native polycyclic aromatic hydrocarbons (pah) in coals …€¦ · hardly recognized source of...

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Review

Native polycyclic aromatic hydrocarbons (PAH) in coals Ahardly recognized source of environmental contamination

C. Achtena,b, T. Hofmanna,aUniversity of Vienna, Department of Environmental Geosciences, Althanstr. 14, 1090 Vienna, AustriabUniversity of Mnster, Department of Applied Geology, Corrensstr. 24, 48149 Mnster, Germany

A R T I C L E D A T A

Corresponding author.E-mail addresses: [email protected]

0048-9697/$ see front matter 2008 Elsevidoi:10.1016/j.scitotenv.2008.12.008

A B S T R A C T

Article history:Received 15 October 2008Received in revised form29 November 2008Accepted 5 December 2008Available online 4 February 2009

Numerous environmental polycyclic aromatic hydrocarbon (PAH) sources have beenreported in literature, however, unburnt hard coal/ bituminous coal is considered onlyrarely. It can carry native PAH concentrations up to hundreds, in some cases, thousands ofmg/kg. The molecular structures of extractable compounds from hard coals consist mostlyof 26 polyaromatic condensed rings, linked by ether or methylene bridges carrying methyland phenol side chains. The extractable phase may be released to the aquatic environment,be available to organisms, and thus be an important PAH source. PAH concentrations andpatterns in coals depend on the original organic matter type, as well as temperature andpressure conditions during coalification. The environmental impact of native unburnt coal-bound PAH in soils and sediments is not well studied, and an exact source apportionment ishardly possible. In this paper, we review the current state of the art.

2008 Elsevier B.V. All rights reserved.

Keywords:Native PAHBituminous coalHard coalSedimentSoil

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24622. Reserves and production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24623. Coal diagenesis and associated PAH formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24634. Coal classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2463

4.1. Coal rank . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24644.2. Types of fossil organic matter. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24644.3. Coal maceral composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2464

5. Native PAH concentrations and distribution patterns: Occurrence and correlations with coal rank and type . . . . 24656. Native hard coal-bound PAH in soils and sediments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2467

6.1. Unburnt coal particles in soils and sediments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24676.2. Identification, patterns and quantification of native PAH from unburnt coal particles in soils and sediments . . 2469

7. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2470References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2470

(C. Achten), [email protected] (T. Hofmann).

er B.V. All rights reserved.

mailto:[email protected]:[email protected]://dx.doi.org/10.1016/j.scitotenv.2008.12.008

2462 S C I E N C E O F T H E T O T A L E N V I R O N M E N T 4 0 7 ( 2 0 0 9 ) 2 4 6 1 2 4 7 3

1. Introduction

Polycyclic aromatic hydrocarbons (PAH) comprise of manycarcinogenic substances and are ubiquitous in the environ-ment. The U.S. Environmental Protection Agency regulated 16priority pollutant PAH (16 EPA-PAH) spanning from 26condensed aromatic rings, which are commonly analyzed.The occurrence of PAH in soils and sediments is oftencorrelated to pyrogenic non-point sources from incompletecombustion of (fossil) organic matter (Costa and Sauer, 2005;Lima et al., 2005; Mller et al., 1977; Suess, 1976). Point sourcesmay originate from e. g. oil spills (Short et al., 2007), usedmotor oil (Stout et al., 2002b; Napier et al., 2008), or con-taminated industrial sites such as manufactured gas plantsites (coal tar, coke) (Khalil and Ghosh, 2006; Saber et al., 2006;Stout and Wasielewski, 2004), sites of wood treatment withcreosote (Murphy and Brown, 2005), aluminum production(Booth and Gribben, 2005) or steel works (Almaula, 2005). Theoccurrence of natural or industrially refined petrogenic PAHhas been reported from crude oil/petroleum, naphtha, fuels,diesel, bunker C (marine) fuels and lubricating oil (Boehmet al., 1998, 2001; Short et al., 2007; Stout et al., 2002b; Wangand Fingas, 2006). Biogenic PAH such as retene (Simoneit et al.,1986), triaromatic triterpenoids/steroids (Tissot and Welte,1978) or partially perylene (Meyers and Ishiwatari, 1993) havebeen identified.

Surprisingly, unburnt coal has rarely been considered as aPAH source in soils and sediments (Ahrens and Morrisey,2005). In addition to sorbed PAH once being exposed to theenvironment, original hard coals from the seam can containPAH up to hundreds and, in exceptional cases, thousands ofmg/kg (Stout and Emsbo-Mattingly, 2008; Willsch and Radke,1995). This neglect was expressed by Walker et al. (2005), whodescribed coal as an unknown or unsuspected source of PAH.In coals of low rank, such as lignite, sub-bituminous coal orbrown coal, significantly lower PAH concentrations weredetected (e. g. 13 mg/kg EPA-PAH, Pttmann, 1988). Up to30 mg/kg alkylnaphthalenes, but no EPA-PAH were observedby Bechtel et al. (2005). Their occurrence in brown coals isexplained by degradation of pentacyclic angiosperm-derivedtriterpenoids (Pttmann and Villar, 1987; Tuo and Philp, 2005).In a sub-bituminous coal from the Wealden Basin at Zwische-nahn, Germany, 243 mg/kg of total PAH and 14 mg/kg of EPA-PAH were detected (Radke et al., 1990). Kashimura et al. (2004)identified semi-quantitatively naphthalene, phenanthrene,anthracene, pyrene, chrysene, benzo[a]anthracene, perylene,benzo[a]pyrene, benzo[e]pyrene, benzo[b]chrysene, dibenzo[a,i]pyrene, dibenzo[a,h]pyrene, and coronene in Victorian browncoals from Australia. Other studies presented qualitativeresults only (Chaffee and Johns, 1982; Stout et al., 2002a).

Besides other environmental concerns regarding coal useand production, in theory their native PAH content could posea risk to soils and sediments, however until today, no studyclearly showed it. Whereas physical effects of coal dust onorganisms have often been investigated (e. g. Ahrens andMorrisey, 2005 and references therein), less is known aboutchemical effects due to coal constituents such as PAH. Theecotoxicological impact of coal particles in soils and sedi-ments has not yet been studied in detail (Ahrens andMorrisey,

2005, Chapman et al., 1996). It is well-known that non-nativePAH and other hydrophobic contaminants present in theenvironment are effectively sorbed to simultaneously presentcoal particles (sink), which is explained by the strong sorptionaffinity, high sorption capacity, and slow desorption kineticscompared to other organic matter (Kleineidam et al., 2002;Wang et al., 2007; Yang et al., 2008a). However, little is knownabout desorption of native PAH from coal (Yang et al., 2008a,cand references therein).

Native PAHs in coal are of particular interest in environ-mental research since coal has been mined on a global scalefor centuries at quantities reaching approx. 5 billion tons in2005 (Thielemann et al., 2007). Unburnt coal particles can bereleased by open pit mining, spills during coal loading, andtransport or accidents releasing coal into freshwater ormarinesystems (Fig. 1) (French, 1998; Johnson and Bustin, 2006; Pieset al., 2007). On industrial sites, coal is stored in stockpiles forthe production of coke, gas or steam and is subject to erosion.Apart from coke and coal tar, manufactured gas plant sites arealso known for present unburnt coal particles (Saber et al.,2006; Stout and Wasielewski, 2004). Recently, the addition ofcarbon particles like activated carbon and coke to reduceavailability of organic contaminants has been discussed andinvestigated (Zimmerman et al., 2004; Werner et al., 2006;Brndli et al., 2008; Sun and Ghosh, 2008). Some of thesematerials may also contain PAH (e.g. coke) and add up to thetotal concentration present in sediments. In some areas, coalnaturally eroded into aquatic systems from sedimentary rockoutcroppings containing coal seams (Stout et al., 2002a).Finally, native and sorbed coal bound PAH may be relocatedby colloidal/particulate transport of the coal particles them-selves enhancing (or reducing) the mobility of hydrophobicorganic contaminants (Hofmann 2002, Hofmann et al., 2003a,b; Hofmann and von der Kammer, 2008).

In this paper we focus on coal being a possible PAH source.The aim of this paper is to review the state of the artaddressing the (1) characterization of PAH predominantly inhard coals/ bituminous coals, (2) the formation of PAH andinfluencing factors such as hard coal maturity and origintogether with (3) the occurrence of hard coals and coal boundPAH in soils and sediments.

2. Reserves and production

Currently, the top eleven hard coal producing countries orcountries with more than 10 billion tons of hard coal reservesare China, U.S.A., India, Australia, South Africa, Russia,Indonesia, Poland, Kazakhstan, Ukraine and Germany(World Coal Institute, 2007). Worldwide hard coal productionhas increased from less than 1 to 4.96 billon tons from 1900 to2005 (Thielemann et al., 2007). The significance of coal as anenergy source has recently been predicted to increase in thefuture (Massachusetts Institute of Technology, 2007). In 2004,China, the U.S.A. and India produced about 2, 1 and 0.4 billiontons of hard coal and held about 60, 100 and more than 80billion tons of reserves, respectively. Australia, South Africaand Russia have reserves of about 4050 billion tons of hardcoal each and annual productions of less than 0.3 billion tonseach. With a share of more than 70%, Australia is the largest

Fig. 1 Coal emission sources to the aquatic environment (modified after Ahrens and Morrisey, 2005).

2463S C I E N C E O F T H E T O T A L E N V I R O N M E N T 4 0 7 ( 2 0 0 9 ) 2 4 6 1 2 4 7 3

export country compared to 8%, 3% and no significantamounts of exports from the U.S.A., China and India,respectively (Max-Planck-Institut fr Plasmaphysik, 2000;2001a,b; 2002a,b). Due to the economic combination of largeopen pit mining near the East Coast and railway connectionsto several coal harbors, Australia is able to export 70% of thecoal to Japan and other Asian countries and about 15% toEurope. Since the 1980s, the export of coal in Australia hasdoubled. In 1991, Russia was the largest hard coal exportingcountry worldwide, however since the break-up of the SovietUnion, the production and export numbers have reducedsignificantly.

3. Coal diagenesis and associated PAHformation

When remains of land plants, particularly peat, are buried, itis converted to coal by prolonged exposure to elevatedtemperatures and pressures in the subsurface. The concur-rent physico-chemical changes are complex (Taylor et al.,1998). Generally, resistant plant biopolymers, e. g. lignin, areconverted into highly aromatic, three-dimensional, networkmatrix in the order of increasing maturity: peat lignite sub-bituminous coal bituminous coal anthracite graphite (Fig. 2). The proportion of conjugated aromatic ringsper structural unit within the matrix determines the aroma-ticity and increases with increasing coalification, ultimatelyresulting in graphite. Dehydroxylation, demethylation andcondensation reactions produce a relative increase in carboncombined with a decrease in oxygen and hydrogen as it issuggested in the van-Krevelen-diagram (Fig. 3, van Krevelen,1993). Aromatic structures are commonly linked by ether ormethylene bridges. Aliphatic side chains consist mainly of

methyl, and less of ethyl, propyl or butyl functional groups.The average number of aromatic rings per structural unit inmost coals is 35 (Stout et al., 2002b) with some individualunits containing up to 10 rings. A typical hard coal ischaracterized by 26 PAH linked by methylene bridges withadditionally bound aliphatic side chains and phenol func-tional groups. With increasing rank, aromatic units increasefrom 34 condensed rings at low rank to about 30 fused ringsin anthracite. Concurrently, the lengths of side chainsdecrease.

In addition to the network structure, a multitude of smallmolecules, i.e. a mobile phase, is present within the network(Given, 1987) and is of particular environmental interest.These molecules can be released from the coal network morerapidly because they are less bound to the macromolecularmatrix compared to the cross-linked molecules within thenetwork. The type and rank of a coal influences theconcentration and composition of the mobile phase, whichis abundantly present in coals ranking within the oil genera-tion window. The mobile phase is eliminated during hotsteam treatment used for active carbon production from e. g.hard coal or charred coconut shells. During coal heating atmanufactured gas plant sites, the linkages between some ofthe carbon units are cleaved, thereby releasing the conjugatedaromatic rings into the mobile fraction (gas and coal tar).

4. Coal classification

Coal is being classified according to its various physico-chemical properties (van Krevelen, 1993). Due to the expectedimpact on the formation of PAH, we consider those classifica-tion systems, which are based on rank, types of fossilsedimentary organic matter and coal maceral composition.

Fig. 2 Small molecule sections of lignin (top), bituminouscoal (middle) and anthracite (bottom) (modified after theCollege of Liberal Arts and Sciences, Western OregonUniversity, and after U.S., Lignin Institute, U.S.A.)

Fig. 3 van Krevelen diagram (modified after van Krevelen,1993).


4.1. Coal rank

Volatile matter content, vitrinite reflectance (% Ro), carbonand water content, calorific value, hydrocarbon indices,temperature of maximum hydrocarbon formation duringheating (Tmax) and other factors (Tissot and Welte, 1978) areused to measure coal rank. Vitrinite reflectance is commonlyused due to its stability over a wide range of coal rank, itsabundance and independency on kerogen types or bitumencontent (Stach et al., 1982). It is ameasure of the percentage oflight reflected from the vitrinite macerals at high magnifica-tion (500) in oil immersion. Lignite is characterized byapprox. 0.3% Ro, the transition zone from brown coal to hardcoal is at approx. 0.65% Ro and from hard coal to anthraciteapprox. 2.22.5% Ro (Fig. 4). The oil generation window rangesfrom 0.51.3% Ro.

Various indices of parent and alkylated naphthalenesor phenanthrenes can also be applied. They are based

on different stabilities of the alkyl functional groups at differentpositions on the molecules. The -positions are more thermo-dynamically stable (e. g. 2- and 3-methylphenanthrenes)compared to the -positions (e. g. 1- and 9-methylphenan-threnes) and their formation is preferred with increasing rank(Willsch and Radke, 1995). Trimethylnaphthalene ratios (TNR-1,TNR-2), methylphenanthrene ratio (MPR) (Radke and Welte,1981), dimethylphenanthrene ratios (DPR-1, DPR-2),methylphe-nanthrene indices (MPI-1 and MPI-4) (Radke et al., 1982b; Radkeet al., 1984; Willsch and Radke, 1995) and dimethylnaphthaleneratios (DNR-1 to -5) (Alexander et al., 1983, 1985) were described.

4.2. Types of fossil organic matter

Kerogen represents about 90% of the fossil organic carbon insediments (van Krevelen, 1993). Three types can be recognized(Tissot andWelte, 1978); Type I is primarily derived from algallipids (hydrogen-rich) and ismainly of aliphatic nature; Type IIis primarily formed of marine plankton and bacteria (bothexhibit a high gas and oil generating potential); Type III, themost common type of coal (humic coals, oxygen-rich)contains organic matter derived from terrestrial higher plantsand exhibits a mostly aromatic nature. Its potential for oilgeneration is low. After successive alteration stages ofdiagenesis, catagenesis andmetagenesis, finally, a chemicallyuniform product (graphite) is generated (Fig. 2).

4.3. Coal maceral composition

A classification system based on the fossilized plant remains(macerals) observed under the microscope is commonly usedin coal research (Teichmller, 1989). Three different maceralgroups can be distinguished: (1) vitrinite, which may beconsidered the standard coalification product of woody tissue,

Fig. 4 Total polycyclic aromatic hydrocarbon concentrations against coal rank of different coals. Dashed line: total aromatichydrocarbons (Radke et al., 1990), solid line: total PAH43 (Stout and Emsbo-Mattingly, 2008), dash-dotted line: EPA-PAHconcentrations (Stout and Emsbo-Mattingly, 2008), dotted line: EPA-PAH concentrations (Zhao et al., 2000); (and data compiledfrom Chen et al., 2004; Pies et al., 2007; 2008a,b; Radke et al., 1990; Willsch and Radke, 1995; Van Kooten et al., 2002).


(2) liptinite, which has a higher hydrogen-content comparedto vitrinite, and (3) inertinite, which shows a lower hydrogen-content compared to vitrinite. The maceral groups of vitriniteand liptinite form the reactive components in the carboniza-tion and liquefaction processes of coal, whereas inertinitebehaves as an inert additive (van Krevelen, 1993).

Macerals originating from woody and cortical tissuesinclude the following (numbers in brackets refer to maceralgroups):

Vitrinite (with wooden structure: telinite, 1, without struc-ture: collinite, 1),

Fusinite (charred cell walls, characteristic maceral of fossilchar coal, 3).

Macerals with a clear origin of plant material and otherwoody tissues include:

Sporinite (fossil remains of spore exines, 2), Cutinite (constituent formed from cuticules, 2), Resinite (fossil remains of plant resins, 2), Alginate (remains of algae bodies, 2) and Sclerotinite (fossil remains of fungal sclerotia, 3).

The properties of different coals are strongly affected bythe types and proportions of the various macerals presenttherein. The aromaticity of coal macerals in coals of different

rank vary and at the same coal rank it decreases in the orderinertiniteNvitriniteN liptinite.

5. Native PAH concentrations and distributionpatterns: Occurrence and correlations with coalrank and type

The presence of PAH in hard coals has been reported fromseveral countries, e. g. Germany (76 samples) (Pttmann andSchaefer, 1990; Radke et al., 1982a, 1990; Radke andWelte, 1981;Willsch and Radke, 1995), Canada (34 samples) (Radke et al.,1982b; Willsch and Radke, 1995), U.S.A. (48 samples, includingAlaska) (Hayatsu et al., 1978; Kruge, 2000; Kruge and Bensley,1994; Stout et al., 2002a; Van Kooten et al., 2002;White and Lee,1980; Zhao et al., 2000; Stout and Emsbo-Mattingly, 2008), Japan(3 samples) (Radke et al., 1990), France (1 sample) (Kruge, 2000),China (5 samples) (Chen et al., 2004; Tang et al., 1991) and Brazil(1 sample) (Pttmann, 1988). However, many studies presentqualitative results only. A summary of the limited publishedquantitative PAH data available (Table 1) shows that concen-trations vary widely, from 1 to about 2500 mg/kg. PAH in asample set of several hard coals from international large coalbasins are currently studied (Micic et al., 2007).

Detected compounds include 16 EPA-PAH, benzo[e]pyrene,perylene, coronene, and their alkylated derivatives (Pttmann,1988; Van Kooten et al., 2002; Willsch and Radke, 1995), as well

Table 1 Summary of total and 16 EPA polycyclic aromatic hydrocarbon concentrations in coals

Total PAHs[mg/kg]

EPA-PAHs[mg/kg]

References

High volatile bituminous coal A, Elmsworth gasfield, 10-11-71-11W6, Canada 2429.1 152.1

Willsch and Radke (1995)

High volatile bituminous coal A, Elmsworth gasfield, 10-03-70-10W6, Canada 2412.3 136.6Medium volatile bituminous coal, Ruhr basin, Osterfeld, Germany 1037.2 153.3Medium volatile bituminous coal, Ruhr basin, Hugo, Germany 933.8 123.6Low volatile bituminous coal, Ruhr basin, Westerholt, Germany 1200.7 163.9Low volatile bituminous coal, Ruhr basin, Blumenthal, Germany 786.5 155.4Low volatile bituminous coal, Elmsworth gasfield, 06-19-68-13W6, Canada 546.4 98.6Low volatile bituminous coal, Ruhr basin, Haard, Germany 567.7 154.8High volatile bituminous coal, Wealden Basin, Nesselberg, Germany 656.2 43.1

Radke et al. (1990)High volatile bituminous coal, Wealden Basin, Barsinghausen, Germany 554.4 56.7High volatile bituminous coal, Saar, Ensdorf, Germany 165.9 50.5

Pies et al. (2007)Medium volatile bituminous coal, Germany 68.0 22.4Bituminous coal, Germany 127.6 28.7Lignite A, Northern Great Plains, Beulah, USA 8.5a 1.2

Stout and Emsbo-Mattingly (2008)

Lignite A, Northern Great Plains, Pust, USA 6.5a 1.0Sub-bituminous coal C, Northern Great Plains, Smith-Roland, USA 12.0a 0.1Sub-bituminous coal C, Gulf Coast, Bottom, USA 14.0a 1.6Sub-bituminous coal B, Northern Great Plaines, Dietz, USA 14.0a 0.8Sub-bituminous coal B, Northern Great Plaines, Wyodak, USA 5.4a 0.3Sub-bituminous coal A, Rocky Mountains, Deadman, USA 12.0a 1.5High volatile bituminous coal C, Rocky Mountains, Blue, USA 77.0a 5.3High volatile bituminous coal B, Eastern Coal, Ohio #4A, USA 60.0a 8.2High volatile bituminous coal A, Rocky Mountains, Blind Canyon, USA 78.0a 4.4High volatile bituminous coal A, Eastern Coal, Pittsburgh, USA 76.0a 11.0Medium volatile bituminous coal, Rocky Mountains, Coal Basin M, USA 29.0a 1.8Low volatile bituminous coal, Eastern Coal, Pocahontas #3, USA 20.0a 3.8Semianthracite, Eastern Coal, PA Semi-Anth. C, USA 5.9a 2.1Anthracite, Eastern Coal, Lykens Valley #2, USA 0.2a b0.1High volatile bituminous coal, Blind Canyon, USA 78.3 Stout et al. (2002b)High volatile bituminous coal C-1, USA 7.5 0.5

Zhao et al. (2000)

High volatile bituminous coal C-2, USA 3.4 0.4High volatile bituminous coal C-3, USA 2.4 0.3High volatile bituminous coal B-1, USA 1.6 0.3High volatile bituminous coal B-2, USA 12.7 2.4High volatile bituminous coal A-1, USA 13.7 5.4High volatile bituminous coal A-2, USA 27.6 6.4Low volatile bituminous coal, USA 1.2 0.3Anthracite, China 2.5 1.8 Chen et al. (2004)Bituminous coal, Brazil 13.0 Pttmann (1988)

a Sum of 43 PAHS.


as retene, methylated chrysenes, methylated picenes, tetra-hydrochrysenes, hydropicenes and methylphenanthrenes incoals ranging from lignite to anthracite (Barrick et al., 1984).

Recently, 15 coal samples of different rank from the U.S.A.were analyzed for PAH concentrations and source character-ization of coal (Stout and Emsbo-Mattingly, 2008). Lowconcentrations of 16 EPA-PAH from 0.03511 mg/kg wereobserved with a mean of 3 mg/kg. Concentrations rangingfrom 0.1878 mg/kg with a mean of 30 mg/kg were reportedfor 43 PAH compounds. Highest concentrations occurred inhigh volatile bituminous coals.

Considering the chemical processes during coalification, asystematic relationship between PAH concentrations and coalmaturity is expected. InFig. 4, total PAHconcentrations fromtheliterature are plotted against corresponding coal rank and nocorrelation can be deduced. However, if coals of similar originare considered, themaximum total aromatic hydrocarbon yield(Radke et al., 1990) and maximum EPA-PAH concentrations(Zhao et al., 2000) were observed at 0.9% Ro and 1.1% Ro,

respectively. Both measurements lie within the oil generationwindow. Stout et al. (2002b) and Stout and Emsbo-Mattingly(2008) observedmaximumPAH concentrations in coals of about0.50.9% Ro. Raises of PAH concentrations up to 1.1% Ro isexplained by increasing condensation, carbon concentrationand aromatization of coal with increasing maturity (Suggateand Dickinson, 2004). However, at high rank (N1.1% Ro) anincrease of the polyaromatic compounds with more than 6condensed rings may occur, at least partially, at the expense of26 ring PAH due to rearrangement and fragmentation reac-tions. This process may be responsible for decreased total PAH(26 ring) concentrations in e. g. anthracite (Chen et al., 2004).

Not only PAH concentrations but also PAH patterns changewith increasing rank. Sub-bituminous coals contain PAH,predominantly in the form of chrysene, picene and theiralkylated derivatives. During coalification, PAH patternschange because primary products of higher thermodynamicstability are generated at the expense of less stable com-pounds. At the boundary between sub-bituminous/high


volatile bituminous coal (or brown/hard coal), distinct lowmolecular weight aromatic compounds are generated. Bi- andtricyclic PAH are formed mainly in the high volatile bitumi-nous coal stage and provide a pattern of compounds showinga structural relationship to natural precursor molecules, e. g.phenanthrene derivatives, which are thought to be derivedfrom plant resins and steroids (Pttmann and Schaefer, 1990).With increasing maturity, a shift occurs in the PAH patternfrom high concentrations of naphthalene and its alkylatedderivatives at low hard coal rank to a relative increase of 46-ring PAH at high rank (Ahrens and Morrisey, 2005). Simulta-neously, the oxygen content is lowered, which results in lowerconcentrations of hydroxylated aromatic compounds, such asphenols, which are most prevalent in lignite. Due to rearran-gement and fragmentation reactions at increasing rank,aromatic hydrocarbons are no longer directly derived frombiological precursors. Similar distribution patterns comparedto those of other coals of comparable rank occur and theindividual PAH patterns of coals become less complex(Pttmann and Schaefer, 1990).

The changes in PAH patternswith increasing rank are shownin Fig. 5. At low hard coal rank (Rob1%, Fig. 5a), C0C4alkylnaphthalenes (up to about 30%) are the dominant PAHgroup. C0C3 alkylphenanthrenes rank second and typicallycomprise b10% of total PAH. Retene is present up to about 25%,whereasC1+C2alkylfluorenesandmethylfluoranthenesareonlydetected at low concentrations (up to about 2% each). Other PAH,if present, only occur at trace concentrations. With increasingrank (Ro=1.261.65%, Fig. 5b), the C0C3 alkylnaphthalenesdominance is diminished, and C4 alkylnaphthalenes and reteneareno longerdetected. Incontrast, thephenanthrenedominanceoften increases with concentrations N10% of the total PAHpresent. C1+C2 alkylfluorene and methylfluoranthene concen-trations increase, often reaching about 5% of the total aromatichydrocarbons. Generally, higher molecular weight PAH concen-trations are increased compared to those observed at lower hardcoal rank, and C0+C1 alkylchrysenes and isomers are present upto about 4%. Significant increases in higher molecular weightPAHoccurathigh ranksuchasanthracite (RoN2.5%, Fig. 5c).Here,naphthalenes are not present and the dominance of parent PAHand methylphenanthrenes is observed in the single reportedsample. Higher molecular weight PAH such as benzo[e]pyreneand benzo[b]fluoranthene are detected at N10% each andcoronene at N2%. The degree of alkylation of aromatic hydro-carbons decreases with increasing coal rank from low volatilebituminouscoal toanthracite. In summary, ashift fromalkylatedbi- and tricyclic PAH at lower hard coal rank to higher molecularparent compounds in anthracite has been observed, which is inaccordance with increasing carbon concentration and aromati-zationduring the coalificationprocess. Apparently, PAHpatternsshift with increasing rank from a bell-type" shape (C0-C4naphthalenes and phenanthrenes) to a slope-type" shapewhich is commonly known to be typical of a pyrogenic PAHorigin.

Correlations between PAH distributions and the originalorganic matter type of coals are expected, since different coalmacerals can produce different mixtures of aromatic com-pounds. For example, liptinites are known as sources fornaphthalenes or vitrinite for biphenyls (Tang et al., 1991). Kruge(2000) observed correlations between dibenzothiophenes/-fur-

ans and dimethylphenanthrenes as an indicator for organicmatter type I, II or III.

6. Native hard coal-bound PAH in soils andsediments

6.1. Unburnt coal particles in soils and sediments

The presence of unburnt coal particles has been reported frommarine and freshwater sediments, aswell as soils. In themarineenvironment, the Exxon Valdez oil spill in Alaska, U.S.A.,triggered detailed discussion whether PAH in sediments ofPrinceWilliamSound originated from the spill or fromnaturallyoutcropping coal seamsnear the shore (Boehmet al., 2001; Shortet al., 1999). In coastal sediments, coal particles in some casesreached sizes of some tens of centimeters in diameter, e. g. atKatalla beach. Earlier, Tripp et al. (1981) concluded that unburntcoal can be a significant source of sediment hydrocarbons in thecoastal marine environment. Barrick et al. (1984) correlatedhydrocarbons from 16 Western Washington coals to sedimentsamples from Puget Sound and Lake Washington.

Estuaries in the vicinity of mining activity can be impactedby coal emissions as reported from the Severn Estuary, GreatBritain, where coal mining dates back to the mid-16th century(French, 1998). Intertidal mudflat sediments are estimated tohold around 105106 tonnes of coal. Coal emissions intosediments were reported from harbors such as HamiltonHarbour (Curran et al., 2000) and Roberts Bank coal terminal,both in Canada (Johnson and Bustin, 2006). Coal particlespresent in sediments made up 10.5 to 11.9% dry weight of thesoil mass in the vicinity of coal-loading terminals and wasreported as non-hydrolysable solids. An increase of the coalconcentration in the uppermost 23 cm within about 3 km2

was observed from 1.8% to 3.6% during the time from 1977 to1999 (Johnson and Bustin, 2006).

In freshwater sediments and floodplain soils, unburnt coalparticles were identified at the Lippe (Klos and Schoch, 1993),Saar and Mosel rivers, Germany, due to former coal mining(Hofmann et al., 2007; Pies et al., 2007, 2008a; Yang et al., 2007).Hard coal particle concentrations of the heavily coal-impactedfloodplain soil samples were in the range of 4574 vol.% of thelight fraction (the fraction with a density b2 g/cm3, predomi-nantly organic carbon). PAH concentrations of the lightfractions in the samples ranged from 370460 mg/kg (sum ofEPA-PAH, 1- and 2- methylnaphthalenes) dry weight andthereby contributed 89.9% to the total (sum of EPA-PAH, 1- and2- methylnaphthalenes) sediment PAH content (Yang et al.,2008b).

In soils, unburnt coal particles and elevated hydrocarbonconcentrations were identified in dust and soil samples fromthe Ojcw National Park, Poland (Schejbal-Chwastek andMarszalek, 1999). During the coal combustion process, flyash notably still contains unburnt coal particles at lowconcentrations (Klaots et al., 2004; Lopez-Anton et al., 2007).These are not commonly investigated in soils and sediments.It cannot be excluded that native PAH from co-emittedunburnt coal particles contribute to health issues resultingfrom coal combustion linked emissions (Liu et al., 2008;Tremblay, 2007). For example, in China, since 2001 an increase

Fig. 5 Total polycyclic aromatic hydrocarbon patterns at different coal ranks: a) b1% vitrinite reflectance (Ro), b) 1.261.65% Ro,and, c) N1.7% Ro; Naph: naphthalene, Acy: acenaphthylene, Ace: acenaphthene, Fl: fluorene, Phe: phenanthrene, Ant:anthracene, Flu: fluoranthene, Pyr: pyrene, BaA: benzo[a]anthracene, Chry+Tri: chrysene and triphenylene, BbF: benzo[b]fluoranthene, BkF: benzo[k]fluoranthene, Bep: benzo[e]pyrene, Bap: benzo[a]pyrene, Incdp: indeno[1,2,3-cd]pyrene, BghiP:benzo[g,h,i]perylene, Ret: retene, Cor: coronene, C0: parent compound, C1C4: C1C4 alkylated derivatives.


Fig. 5 (continued).


of 40% in birth defectswas reported in regions of intensive coalmining and burning, i.e. in Shanxi Province. However, nostatistical significance was detected between malformationsduring early embryogenesis and distance from coal plants (Guet al., 2007).

Several investigations on emitted unburnt coal particlesfrom opencast mining have been reported from India: Jhariacoalfield (Ghose and Majee, 2000a,b), Raniganj coalfield (Singhand Sharma, 1992), Manuguru coal belt area of AndhraPradesh (Sekhar and Rao, 1997) and Lakhanpur area of IbValley coalfield (Chaulya, 2004). In the Block II opencastproject at the Jharia coalfield, different emission sourceswere quantified. Based on the project holding coal reservesof 37 Mt occupying 674 ha of land, an estimated total amountof 9368 kg/day of coal dust is emitted mainly due to miningactivities and wind erosion of the exposed area (Ghose, 2007).The predominant emission sources were the crushing andfeeding point for size reduction (40%), the unloading point ofthe conveyor belt (31%), wind erosion of the total area (17%),transportation on haul road (5.2%), loading into dumper (3%)and onto the conveyor belt (2%). Also, in the Manuguru coalbelt area of Andhra Pradesh, an increase in coal emissions inrecent years was observed (Sekhar and Rao, 1997).

6.2. Identification, patterns and quantification of nativePAH from unburnt coal particles in soils and sediments

Unburnt coal particles in soils and sediments can be identifiedby coal petrography (Ligouis et al., 2005; Taylor et al., 1998;

Yang et al., 2008b). However, since the method is complex andtime-consuming it is seldom resorted to. In the coal miningarea of Ruhr-Lippe, Kls and Schoch (1993) could correlatedifferent historical periods of low coal-production due to aneconomic crisis to reduced PAH concentrations found in age-dated sediments. However, it was not investigated whetherthe PAH emissions originated from coal combustion orunburnt coal particles.

Frequently, hydrocarbon fingerprints and indices are usedto distinguish between petrogenic and pyrogenic PAH in soilsand sediments (Budzinski et al., 1997; Stout et al., 2002b;Wang,2007; Pies et al., 2008b), but it is difficult to identify PAH derivedfrom coal vs. PAH from oil. These uncertainties are assumed tobe predominantly responsible for the lack of information onnative coal-bound PAH in soils and sediments. This gap ofknowledge can easily confound forensic attempts of sourceidentification (Stout et al., 2002b), as evident in the case of theExxon Valdez oil spill (Boehmet al., 1998, 2001; Short et al., 1999;Van Kooten et al., 2002). In the investigated sediments, Barricket al. (1984) and Stout et al. (2002a,b) observed dominatingalkylatednaphthaleneswitha bell-shapedpattern typical forpetrogenic sources. Regarding the aliphatic fraction, n-alkanesexhibited a characteristic odd-even predominance within theC25-C31 range in a high volatile bituminous coal (Stout et al.,2002b). Low ratios of triaromatic steranes to methylchrysenesin coal (b0.2) compared to high ratios (11 and 13) were detectedin oil (Short et al., 1999).

Barrick and Prahl (1987) described alkylphenanthrenes,alkylchrysenes and alkylpicenes concentrated in coal


fragments of sediments near river mouths in the central andsouthern Puget Sound region, U.S.A., originating from riversystems draining coal-bearing strata. Surely, themost obviouscharacteristics of native PAH from coals are the predominanceof naphthalene, phenanthrene and their alkylated derivatives,however, these are also typical of PAH from other petrogenicsources such as oil. Soil from a manufactured gas plant sitecontained a dominance of naphthalene, phenanthrene, chry-sene and their alkylated derivatives in a coal sample separatedfrom the soil, but not in other samples containing tar orresidual petroleum (Stout and Wasielewski, 2004). EPA-PAHconcentrations of the coal sample were around 10 mg/kg.Increased concentrations of fluoranthene, phenanthrene,pyrene and chrysene were reported from a coal pile runoff inHamilton Harbour, Canada (Curran et al., 2000).

The PAH patterns of the coals investigated in the aftermathof the Exxon Valdez oil spill were also dominated by naphtha-lene, phenanthrene and alkylated derivatives (Short et al.,1999; Boehm et al., 2001). EPA-PAH concentrations areestimated at approx. 500 mg/kg in coals from the KulthiethFormation (Van Kooten et al., 2002). In these coals, thepresence of naphthalene, C1 and C2 naphthalenes tended tobe greater than in seep oils, whereas the higher molecularweight PAH were more abundant in seep oils. Low molecularweight PAH can easily volatilize during sample preparation,e. g. if the extract is dried, whichwas not the case in this study.Naphthalenes volatilize more easily from oil or tar comparedto coal since coal is a very strong sorbent. Therefore, thedecrease in naphthalene concentrations in soils and sedi-ments, after being subject to gentle evaporation, could beregarded as an indicator for oil-bound PAH but not coal-boundPAH. At the Mosel River, Germany, naphthalenes were alsoshown to be the key compounds for source apportionment ofPAH. Native PAH in Saar coals (70165 mg/kg EPA-PAH) are themajor reason for elevated PAH concentrations in Saar andMosel River floodplain soils downstream from mining activity(Hofmann et al., 2007; Pies et al., 2007, 2008a; Yang et al., 2007,2008b,). Althoughmajor mining activity occurred between 200to 50 years ago, naphthalenes and alkylated derivatives stilldominate the PAH patterns in the floodplain soils (Pies et al.,2008a,b). Recently, Stout and Emsbo-Mattingly (2008) showedthat PAH distributions and indices varied with coal rank andconcluded that particulate coal in soils and sediments cannotbe universally represented by a single set of diagnosticparameters based on the investigated samples.

7. Conclusions

Coal-bound native PAH in soils and sediments have beenstudied to a minor extent, despite 30 years of research on PAHin the environment. Their impact on the environment is notwell understood. Unburnt hard / bituminous coal emissionsfrom mining activity particularly impact those countries hold-ing large coal basins. Coal particles were found in concentra-tions up to approx. 75 vol. % of the light fraction (b2 g/cm3) ofsoils and sediments and they contain PAH concentrationsranges from trace level up to thousands of mg/kg.

Hard coal consists of amacromolecular network phase anda mobile phase, and PAH are part of both. However, the latter

phase is of special environmental interest because it ismore mobile and is expected to have higher bioavailability.Aromatization of coals increases with increasing rank fromsub-bituminous coal to anthracite. In coals, oil (mobile phase,including 26 ring PAH) is generated at low to medium hardcoal rank from 0.51.3% Ro. In this range also maximum PAHconcentrations may occur but they also depend on origin (e. g.maceral composition). Naphthalene, phenanthrene, chryseneand alkylated derivatives are characteristic petrogenic PAH. Todate, it is hardly possible to distinguish PAH derived from oilvs. PAH from coal. If other geosorbents such as black carbonare not present at higher levels, limited evaporation ofnaphthalenes compared to the greater losses in other samplesmay be a helpful indicator of the presence of coal. Othertechniques, like organic petrography, are of major importancefor source identification. The data is presently insufficient forus to ascertain if native PAH derived from unburnt hard coalparticles pose a severe risk for humans or organisms of thebenthos and soil. In addition, coal particles might also berelocated by wind erosion, transport/loading, or accidentalreleases (Ghoose and Majee, 2000a,b). Coal particles in theenvironment may sorb hydrophobic organic contaminantsand enhance their relocation by colloidal/particulate transport(Hofmann et al., 2003a; Hofmann and Wendelborn, 2007;Hofmann and von der Kammer, 2008). For most of the largecoal basins, these topics are not well studied. They should beincluded into an assessment of the environmental impacts ofcoal.

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http://www.worldcoal.org

Native polycyclic aromatic hydrocarbons (PAH) in coals A hardly recognized source of environm.....IntroductionReserves and productionCoal diagenesis and associated PAH formationCoal classificationCoal rankTypes of fossil organic matterCoal maceral composition

Native PAH concentrations and distribution patterns: Occurrence and correlations with coal rank.....Native hard coal-bound PAH in soils and sedimentsUnburnt coal particles in soils and sedimentsIdentification, patterns and quantification of native PAH from unburnt coal particles in soils .....

ConclusionsReferences

native polycyclic aromatic hydrocarbons (pah) in coals …€¦ · hardly recognized source of...

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