 209ndash238 2004

[45] C M Preston ldquoApplications of NMR to soil organic matteranalysis history and prospectsrdquo Soil Science vol 161 no 3 pp144ndash166 1996

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 8: Research Article Spectroscopic Characteristics of ...downloads.hindawi.com/journals/jamc/2016/1480857.pdf · Microbial biomass carbon (MBC) analysis was determined by the chloroform

8 Journal of Analytical Methods in Chemistry

Table 6 Results of the 1H NMR analyses

Samplesites

aliphatics(05ndash300 ppm)

carbohydrates(300ndash42 ppm)

aromatics(600ndash800 ppm)

Y-1 42 922 36Y-4 618 335 47Y-10 645 335 2Y-15 367 598 35Y-20 34 642 18

H-C H-C-C= H-Ar0

20

40

60

80

100

Perc

enta

ge (

)

Y-1Y-4

Y-15Y-20

Y-10

Figure 5The relative abundance of each type of protons estimatedas the partial integrals of the spectra reported in Figure 4

4 Conclusions

With this study a preliminary soil quality evaluation werecarried out based on soil texture and some chemical indi-cators like TOC TN TP K+ MBC and DOC Particularlythe DOM in the soil samples with different afforestation timewas further characterized via DOC UV-Visible spectroscopyEEM fluorescence spectroscopy and 1H NMR spectroscopyThe results of EEM fluorescence spectroscopy demonstratedthat UV humic-like substances were the major fluorophorescomponents in the DOM of the soil samples The DOM inthe soil samples wasmainly composed of aliphatic chains andaromatic components with carbonyl carboxyl and hydroxylgroups DOM in soils plays a crucial role in soil physicalchemical and biological processes but little information isavailable on the formation and biodegradability of plant-derived DOM in afforestation forest soil With the develop-ment of afforestation forest in Beijing it is necessary to fur-ther investigate the DOMdistribution and the correspondinginfluence on soil quality plants growth and ecosystem

Competing Interests

The authors declare that there are no competing interestsregarding the publication of this paper

Acknowledgments

This study was supported by the Fund of 12th Five-Year National Science and Technology Support Program(2013BAJ02B0404)

References

[1] S Cao ldquoWhy large-scale afforestation efforts in China havefailed to solve the desertification problemrdquo EnvironmentalScience and Technology vol 42 no 6 pp 1826ndash1831 2008

[2] Y Qiao J Wang and J Li ldquoThe summary and reflection ofBeijingrsquos plain reforestation taking Qingyundian of Daxingdistrict as an examplerdquo Forestry Economics vol 4 article 0052014

[3] K Kaiser G Guggenberger and W Zech ldquoSorption of DOMand DOM fractions to forest soilsrdquo Geoderma vol 74 no 3-4pp 281ndash303 1996

[4] R G Qualls and B L Haines ldquoBiodegradability of dissolvedorganic matter in forest throughfall soil solution and streamwaterrdquo Soil Science Society of America Journal vol 56 no 2 pp578ndash586 1992

[5] R Bi Q Lu T Yuan S Zhou Y Yuan and Y Cai ldquoElectro-chemical and spectroscopic characteristics of dissolved organicmatter in a forest soil profilerdquo Journal of Environmental Sciencesvol 25 no 10 pp 2093ndash2101 2013

[6] X-J Guo N-M Zhu L Chen D-H Yuan and L-S HeldquoCharacterizing the fluorescent properties and copper complex-ation of dissolved organic matter in saline-alkali soils usingfluorescence excitation-emission matrix and parallel factoranalysisrdquo Journal of Soils and Sediments vol 15 no 7 pp 1473ndash1482 2015

[7] B Marschner and K Kalbitz ldquoControls of bioavailability andbiodegradability of dissolved organic matter in soilsrdquo Geo-derma vol 113 no 3-4 pp 211ndash235 2003

[8] K Kalbitz S Solinger J-H Park B Michalzik and E MatznerldquoControls on the dynamics dissolved organic matter in soils areviewrdquo Soil Science vol 165 no 4 pp 277ndash304 2000

[9] D L Jones P Simfukwe P W Hill R T E Mills and B AEmmett ldquoEvaluation of dissolved organic carbon as a soil qual-ity indicator in national monitoring schemesrdquo PLoS ONE vol9 no 3 Article ID e90882 2014

[10] T Yuan Y Yuan S Zhou F Li Z Liu and L Zhuang ldquoA rapidand simple electrochemical method for evaluating the electrontransfer capacities of dissolved organic matterrdquo Journal of Soilsand Sediments vol 11 no 3 pp 467ndash473 2011

[11] T Ohno I J Fernandez S Hiradate and J F Sherman ldquoEffectsof soil acidification and forest type on water soluble soil organicmatter propertiesrdquoGeoderma vol 140 no 1-2 pp 176ndash187 2007

[12] G F Vance and M B David ldquoChemical characteristics andacidity of soluble organic substances from a northern hardwoodforest floor central Maine USArdquo Geochimica et CosmochimicaActa vol 55 no 12 pp 3611ndash3625 1991

[13] Q-Y Wang Y Wang Q-C Wang et al ldquoEffects of land usechanges on the spectroscopic characterization of hot-waterextractable organic matter along a chronosequence correla-tionswith soil enzyme activityrdquoEuropean Journal of Soil Biologyvol 58 pp 8ndash12 2013

[14] M A Rab ldquoSoil physical and hydrological properties followinglogging and slash burning in the Eucalyptus regnans forest ofsoutheastern Australiardquo Forest Ecology and Management vol84 no 1ndash3 pp 159ndash176 1996

Journal of Analytical Methods in Chemistry 9

[15] M Han G Ji and J Ni ldquoWashing of field weathered crude oilcontaminated soil with an environmentally compatible surfac-tant alkyl polyglucosiderdquo Chemosphere vol 76 no 5 pp 579ndash586 2009

[16] X Bi L Ren M Gong Y He L Wang and Z Ma ldquoTransfer ofcadmium and lead from soil to mangoes in an uncontaminatedarea Hainan Island ChinardquoGeoderma vol 155 no 1-2 pp 115ndash120 2010

[17] J Akagi A Zsolnay and F Bastida ldquoQuantity and spectroscopicproperties of soil dissolved organic matter (DOM) as a func-tion of soil sample treatments air-drying and pre-incubationrdquoChemosphere vol 69 no 7 pp 1040ndash1046 2007

[18] N Roig J Sierra E Martı M Nadal M Schuhmacher and J LDomingo ldquoLong-term amendment of Spanish soils with sewagesludge effects on soil functioningrdquo Agriculture Ecosystems andEnvironment vol 158 pp 41ndash48 2012

[19] J L Weishaar G R Aiken B A Bergamaschi M S FramR Fujii and K Mopper ldquoEvaluation of specific ultravioletabsorbance as an indicator of the chemical composition andreactivity of dissolved organic carbonrdquo Environmental Scienceand Technology vol 37 no 20 pp 4702ndash4708 2003

[20] S A Green and N V Blough ldquoOptical absorption and fluores-cence properties of chromophoric dissolved organic matter innatural watersrdquo Limnology and Oceanography vol 39 no 8 pp1903ndash1916 1994

[21] P J Seaton R J Kieber J DWilley G B Avery and J L DixonldquoSeasonal and temporal characterization of dissolved organicmatter in rainwater by proton nuclear magnetic resonancespectroscopyrdquo Atmospheric Environment vol 65 pp 52ndash602013

[22] J Amador P J Milne C A Moore and R G Zika ldquoExtractionof chromophoric humic substances from seawaterrdquo MarineChemistry vol 29 pp 1ndash17 1990

[23] C A Stedmon and R Bro ldquoCharacterizing dissolved organicmatter fluorescence with parallel factor analysis a tutorialrdquoLimnology and Oceanography Methods vol 6 no 11 pp 572ndash579 2008

[24] P S M Santos M Otero R M B O Duarte and A C DuarteldquoSpectroscopic characterization of dissolved organicmatter iso-lated from rainwaterrdquoChemosphere vol 74 no 8 pp 1053ndash10612009

[25] C ZhaoC-CWang J-Q Li C-YWang PWang andZ-J PeildquoDissolved organic matter in urban stormwater runoff at threetypical regions in Beijing chemical composition structuralcharacterization and source identificationrdquo RSC Advances vol5 no 90 pp 73490ndash73500 2015

[26] Z Wang and Q Wang ldquoThe spatial heterogeneity of soilphysical properties in forestsrdquoActa Ecologica Sinica vol 20 no6 pp 945ndash950 1999

[27] M L Fernandez-Romero J M Clark C D Collins L Parras-Alcantara and B Lozano-Garcıa ldquoEvaluation of optical tech-niques for characterising soil organic matter quality in agricul-tural soilsrdquo Soil and Tillage Research vol 155 pp 450ndash460 2016

[28] K Kalbitz J Schmerwitz D Schwesig and E MatznerldquoBiodegradation of soil-derived dissolved organic matter asrelated to its propertiesrdquo Geoderma vol 113 no 3-4 pp 273ndash291 2003

[29] R M B O Duarte and A C Duarte ldquoApplication of non-ionic solid sorbents (XADResins) for the isolation and fraction-ation of water-soluble organic compounds from atmosphericaerosolsrdquo Journal of Atmospheric Chemistry vol 51 no 1 pp79ndash93 2005

[30] N Senesi T M Miano M R Provenzano and G BrunettildquoSpectroscopic and compositional comparative characteriza-tion of IHSS reference and standard fulvic and humic acidsof various originrdquo Science of the Total Environment vol 81-82pp 143ndash156 1989

[31] X-S He B-D Xi Y-H Jiang et al ldquoStructural transformationstudy of water-extractable organic matter during the industrialcomposting of cattle manurerdquo Microchemical Journal vol 106pp 160ndash166 2013

[32] T Jamieson E Sager and C Gueguen ldquoCharacterizationof biochar-derived dissolved organic matter using UV-visibleabsorption and excitation-emission fluorescence spectrosco-piesrdquo Chemosphere vol 103 pp 197ndash204 2014

[33] J R Helms A Stubbins J D Ritchie E C Minor D J Kieberand K Mopper ldquoAbsorption spectral slopes and slope ratiosas indicators of molecular weight source and photobleachingof chromophoric dissolved organic matterrdquo Limnology andOceanography vol 53 no 3 pp 955ndash969 2008

[34] C A Stedmon S Markager and H Kaas ldquoOptical proper-ties and signatures of chromophoric dissolved organic matter(CDOM) in Danish coastal watersrdquo Estuarine Coastal and ShelfScience vol 51 no 2 pp 267ndash278 2000

[35] J B Fellman D V DrsquoAmore E Hood and R D BooneldquoFluorescence characteristics and biodegradability of dissolvedorganic matter in forest and wetland soils from coastal temper-atewatersheds in southeastAlaskardquoBiogeochemistry vol 88 no2 pp 169ndash184 2008

[36] J Sanderman J A Baldock and R Amundson ldquoDissolvedorganic carbon chemistry and dynamics in contrasting forestand grassland soilsrdquo Biogeochemistry vol 89 no 2 pp 181ndash1982008

[37] K Fujii M Uemura C Hayakawa et al ldquoFluxes of dissolvedorganic carbon in two tropical forest ecosystems of East Kali-mantan Indonesiardquo Geoderma vol 152 no 1-2 pp 127ndash1362009

[38] A Huguet L Vacher S Relexans S Saubusse J M Froidefondand E Parlanti ldquoProperties of fluorescent dissolved organicmatter in the Gironde Estuaryrdquo Organic Geochemistry vol 40no 6 pp 706ndash719 2009

[39] A Huguet L Vacher S Saubusse et al ldquoNew insights intothe size distribution of fluorescent dissolved organic matter inestuarine watersrdquo Organic Geochemistry vol 41 no 6 pp 595ndash610 2010

[40] P R Salve H Lohkare T Gobre et al ldquoCharacterization ofchromophoric dissolved organic matter (CDOM) in rainwaterusing fluorescence spectrophotometryrdquoBulletin of Environmen-tal Contamination and Toxicology vol 88 no 2 pp 215ndash2182012

[41] D M McKnight E W Boyer P K Westerhoff P T DoranT Kulbe and D T Andersen ldquoSpectrofluorometric characteri-zation of dissolved organic matter for indication of precursororganic material and aromaticityrdquo Limnology and Oceanogra-phy vol 46 no 1 pp 38ndash48 2001

[42] R Jaffe J N Boyer X Lu et al ldquoSource characterization ofdissolved organic matter in a subtropical mangrove-dominatedestuary by fluorescence analysisrdquoMarine Chemistry vol 84 no3-4 pp 195ndash210 2004

[43] T Ohno ldquoFluorescence inner-filtering correction for deter-mining the humification index of dissolved organic matterrdquoEnvironmental Science amp Technology vol 36 no 4 pp 742ndash7462002

10 Journal of Analytical Methods in Chemistry

[44] L A Cardoza A K Korir W H Otto C J Wurrey and C KLarive ldquoApplications of NMR spectroscopy in environmentalsciencerdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 45 no 3-4 pp 209ndash238 2004

[45] C M Preston ldquoApplications of NMR to soil organic matteranalysis history and prospectsrdquo Soil Science vol 161 no 3 pp144ndash166 1996

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 9: Research Article Spectroscopic Characteristics of ...downloads.hindawi.com/journals/jamc/2016/1480857.pdf · Microbial biomass carbon (MBC) analysis was determined by the chloroform

Journal of Analytical Methods in Chemistry 9

[15] M Han G Ji and J Ni ldquoWashing of field weathered crude oilcontaminated soil with an environmentally compatible surfac-tant alkyl polyglucosiderdquo Chemosphere vol 76 no 5 pp 579ndash586 2009

[16] X Bi L Ren M Gong Y He L Wang and Z Ma ldquoTransfer ofcadmium and lead from soil to mangoes in an uncontaminatedarea Hainan Island ChinardquoGeoderma vol 155 no 1-2 pp 115ndash120 2010

[17] J Akagi A Zsolnay and F Bastida ldquoQuantity and spectroscopicproperties of soil dissolved organic matter (DOM) as a func-tion of soil sample treatments air-drying and pre-incubationrdquoChemosphere vol 69 no 7 pp 1040ndash1046 2007

[18] N Roig J Sierra E Martı M Nadal M Schuhmacher and J LDomingo ldquoLong-term amendment of Spanish soils with sewagesludge effects on soil functioningrdquo Agriculture Ecosystems andEnvironment vol 158 pp 41ndash48 2012

[19] J L Weishaar G R Aiken B A Bergamaschi M S FramR Fujii and K Mopper ldquoEvaluation of specific ultravioletabsorbance as an indicator of the chemical composition andreactivity of dissolved organic carbonrdquo Environmental Scienceand Technology vol 37 no 20 pp 4702ndash4708 2003

[20] S A Green and N V Blough ldquoOptical absorption and fluores-cence properties of chromophoric dissolved organic matter innatural watersrdquo Limnology and Oceanography vol 39 no 8 pp1903ndash1916 1994

[21] P J Seaton R J Kieber J DWilley G B Avery and J L DixonldquoSeasonal and temporal characterization of dissolved organicmatter in rainwater by proton nuclear magnetic resonancespectroscopyrdquo Atmospheric Environment vol 65 pp 52ndash602013

[22] J Amador P J Milne C A Moore and R G Zika ldquoExtractionof chromophoric humic substances from seawaterrdquo MarineChemistry vol 29 pp 1ndash17 1990

[23] C A Stedmon and R Bro ldquoCharacterizing dissolved organicmatter fluorescence with parallel factor analysis a tutorialrdquoLimnology and Oceanography Methods vol 6 no 11 pp 572ndash579 2008

[24] P S M Santos M Otero R M B O Duarte and A C DuarteldquoSpectroscopic characterization of dissolved organicmatter iso-lated from rainwaterrdquoChemosphere vol 74 no 8 pp 1053ndash10612009

[25] C ZhaoC-CWang J-Q Li C-YWang PWang andZ-J PeildquoDissolved organic matter in urban stormwater runoff at threetypical regions in Beijing chemical composition structuralcharacterization and source identificationrdquo RSC Advances vol5 no 90 pp 73490ndash73500 2015

[26] Z Wang and Q Wang ldquoThe spatial heterogeneity of soilphysical properties in forestsrdquoActa Ecologica Sinica vol 20 no6 pp 945ndash950 1999

[27] M L Fernandez-Romero J M Clark C D Collins L Parras-Alcantara and B Lozano-Garcıa ldquoEvaluation of optical tech-niques for characterising soil organic matter quality in agricul-tural soilsrdquo Soil and Tillage Research vol 155 pp 450ndash460 2016

[28] K Kalbitz J Schmerwitz D Schwesig and E MatznerldquoBiodegradation of soil-derived dissolved organic matter asrelated to its propertiesrdquo Geoderma vol 113 no 3-4 pp 273ndash291 2003

[29] R M B O Duarte and A C Duarte ldquoApplication of non-ionic solid sorbents (XADResins) for the isolation and fraction-ation of water-soluble organic compounds from atmosphericaerosolsrdquo Journal of Atmospheric Chemistry vol 51 no 1 pp79ndash93 2005

[30] N Senesi T M Miano M R Provenzano and G BrunettildquoSpectroscopic and compositional comparative characteriza-tion of IHSS reference and standard fulvic and humic acidsof various originrdquo Science of the Total Environment vol 81-82pp 143ndash156 1989

[31] X-S He B-D Xi Y-H Jiang et al ldquoStructural transformationstudy of water-extractable organic matter during the industrialcomposting of cattle manurerdquo Microchemical Journal vol 106pp 160ndash166 2013

[32] T Jamieson E Sager and C Gueguen ldquoCharacterizationof biochar-derived dissolved organic matter using UV-visibleabsorption and excitation-emission fluorescence spectrosco-piesrdquo Chemosphere vol 103 pp 197ndash204 2014

[33] J R Helms A Stubbins J D Ritchie E C Minor D J Kieberand K Mopper ldquoAbsorption spectral slopes and slope ratiosas indicators of molecular weight source and photobleachingof chromophoric dissolved organic matterrdquo Limnology andOceanography vol 53 no 3 pp 955ndash969 2008

[34] C A Stedmon S Markager and H Kaas ldquoOptical proper-ties and signatures of chromophoric dissolved organic matter(CDOM) in Danish coastal watersrdquo Estuarine Coastal and ShelfScience vol 51 no 2 pp 267ndash278 2000

[35] J B Fellman D V DrsquoAmore E Hood and R D BooneldquoFluorescence characteristics and biodegradability of dissolvedorganic matter in forest and wetland soils from coastal temper-atewatersheds in southeastAlaskardquoBiogeochemistry vol 88 no2 pp 169ndash184 2008

[36] J Sanderman J A Baldock and R Amundson ldquoDissolvedorganic carbon chemistry and dynamics in contrasting forestand grassland soilsrdquo Biogeochemistry vol 89 no 2 pp 181ndash1982008

[37] K Fujii M Uemura C Hayakawa et al ldquoFluxes of dissolvedorganic carbon in two tropical forest ecosystems of East Kali-mantan Indonesiardquo Geoderma vol 152 no 1-2 pp 127ndash1362009

[38] A Huguet L Vacher S Relexans S Saubusse J M Froidefondand E Parlanti ldquoProperties of fluorescent dissolved organicmatter in the Gironde Estuaryrdquo Organic Geochemistry vol 40no 6 pp 706ndash719 2009

[39] A Huguet L Vacher S Saubusse et al ldquoNew insights intothe size distribution of fluorescent dissolved organic matter inestuarine watersrdquo Organic Geochemistry vol 41 no 6 pp 595ndash610 2010

[40] P R Salve H Lohkare T Gobre et al ldquoCharacterization ofchromophoric dissolved organic matter (CDOM) in rainwaterusing fluorescence spectrophotometryrdquoBulletin of Environmen-tal Contamination and Toxicology vol 88 no 2 pp 215ndash2182012

[41] D M McKnight E W Boyer P K Westerhoff P T DoranT Kulbe and D T Andersen ldquoSpectrofluorometric characteri-zation of dissolved organic matter for indication of precursororganic material and aromaticityrdquo Limnology and Oceanogra-phy vol 46 no 1 pp 38ndash48 2001

[42] R Jaffe J N Boyer X Lu et al ldquoSource characterization ofdissolved organic matter in a subtropical mangrove-dominatedestuary by fluorescence analysisrdquoMarine Chemistry vol 84 no3-4 pp 195ndash210 2004

[43] T Ohno ldquoFluorescence inner-filtering correction for deter-mining the humification index of dissolved organic matterrdquoEnvironmental Science amp Technology vol 36 no 4 pp 742ndash7462002

10 Journal of Analytical Methods in Chemistry

[44] L A Cardoza A K Korir W H Otto C J Wurrey and C KLarive ldquoApplications of NMR spectroscopy in environmentalsciencerdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 45 no 3-4 pp 209ndash238 2004

[45] C M Preston ldquoApplications of NMR to soil organic matteranalysis history and prospectsrdquo Soil Science vol 161 no 3 pp144ndash166 1996

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 10: Research Article Spectroscopic Characteristics of ...downloads.hindawi.com/journals/jamc/2016/1480857.pdf · Microbial biomass carbon (MBC) analysis was determined by the chloroform

10 Journal of Analytical Methods in Chemistry

[44] L A Cardoza A K Korir W H Otto C J Wurrey and C KLarive ldquoApplications of NMR spectroscopy in environmentalsciencerdquo Progress in Nuclear Magnetic Resonance Spectroscopyvol 45 no 3-4 pp 209ndash238 2004

[45] C M Preston ldquoApplications of NMR to soil organic matteranalysis history and prospectsrdquo Soil Science vol 161 no 3 pp144ndash166 1996

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Page 11: Research Article Spectroscopic Characteristics of ...downloads.hindawi.com/journals/jamc/2016/1480857.pdf · Microbial biomass carbon (MBC) analysis was determined by the chloroform

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of