env pol trends haps sources antartica

8/13/2019 ENv Pol Trends HAPS Sources Antartica

1/9

Historical record of polycyclic aromatic hydrocarbons (PAHs) and spheroidalcarbonaceous particles (SCPs) in marine sediment cores from Admiralty Bay,King George Island, AntarcticaCesar C. Martins a , * , Marcia C. Bcego b, Neil L. Rosec, Satie Taniguchi b, Rafael A. Loureno b,Rubens C.L. Figueira b, Michel M. Mahiques b, Rosalinda C. Montone ba Centro de Estudos do Mar da Universidade Federal do Parana , Caixa Postal 50.002, 83255-000 Pontal do Sul, Pontal do Parana PR, Brazilb Instituto Oceanogra co da Universidade de Sa o Paulo (IO/USP), Praa do Oceanogra co, 191, 05508-120 Sa o Paulo SP, Brazilc Environmental Change Research Centre, University College London, Gower Street, London, WC1E 6BT, UK

SCPs and PAHs indicate the increase in human activities in a sub-Antarctic region.

a r t i c l e i n f o

Article history:Received 5 May 2009Received in revised form6 July 2009Accepted 17 July 2009

Keywords:AntarcticaFly-ashHydrocarbonsSediments

a b s t r a c t

This paper describes the rst results of polycyclic aromatic hydrocarbons (PAHs) and spheroidal carbo-naceous particles (SCPs) in sediment cores of Admiralty Bay, Antarctica. These markers were used toassess the local input of anthropogenic materials (particulate and organic compounds) as a result of theinuence of human occupation in a sub-Antarctic region and a possible long-range atmospheric trans-port of combustion products from sources in South America. The highest SCPs and PAHs concentrationswere observed during the last 30 years, when three research stations were built in the area and industrialactivities in South America increased. The concentrations of SCPs and PAHs were much lower than thoseof other regions in the northern hemisphere and other reported data for the southern hemisphere. ThePAH isomer ratios showed that the major sources of PAHs are fossil fuels/petroleum, biomass combustionand sewage contribution generally close to the Brazilian scientic station.

2009 Elsevier Ltd. All rights reserved.

1. Introduction

Antarctica can no longer be considered a pristine environmentdue to both direct and indirect contaminant input from anthropo-genic sources. Human presence on the continent has resulted inatmospheric pollution, fuel spills to both marine and terrestrialenvironments and the dumping of refuse and release of sewagewaste into the surrounding Southern Ocean ( Waterhouse, 2001 ). Inaddition, the presence of persistent organic pollutants (POPs), suchas chlorinated pesticides and polychlorinated biphenyls (PCBs)(Montoneet al., 2005 ), and anthropogenic radionuclides as 90Srand137Cs (Desideri et al., 2003 ) have shown the long-range atmo-spheric transport of emissions from tropical and temperate regionsto the south polar areas.

King George Island has been one of the most visited and denselypopulated areas of Antarctica since 1819 when it was discovered byWilliam Smith ( Braun et al., 2001 ). The late-19th to early-20thcentury was a great period of exploration of the sub-Antarcticislands as well as the beginning of large-scale factory ship whaling

while the natural sheltered harbours of King George Island wereexploited by sealers and whalers ( Headland, 1989 ). The rstpermanent scientic station (Station G, UK) on the island wasestablished at Admiralty Bay in 1947 and was occupied until 1961(Headland and Keagep, 1985 ). In 1977, the Polish station HenrykArctowski was established followed by the Brazilian Estaa oAnta rtica Comandante Ferraz (EACF) station in 1984. The currentscientic presence in the Bay was completed in 1989 with thePeruvian research station Machu Picchu ( Martins et al., 2004 ). Inaddition to the scientic stations, there has been intense touristactivity in the area. From 1989/1990 to 1998/1999, the number of tourists visiting King George Island in the austral summer increasedfrom c.3200 to 4200 and is projected to increase to more than11000 for the austral summer season in 2008/2009 ( http://www.iaato.org/tourism_stats.htm ).

The human presence in the region has been made possible bythe extensive use of fossil fuels, both as fuel for re-supply vessels,tourist ships, small research boats and terrestrial vehicles and as anenergy source for the heating and lighting of the research stations.Fossil fuel combustion can be consideredone of the most importantanthropogenic sources in terms of environmental contaminationand the use of specic indicators, such as polycyclic aromatichydrocarbons (PAHs) and spheroidal carbonaceous particles (SCPs),

* Corresponding author. Tel./fax: 55413455 3623.E-mail address: [email protected] (C.C. Martins).

Contents lists available at ScienceDirect

Environmental Pollution

j ou rna l homepage : www.e l sev i e r. com/ loca t e / envpo l

0269-7491/$ see front matter 2009 Elsevier Ltd. All rights reserved.

doi:10.1016/j.envpol.2009.07.025

Environmental Pollution 158 (2010) 192200
http://www.iaato.org/tourism_stats.htmhttp://www.iaato.org/tourism_stats.htmmailto:[email protected]://www.sciencedirect.com/science/journal/02697491http://www.elsevier.com/locate/envpolhttp://www.elsevier.com/locate/envpolhttp://www.sciencedirect.com/science/journal/02697491mailto:[email protected]://www.iaato.org/tourism_stats.htmhttp://www.iaato.org/tourism_stats.htm


2/9

produced by this process, may therefore be used to determine therecord of human activities in Antarctica and remote contaminationtransported to the continent.

Polycyclic aromatic hydrocarbons are organic pollutants preva-lent in the sediments of marineand freshwater environments. PAHsare mainly derived from anthropogenic sources including thecombustion of fossil fuels, sewage, vehicular emissions and spill-ages of petroleum and its by-products containing complexmixtures of petrogenic PAHs ( Bouloubassi and Saliot, 1993; Yunkerand Macdonald, 2004 ). The higher molecular weight PAHs(MW 202) with 46 aromatic rings, such as uoranthene, pyrene,benzo(a)anthracene, chrysene, benzo(b k)uoranthene, ben-zo(a e)pyrene, indene(1,2,3-c,d)pyrene, dibenzo(a,h)anthraceneand benzo(g,h,i)perylene, are frequently related to combustionprocesses ( Yunker et al., 2002 ) and are highly toxic to organismsdue to their carcinogenic and mutagenic potential ( UNEP, 1992;Yang et al., 2008 ). Heavier PAHs are less subject to microbialdegradation than PAHs with 23 rings, particularly in Antarcticregions where low air temperatures inuence degradation rate(Pelletier et al., 2004; Coulon et al., 2005 ). Once in the watercolumn, these compounds bind to suspended particulate matterand can be easily transported to the surface sediments. Therefore,these compounds are suitable for investigating historical inputs of anthropogenic matter into sedimentary environments.

Spheroidal carbonaceous particles (SCPs) are a component of y-ash produced from the high temperature combustion of fossilfuels ( Fig. 1). They are not formed by any natural process andtherefore, in the environment, provide an unambiguous indicationof atmospherically deposited contamination from human sources(Rose and Rippey, 2002; Rose and Monteith, 2005 ). As a conse-quence, SCPs have been used extensively in lake sediment studiesto provide a historical record of trends in atmospheric contami-nation ( Rose et al., 1995; Ferna ndez et al., 2002; Yang and Rose,2003 ). As well as being indicators of atmospheric deposition, SCPsare also contaminants in their own right as trace metals (e.g. Coleset al., 1979; Seigneur et al., 2005 ) and organic pollutants ( Ohsaki

et al., 1995; Ghosh et al., 2003 ) are adsorbed onto their surfaces.The aims of the present study were to describe the temporal

distribution of higher molecular weight PAHs in short sedimentcores ( < 20 cm) collected in three different inlets of Admiralty Bay,where human activities have intensied over the last 30 years, andto assess the local input of anthropogenic material (particulate andorganic compounds) as result of the inuence of human occupationin this sub-Antarctic region. As there are no sources of SCPs inAntarctica they were used to evaluate possible long-range atmo-spheric transport of combustion products from sources in SouthAmerica.

2. Site and methods

2.1. Study area

King George Island is located at approximately 63 S in the South ShetlandsIslands ( Fig. 2). About 92% of its land surface is covered by ice ( Santos et al., 2007 ).Admiralty Bay is the largest bay on the island and is a deep fjord-like embaymentwith an area of 131 km 2 and maximum depth of 530 m ( Rakusa-Suszczewski, 1980 ).Thepresenceof this deep natural bayleddirectly totheestablishmentand useof the

area for scientic research stations, while the considerable ice-cover of the islandand practicalities associated with the re-supply of research stations by sea meansthat most human activities remain close to the bay. The high ecological importanceof this region led to the creation of an Antarctic Site of Special Scientic Interest (SSI8) in the west of the bay where tourism activities are prohibited. In addition,Admiralty Bay and its catchment are classied as an Antarctic Specially ManagedArea (ASMA) and the Scientic Committee on Antarctic Research (SCAR) has rec-ommended environmental studies on present-day conditions of the region ( Santoset al., 2006 ).

The main local sources of emissions from fossil fuel combustion are associatedwith the three research stations located in Admiralty Bay. The Brazilian EACF islocated on the Martel Inlet ( Fig. 2) and is a medium sized research station suppliedby six diesel generators. Each year the station uses 320,000 L of Arctic grade dieseloil with an average monthly consumption of about 23 tons of fuel ( Bcego et al.,2009 ). Furthermore, an incinerator and vehicular exhaust emissions are potentialsources of PAHs to the local atmosphere. About 92.5% of total particulate massgenerated at EACF is concentrated in the Keller Peninsula region (the ice-free areawhere the Brazilian Station is located) within a radius of c.1500 m ( Leal et al., 2008 ).The Polish Henryk Arctowski station is located in the entrance of Ezcurra Inlet(Fig. 2) andconsumes a totalof around100,000 L of dieselfuelper year. ThePeruvianMachu Picchu Station is located on the Mackellar Inlet ( Fig. 2) and presently isused only for summer operations ( COMNAP, 2001).

2.2. Sampling and analytical methodologies

2.2.1. Sediment sampling Sedimentcores weretaken byscubadiver from sitesA, B,and D andby mini-box

corer (25 25 55cm) ( Figueiredo and Brehme,2000 ) fromsitesC and E duringthe2005/2006 austral summer ( Table 1 , Fig. 2). In general, the cores were sectioned at1 cm intervals, placed into pre-cleaned aluminum foil and stored at 20 C. Thesediments were freeze-dried. Around 1 g was sub-sampled for SCP analysis and therest was carefully homogenized in a mortar, sieved through a stainless steel mesh(250 mm) and stored in glass bottles until laboratory analysis.

2.2.2. SCPs analysisSCPs were determined according to the procedure described in Rose (1994) and

involved the removal of unwanted sediment fractions by sequential acid attack. Asub-sample of the resulting suspension was evaporated onto a coverslip, mountedonto a microscope slide and the SCPs counted at 400 magnication using a lightmicroscope. SCP concentrations are expressed as number of particles per gram drymass (gDM 1). The methodology has a detection limit of 50100 gDM 1 anda mean recovery rate of > 95%. Reproducibility was good, with the 95% condenceinterval being less than 10% of the mean (based on n 15 samples) ( Rose, 1990,1994 ). Analysis of sample blanks resulted in no detectable SCP concentrations.Reference standard samples ( Rose, 2008 ) were analysed along with the sedimentsamples and the results were not signicantly different from the publishedconcentration.

Fig. 1. Spheroidal carbonaceous particle (SCP) photographed by scanning electron microscopy (A) and a conventional light microscope (400 ) (B).

C.C. Martins et al. / Environmental Pollution 158 (2010) 192200 193


3/9

2.2.3. PAH analysis

Thecomplete analytical protocol for PAH analysishas beendescribed in detail byUNEP (1992) . Briey, 25 g of sediment was Soxhletextracted over 8 h using 80 mL of a mixture of (1:1) dichloromethane (DCM) and n-hexane. A mixture of surrogates(naphthalene-d 8, acenaphthene-d 10, phenanthrene-d 10, chrysene-d 12, andperylene-d12) was added beforeeach blankand sample extraction. The DCM/n-hexaneextractwas puried by column chromatography using 5% deactivated alumina (1.8 g) andsilica (3.2g). The elutionwas undertaken with10 mL n-hexane(fraction 1 aliphatichydrocarbons not analysed) and 15 mL (3:7) DCM/n-hexane mixture (fraction 2 PAHs). An aliquot of 2 mL from each extract was injected for gas chromatographicanalysis. The PAH analyses were performed with an Agilent GC model 6890 coupledto a Agilent MassSpectrometer Detector (model 5973) and an Ultra-2 capillaryfusedsilica column coated with 5% diphenyl/dimethylsiloxane (50 m, 0.32 mm ID and0.17 mm lm thickness). Helium was used as the carrier gas. The oven temperaturewas programmed from 40 C, holding for 2 min, 4060 C at 20 C min 1, then to250 C at 5 C min 1 and nally to 320 C at 6 C min 1 where this temperature washeld for 20 min. Data acquisition was undertaken in the single ion monitoring mode(SIM). Compounds were identied by matching retention times and ion mass frag-ments with results from standard mixtures of PAHs from the National Institute of Standards and Technology, USA.

Procedural blanks contained a few minor contaminant peaks but these did notinterfere with the analyses of target compounds. Detection limits (DL) for each PAH

was approximately 0.50 ng g 1 dry weight. A spiked-recovery experiment was

conducted simultaneously with the extraction of the samples and the recoveriesranged from 53% 11(benzo(k)uoranthene) to 70% 16 (indene(1,2,3-c,d)pyrene)(N 4) for the 11 higher molecular weight PAHs analysed (uoranthene, pyrene,benzo(a)anthracene, chrysene, benzo(b k)uoranthene, benzo(a e)pyrene,indene(1,2,3-c,d)pyrene, dibenzo(a,h)anthracene and benzo(g,h,i)perylene). Surro-gate recoveries were ( N 72): 110% 15 (phenanthrene-d 10),124% 16 (chrysene-d12) and 97% 15 (perylene-d 12). To evaluate the precision of the analysis, tworeplicates of the eld samples were analysed. The relative standard deviation (RSD)of the replicates varied between 4 and 11%. Regular analyses of reference materialfrom the National Institute of Standards and Technology, USA, and annual partici-pation in the intercomparison exercises promoted by the Marine EnvironmentLaboratory of International Atomic Energy Agency (MEL-IAEA) have shown satis-factory quality control.

2.2.4. Dating of the sedimentary coresSediment samples of 2030 g were homogenized and transferred to plastic

containers for gamma spectrometry. Samples were counted for 90,000120,000 susing a hyper-pure Gedetector (modelGEM 60190,by EGG&ORTEC)with a resolutionof 1.9 keVfor the1332.40keV 60Co peak. Cesium-137 activity wasassayed bymeansof its peak at 661 keV ( Figueira et al.,1998 ). Background energies were subtracted fromthe photo-peak areas and self-absorption corrections were calculated. Countingerrorswerealwayswithin9%. Comparisonbetweenthe linearregression curves of thebackground and sediment samples permitted the determination of sediment radio-nuclide activity, after removing the background activity for each. Detector calibrationwasperformedby means of several gamma emitting nuclides( 210Pb, 226Ra and 137 Cs).International Atomic Energy Agency (IAEA) reference materials were employed todetermine the detector counting efciency in the radionuclide peak region.

3. Results and discussion

3.1. 137 Cs sediment proles

The vertical distribution of 137Cs activity for each core is pre-

sented in Fig.3. Previous studies on sedimentation in Admiralty Bay

AB

C

D

E

Map-03

A d m i r a l t y

B a y

12

3

(1) Martel Inlet(2) Mackellar Inlet(3) Ezcurra Inlet

A ABB

CC

DD

EE

A d m i r a l t y

B a y

(1) Martel Inlet(2) Mackellar Inlet(3) Ezcurra Inlet

Fig. 2. Map 01: Antarctic Continent; Map 02: King George Island; Map 03: Sampling stations at Admiralty Bay.

Table 1Sediment cores collected at Admiralty Bay, King George Island, Antarctica.

Site Name LATITUDE LONGITUDE Depth(m)

Mean post-1963sedimentationrate (cm.y 1)

A Ferraz Station 62 05.033 0S 058 22.898 0W 20 0.35 0.03B Ulmann Point 62 05.169 0S 058 22.159 0W 20 0.11 0.01C Botany Point 62 05,831 0S 058 21,047 0W 30 0.28 0.03D Mackelar Inlet 62 04,771 0S 058 25,647 0W 17 n.cE Monsimet Cove 62 10.420 0S 058 34.060 0W 20 0.13 0.01

n.c: not calculated.

C.C. Martins et al. / Environmental Pollution 158 (2010) 192200194


4/9

found rates of 0.35 cmy 1 close tosite A ( Figueira et al., 2005 ) whileYoon et al. (2000) found a mean sedimentation rate of 0.23 cm y 1

(since 1200 yr BP) from 14C-dating. In general, our results werefound to be relatively close to these data.

The estimated age for each section of the cores was based on themaximum activity of 137Cs, corresponding to 19631965, theperiodof maximum fallout in the Southern Hemisphere due to atmo-spheric nuclear weapons testing ( Mackenzie, 2000; Abril, 2003 ).The sediment thickness between the depth of maximum 137Csactivity and the core top was used to estimate the mean sedi-mentation rate for this period ( Zuo et al., 1991 ), and these resultsare presented in Table 1.

The elevated levels of 137Cs activity in sections deeper than thosecorresponding tothe maximum fallout (e.g. 17 cm core A; 5.5 cm coreB; 13.5 cm core C,and7.5cm core E;indicatedby * in Fig. 3)can be attributed to thermonuclear tests performed in the Antarcticatmosphere. According to Stevens (1997) , an American nuclear testdetonatedthree bombs over Antarctica on 27th and30th Augustand6th September 1958 ( Farrell, 2005 ). Wolff et al. (1999) , showingchanges in betaradioactivityin uncompacted snowat locationscloseto the Weddell Sea, reported peaks in the late-1950s and slightlyhigher peaksin theearly-1960sfollowedby a signicantdecline.Thistemporal pattern shows good agreement with our results.

By contrast, the elevated 137Cs activity found close to the top of the cores (e.g. 1.5 cm core B; 4.5 cm core C; and 2.5 cm core E;marked with ** on Fig. 3), may be associated with previously

deposited 137

Cs stored in catchment snow since the 1950s whichhas been released due to intensive snow melt in recent years andsubsequent runoff to the marine environment. This has also beenrecorded by Godoy et al. (1998) in surface soil and sedimentsamples collected during 1986 and 1992. Setzer and Roma o (2008)studied a temporal series of air temperatures from Admiralty Baycovering the last 60 years and showed the highest temperatureoccurred in 1989 and a systematic increase for the last 20 years(19862006). Trends calculated by Chapman and Walsh (2007) forthe 19582002 period suggest modest warming over much of the60 90 S domain. All seasons show warming, with winter trendsbeing the largest at 0.172 C decade 1 while summer warmingrates are only 0.045 C decade 1.

The precision of sedimentation rates determined by 137Cs

activity may be affected by processes related to vertical migration

of this radionuclide. Factors such as sediment-type, chemicalproperties, organic matter content and climatic conditions of thestudy area could affect the 137Cs distribution in sediment proles( Jia et al., 1999; Al-Masri, 2005 ). Taking this limitation intoconsideration, the established dates obtained in this study remainuseful in explaining the variation in SCP and PAH sedimentconcentrations.

3.2. SCP concentrations

The SCP concentration proles are shown in Fig. 4. Wheredetectable, all concentrations were very low. Core A, collected close

to the Brazilian station, showed the highest number of samples inwhich SCPs were detected as well as the highest SCP concentrationinAdmiraltyBay(c.650gDM 1; in 1995/1997). Theearliest presenceof SCPs in core A was detected in 1983/1986 and the concentrationremained reasonably consistent until the present, except between1989/1995 and 1997/2000 when SCPs were not found. SCPs inCore B, collected at Ulmann Point and located 2.0 km east of theBrazilian station, were rst detected in 1988/97 after which theconcentration remainedreasonablyconstantthrough to thepresent.SCPs were only found in one section (23 cm) of core D fromMackellar inlet, close to the Peruvian station, where the concen-trationwasc. 300 gDM 1. No SCPs weredetected in core E, collectedinsideof Ezcurra inlet andSCP analysis was notundertaken oncore Ccollected at Botany Point in the Martel Inlet ( Fig. 2). These data

indicate a low level of SCP contamination across Admiralty Bay andgiven the very low concentrations, we can only record a low butdetectable level. Although the highest concentrations are observedclose to the Brazilian station, the condence intervals on the data(Fig. 4) are such that no spatial inferences can be made.

Where SCP concentrations in Admiralty Bay exceed the limit of detection, concentrations (c. 200650 gDM 1) are much lower thanin other remote areas of the world or in other regions of thesouthern hemisphere. For example: a remote lake in north-westScotland, Loch Coire nan Arr ( > 10,000 gDM 1) (Rose and Rippey,2002 ); European mountain lakes from Svalbard, Norway, U.K. andIreland, Tatra Mountains, Tyrol and Slovenia, the Western Alps, thePyrenees and the Iberian Peninsula ( Rose et al.,1999 ); Laguna Chicade Sa o Pedro, close to Concepcion city (around 900.000 inhabi-

tants), Chile (>

8000 gDM1

) (Chirinos et al., 2006 ). It is known that

Core E - Monsimet Cove

0

2

4

6

8

01

21

41

61

81

02

22

42

62

0.65.40.35.10.0

[ 731 gk.qB(]sC 1- )

d e p

t h ( c m

)

5691-3691

Core C - Botany Point

0

2

4

6

8

01

21

41

61

81

02

22

42

62

0.65.40.35.10.0

[ 731 gk.qB(]sC 1- )

d e p

t h ( c m

)5691-3691

Core B - Ulmann Point

0

2

4

6

8

01

21

41

61

81

02

22

42

62

0.65.40.35.10.0

[ 731 gk.qB(]sC 1- )

d e p

t h ( c m

)

5691-3691

Core A - Ferraz station

0

2

4

6

8

01

21

41

61

81

02

22

42

62

0.65.40.35.10.0

[ 731 gk.qB(]sC 1- )

d e p

t h ( c m

)

5691-3691

*

*

*

*

****

**

Fig. 3. 137Cs activity concentration (in Bq.kg 1 dry weight) for different sediment cores of Admiralty Bay, King George Island, Antarctica. * represents 1958 bomb tests over

Antarctica; **

marks the possible inuence of intense snow melt (see text for details).



5/9

SCPs are only produced by the high temperature combustion of fuels such as coal and oil in industrial facilities and these are notpresent anywhere in the Antarctic region. The long-range transportof these particulate contaminants from remote sources is therefore

the means by whichSCPs canreach the sediments of Admiralty Bay.A compilation of worldwide measurements for black carbon (BC),produced by burning biomass and fossil fuel combustion, showsthat Brazil and Africa may be considered the major sources of BC inthe southern hemisphere ( Pereira et al., 2006 ). Similarly, Pereiraet al. (2004) , employing SEM-EDS microanalysis of insolubleparticulates from an ice core from King George Island and from theatmosphere in Chilean Patagonia, found that 95% of continentaldust in the north of the Antarctic Peninsula could be explained byatmospheric transport from Patagonia and it seems likely that sucha mechanism is also responsible for the transport of SCPs fromSouth America.

The detectable presence of SCPs in Admiralty Bay was observedover a similar period to that in which scientic activities have

increased in thearea.However, sucha comparisonis coincidental asSCP concentrations have remained low and reasonably consistentover the last 25 years as scientic activities have increased. Thepresence of SCPs in Admiralty Bay sediments therefore reectsthe increase of emissions from fossil fuel combustion in South

America from electricity generation and other sources. A similartrend is also seen in lake sediment records from the AntarcticPeninsula (Rose, unpublished data). Any spatial differences in SCPconcentrations across Admiralty Bay are likely to be the result of

sedimentological processes and possibly the release of SCPs previ-ously deposited and released with melted snow and ice as specu-lated for the 137Cs data. The presence of SCPs in Admiralty Bayconrms previous studies (e.g. Montone et al., 2005; Evangelistaetal.,2007 ) of long-rangetransportof anthropogenic materials fromseveral regions of the globe to the Antarctic Peninsula.

3.3. PAH concentrations

The sediment concentration proles for PAHs are shown inFig. 5. As with the SCPs, the highest mean concentrations weredetected in the most recent sediments of core A. The maximumconcentration occurred at 3.5 cm (454.9 ng g 1) in the sedimentsdated to 1995/1997, the same section in which the highest

concentration of SCPs was observed. Relatively high concentrationsof PAHs were also detected in the lower sections of this core, e.g. in1969/1972 (106.3 ng g 1) and 1957/1966 (46.9 ng g 1). This couldbe associated with activities at the British Station G (establishedwhere Ferraz station is now located) until the early 1960s and the

Core A - Ferraz station

081021060

6002-0002

0002-7991

7991-5991

5991-2991

2991-9891

9891-6891

6891-3891

3891-0891

0891-7791

7791-2791

2791-9691

9691-6691

6691-7591

e s

t i m a

t e d d a t e

PAHs (ng.g -1) PAHs (ng.g -1)PAHs (ng.g -1)PAHs (ng.g -1)

005

Core E - Monsimet Cove

9362310

6002-8991

8991-1991

1991-3891

3891-5791

5791-8691

8691-0691

0691-2591

2591-4491

4491-7391

7391-9291

9291-1291

9291-4191

4191-6091

6091-8981

d.n

Core B - Ulmann Point

9362310

1997-2006

1988-1997

1979-1988

1970-1979

1961-1970

1951-1961

1942-1951

1933-1942

1915-1933

1906-1915

1897-1906

1888-1897

1879-1888

1870-1879

1861-1870

Core C - Botany Point

9362310

2002-2006

1999-2002

1995-1999

1992-1995

1988-1992

1985-1988

1981-1985

1977-1981

1974-1977

1970-1974

1967-1970

1963-1970

1960-1963

1956-1960

1952-1956

1949-1952

A

B

C

D

Fig. 5. Combustion-derived PAHs concentration (in ng g 1 dry weight) in different sediment cores of Admiralty Bay, King George Island, Antarctica. Lines AD indicate the

correspondent dates between the cores. A (1997/992006); B (1988/911996/98); C (1979/831987/90); D (1978/821968/70). n.d: not detected.

276

504

275 302

450

285253

643

0

200

400

600

800

1000

1200

A 0-1 A 1-2 A 3-4 A 6-7 A 7-8 B 0-1 B 1-2 D 2-3

M D g ( s

P C S

1 - )

(2003/06) (2000/03) (1986/89)(1995/97) (1983/86) (1997/2006) (1988/1997) not dated

limit of detection (100 gDM -1)

Fig. 4. Spheroidalcarbonaceous particles(in gDM 1) fordifferent detectablesediment coresof AdmiraltyBay,King George Island, Antarctica. Error barscalculatedwith 90%condenceinterval. The marked area represents the minimum value attributed for the highest SCPs concentration (Core A 34) and the maximum value to the lowest SCPs (Core A 67).



6/9

increase of shipping trafc in the region of the Antarctic Peninsulaafter the World War II, motivated by the establishment of severalArgentine and Chilean stations, such as Almirante Brown AntarcticBase (1951), Bernardo OHiggins Station (1948), Captain Arturo PratBase (1947), Jubany Station (1953) and Presidente Eduardo FreiMontalva Base/Villa Las Estrellas (1969). SCPs were not detected incore A during this period probably due to the absence of largeindustrial sources in South America in the 1960s and early-1970scompared with the last 20 years. This suggests that PAHs could bemainly be derived from local sources, such as low temperature coaland wood combustion, which do not produce SCPs. A slightincrease in PAH concentration in core A can be seen between theperiod of 1977/1980 and 1992/1995 (10.868.1 ng g 1) and iscoincident with the period when three research stations wereestablished in the region, during the early-1980s, when theincrease in the use of snow vehicles and local boating associatedwith station activities occurred.

The sewageefuent discharged by theBrazilian stationmight beconsidered an important source of PAHs to the bay over the last 15years. In the 1995/1996 austral summer, efuents from the Brazil-ian Research Station began to be discharged close to site A andcould explain the high concentration in 1995/1997, possibly causedby a sewage spillage, a lack of maintenance or by cleaning proce-dures in the rst years of sewage treatment. The decreasedconcentrations between 1997 and 2006 may then reect theimprovementof sewage treatment facilities when a septic tank wasreplaced by a better system incorporating lters to reduce therelease of organic matter and associated PAHs.

The PAH concentrations for core B are low but show anincreasing trend from the 1950s to a peak in 1988/1997 followed bya decline to the surface. PAH concentrations in core C are also lowbut show a considerable increase in the most recent sample 2002/2006. The concentration of PAHs observed in core C related to theperiod of 1952/1956 (11.8 ng g 1) is slightly increased over themean concentration either side of this period and the timing of thisrelatively high value appears be coincident with the establishment

of the British station G.The distribution of PAHs in Martel Inlet can be related to the

scientic activities of Comandante Ferraz station, established in1984 where personnel numbers and research activities haveincreased over the last 25 years. In the ve rst years of its oper-ation, the population of the station varied between 10 and 15people and research activities were limited to studies on terrestrialand atmospheric environments. More recently, the station hasexpanded with a summer population of between 40 and 60 people,and 10 to 15 people in winter. Thus more vehicles, fuel, food andfacilities have been required to support this expansion ( Bcegoet al., 2009 ). A further consideration relates to the atmospherictransport of particulate matter produced by the Brazilian station.A model proposed by Leal et al. (2008) estimated the atmospheric

dispersion of total aerosols generated by the two main local sources(Comandante Ferraz and Henryk Arctowski Antarctic stations) inAdmiralty Bay and predicted that the highest levels of particlesemitted would be concentrated around 1 km east and 3 km north of the Brazilian station. This model also showed the occurrence of anelevated concentration of particulate matter at a location close toUlmann Point, in agreement with our PAH data.

The PAH concentrations in core D were very low ( < 6.0 ng g 1)and close to the detection limits for the majority of the 11combustion-derived PAHs analysed. The historical record of humanoccupation in Mackellar Inlet could not be inferred from thesedata. By contrast, the vertical prole of PAHs in core E indicates theincrease in scientic activities undertaken around the EzcurraInlet. The highest concentrations occurred between 1977 and

1989, coincident with the establishment of the Arctowski Polish

station, but remain elevated through to the uppermost sedimentlevels. These results are in agreement with the atmosphericdispersion model proposed by Leal et al. (2008) which indicatedthat dispersion of particles emitted by Comandante Ferraz andArctowski stations to the Mackellar and Ezcurra Inlets was notimportant probably due to the topographic retention of particlesand compounds.

The monitoring of PAH concentrations in the sediments of Antarctica has been described in a series of studies related tosporadic anthropogenic hydrocarbon inputs for different Antarcticenvironments such as Palmer station, USA ( Kennicutt et al., 1992 )and Admiralty Bay ( Martins et al., 2004 ). The maximum concentra-tion observed in our study was in core A (454.9 ng g 1), and around78% of all samples analysed contained PAH concentrations below30.0ngg 1. Ingeneral,these PAHconcentrationswere lowcomparedto other recent studies in Antarctic regions for example, McMurdoStation, USA (6215024 ng g 1 sum of 45 compounds) ( Kim et al.,2006 ); Jubany Station, Argentina (281908 ng g 1 for 25 PAH ana-lysed) ( Curtosi et al., 2007 ), James Ross Island, close Czech Republicstation (12005 ng g 116 US EPA PAH) (Klanova et al., 2008 ).

3.4. Sources of PAHs

Although the higher molecular weight PAHs are normallyassociated with combustion processes, they are also found insewage efuents, small oil spillages and natural sources includingpetroleum seeps and post-depositional transformation of biogenicprecursors ( Young and Cerniglia, 1995 ).

To conrm the combustion origin of PAHs, the following threePAH isomer pair ratios were used as tracers to identify possiblesources of PAH in sediments: benzo(a)anthracene/(benzo(a)-anthracene chrysene) (BaA/228); uoranthene/(uoranthene pyrene) (Fl/(Fl Py)); and indene(1,2,3-c,d)pyrene/(indene(1,2,3-c,d)pyrene benzo(g,h,i)perylene) (IP/(IP BghiP)). Based onthe PAH isomer pair ratio measurements compiled by Yunker et al.(2002) , the ranges for different sources are: (a) Fl/(Fl Py)

ratio < 0.40 indicates dominance of petroleum, 0.400.50 indicatespetroleum combustion, and > 0.50 combustion of coal, grasses andwood; (b) BaA/228 ratio < 0.20 indicates petroleum, 0.200.35petroleum and combustion, and > 0.35 combustion; and, (c) IP/(IP BghiP) < 0.20 indicates petroleum, 0.200.50 petroleumcombustion, and > 0.50 combustion of coal, grasses and wood.These ratios were only calculated for those sediment sampleswhere the combustion-derived PAH concentrations exceeded10.0 ng g 1 as concentrations of individual PAHs close to detectionlimit could produce a false interpretation.

PAH ratios were calculated for each sample of core A and theseare shown in Fig. 6. The Fl/(Fl Py) isomer pair ratio suggests thatPAHs are derived primarily from biomass and coal combustion(67%) with a smaller contribution from petroleum combustion

sources (33%) and no contribution from unburned petroleum. TheBzA/228 and IP/(IP BghiP) ratios show the predominance of combustion processes, specically biomass and coal combustion asindicated by the second ratio. For the other cores, the elevatedconcentrations in the upper samples of cores B and C indicateda petroleumcombustionsource(coreB,12 cm;Fl/(Fl Py) 0.48),(core C, 01 cm; Fl/(Fl Py) 0.50; IP/(IP BghiP) 0.44) (core E04 cm: Fl/(Fl Py) 0.420.45; IP/(IP BghiP) 0.440.46). Thevalues of BaA/228 ratio varied between 0.39 and 0.47 conrmingcombustion processes as the main origin of PAHs in these sections.These combustion sources may be the diesel generators at theresearch stations, the fuel for boats and terrestrial vehicles (such asquad-bikes) or heavier fuels such as kerosene (used for helicopters)used within the vicinity of the Brazilian station and other sites

around Admiralty Bay. The isomer pair PAH ratios showed that the



7/9

contribution from these sources is more evident close to the Polishstation from the date of its foundation (1977) through to thepresent; during the implementation period for the Brazilian station(1983/1989) and over the last ten years as a result of increasedactivity across Martel Inlet (Botany and Ulmann point). Thepredominance of PAHs from biomass or coal combustion was onlyfound close to the Brazilian station and biomass PAHs might beattributed to organic material burned in the incinerator establishedin 1987 and operating at a temperature between 450 and 600 C.Possible sources of PAHs in older sediments include thecombustionof coal and wood as a result of activities at the British station G.

Although Station G was demolished and removed by members of the Brazilian station in 1995/1996, fragments of coal and charredwood may be still be found in the vicinity of the old station.

An additional, and important, source of heavier PAHs in MartelInlet seems to be the sewage efuent discharged by the Brazilianstation between 1995 and 2006. The local sewage input is close tothe site of core A and may be responsible for the introduction of biomass PAH from domestic waste. Sewage efuents have previ-ously been considered a potential source of heavier PAHs ( Villaret al., 2006 ). Sludge samples from six wastewater treatment plantsshowed a high content (mean 89.7%) of individual PAHs with 46aromatic rings out of the total PAH extractable fraction ( Oleszczuk,2008 ). Lazzari et al. (2000) found uoranthene and pyreneto be themost abundant PAH in sewage sludge and these high concentra-

tions can be explained by the presence of domestic sewage water(Gomez-Rico et al., 2007 ). Medeiros and B cego (2004) founda value of 0.58 for the ratio Fl/(Fl Py) in sediments collectedimmediately beyond a sewageoutfall in Santos City, Brazil. Samplesfrom the sewagesludge of the Brazilian station, collected during theaustral summer of 1996/97 gave values for the Fl/(Fl Py) and IP/(IP BghiP) ratios of 0.580.71 and 0.530.64, respectively. Thesevalues werecloseto thosefound forthe sediment of core A after theimplantation of sewage facilities at the EACF station (Fl/(Fl Py) 0.480.57) and (IP/(IP BghiP) 0.520.54).

The long-range transport of PAHs produced by biomass or fossilfuel combustion in other regions of the world may be of littleimportance compared to this local source and this is supported bythe low concentrations of SCPs found in Admiralty Bay. It is

important to note that the PAH signature could be altered by

biological (e.g., bacterial degradation), chemical (e.g., oxidation andreduction), and physical (e.g., air mass mixing and sedimentresuspension) processes during transport and after deposition tothe sediments ( Oros and Ross, 2004 ). However, the application of these ratios indicates that the primary source of PAHs to AdmiraltyBay are combustion processes and sewage efuent from the Bra-zilian station. Sewage disposal has been attributed as a source of trace metals and organic compound enrichment in sedimentscollected near Ferraz station ( Martins et al., 2002; Santos et al.,2005 ) in support of our results.

4. Conclusions

The record of human impact on Admiralty Bay, King GeorgeIsland wasassessedby the use of the sediment indicators polycyclicaromatic hydrocarbons (PAHs) and spheroidal carbonaceousparticles (SCPs).

Theconcentrations of SCPs are low, reasonablyconsistent acrossAdmiralty Bay, and consistent with the long-range transport of anthropogenic emissions from several regions of the globe,particularly South American countries.

The highest levels of PAHs were detected in the upper layers of sediment cores relating to the last 30 years and reecting theincrease in human occupation of the area, resulting in more fossil

fuel consumption, combustion of organic matter and petroleumderivatives and input of sewage efuent.The PAH isomer pair ratio analysis showed that the major

sources of high molecular weight PAHs are fossil fuels/petroleum(gasoline and diesel) in the upper levels of cores from MonsimetCove and Botany Point. Biomass combustion and sewage are themost important sources of PAHs close to the Brazilian station.

The absence of correlation between SCPs and PAHs is a result of multiple local sources of PAHs such as combustion of wood, organicmatter, vehicular emissions and the input of sewage efuent, whileSCPs are derived solely from industrial fossil fuel combustion fromoutside Antarctica. Since SCPs were detected in the sediments of Admiralty Bay, they may be considered an important tool in iden-tifying long-range transport of fossil fuel derived pollutants to

Antarctica from other regions of the world.

55.054.053.052.0

BzA/228

MixedSources

Combustion

0050520

6002-0002

0002-7991

7991-5991

5991-2991

2991-9891

9891-6891

6891-3891

3891-0891

3891-7791

7791-2791

2791-9691

9691-6691

6691-7591

g.gn(PAHs 1- )

06.005.004.003.0

Fl/(Fl + Py)

Petroleum

PetroleumCombustion

Biomass,Sew age Coal Combustion&

07.006.005.004.0

IP/(IP + BghiP)

PetroleumCombustion

Biomass &Coal Combustion

**

*

e s

t i m a

t e d d a

t e

Fig. 6. Total PAHs (in ng g 1 dry weight) and plots of PAH ratios for source identication: Fl/Fl Py, BaA/228 and IP/IP BghiP to Core A (Ferraz station). Ratios were calculated forall individual stations whenpossible. Source boundary lines are based on Yunkeret al. (2002) . ForFl/Fl Py ratio, sewagesource was assumed based on analyzes of sewage sludge of Ferraz station. * represents the sections where the Fl/Fl Py ratio indicates petroleum combustion as the main source of PAHs.



8/9

Theresultsof this work provide aninsight into thehistoricalinputof organic pollutantsfrom local andlong-range sourcesto Antarcticaand show that even low level human occupation is responsible fordetectable changes. While the sediment record provides a usefulbaseline and historical archive of contaminant input, monitoringprogrammes are required to determine continuing trends and ratesof change.

Acknowledgements

C.C. Martins wishes to thank CNPq (Brazilian National Councilfor Scientic and Technological Development) for the Post-Ph.D.Grant (154938/20068), Dr. Simon Tuner (Environmental ChangeResearch Centre, University College of London) for help with SCPanalysis, Lourival Pereira de Souza from Instituto Oceanogra co,Universidade de Sa o Paulo for help with PAH analyses, MyleneGisele do Nascimento for help with the cesium analyses and threeanonymous reviewers for their comments on the manuscript. Thisresearch forms part of the project Historic evolution of the humanactivities based on indicators of burning of fossil fuels in sedimentof the Admiralty Bay, King George Island, Antarctic Peninsula.

(CNPq 557306/20051) coordinatedby Prof. Dr. R. C. Montone. Theauthors express their gratitude to the Ferraz station staff and scubadiver Marta Markowka from the Polish station for their assistancein the collection of samples.

References

Abril, J.M., 2003. Constraints on the use of 137 Cs as a time-marker to support CRSand SIT chronologies. Environmental Pollution 129, 3137.

Al-Masri, M.S., 2005. Vertical distribution and inventories of 137Cs in the Syrian soilsof the eastern Mediterranean region. Journal of Environmental Radioactivity 86,187198.

Bcego, M.C., Zanardi-Lamardo, E., Taniguchi, S., Martins, C.C., Silva, D.A.M.,Sasaki, S.T., Albergaria-Barbosa, A.C.R., Paolo, F.S., Weber, R.R., Montone, R.C.,2009. Results from a 15-year study on hydrocarbon concentrations in water andsediment from Admiralty Bay, Antarctica. Antarctic Science 21, 209220.

Bouloubassi, I., Saliot, A., 1993. Investigation of anthropogenic and natural organicinputs in estuarine sediments using hydrocarbon markers (NAH, LAB, PAH).Oceanologica Acta 16, 145161.

Braun, M., Simoes, J.C., Vogt, S., Bremer, U., Blindow, N., Pfender, M., Saurer, H.,Aquino, F.E., Ferronz, F.A., 2001. An improved topographic database for KingGeorge Island: compilation, application and outlook. Antarctic Science 13,4152.

Chapman, W.L., Walsh, J.E., 2007. A synthesis of Antarctic temperatures. Journal of Climate 20, 40964117.

Chirinos, L., Rose, N.L., Urrutia, R., Munoz, P., Torrejo, F., Torres, L., Cruces, F.,Araneda, A., Zaror, C., 2006. Environmental evidence of fossil fuel pollution inLaguna Chica de San Pedro lake sediments (Central Chile). EnvironmentalPollution 141, 247256.

Coles, D.G., Ragaini, R.C., Ondov, J.M., Fisher, G.L., Silberman, D., Prentice, B.A., 1979.Chemical studies of stack y-ash from a coal red power plant. EnvironmentalScience and Technology 13, 455459.

COMNAP (Council of Managers of National Antarctic Programs) 2001. https://www.comnap.aq .

Coulon, F., Pelletier, E., Gourhant, L., Delille, D., 2005. Effects of nutrient andtemperature on degradation of petroleum hydrocarbons in contaminated sub-Antarctic soil. Chemosphere 58, 14391448.

Curtosi, A., Pelletier, E., Vodopivez, C.L., MacCormack, W.P., 2007. Polycyclicaromatic hydrocarbons in soil and surface marine sediment near Jubany Station(Antarctica). Role of permafrost as a low-permeability barrier. Science of theTotal Environment 383, 193204.

Desideri, D., Giuliani, S., Testa, C., Triulzi, C., 2003. 90 Sr, 137Cs, 238 Pu, 239 240 Pu and241Am levels in terrestrial and marine ecosystems around the Italian base inAntarctica. Journal of Radioanalytical and Nuclear Chemistry 258, 221225.

Evangelista, H., Maldonado, J., Godo i, R.H.M., Pereira, E.B., Koch, D., Tanizaki-Fonseca, K., Van Grieken, R., Sampaio, M., Setzer, A., Alencar, A., Gonalves, S.C.,2007. Sources and transport of Urban and biomass burning aerosol black carbonat theSouthWest AtlanticCoast.Journal of AtmosphericChemistry56, 225238.

Farrell, J.P., 2005. Reich of the Black Sun. Adventures Unlimited Press, Kempton,Illinois.

Ferna ndez, P., Rose, N.L., Vilanova, R.M., Grimalt, J.O., 2002. Spatial and temporalcomparison of polycyclic aromatic hydrocarbons and spheroidal carbonaceousparticles in remote European lakes. Water Air and Soil Pollution, Focus 2,261274.

Figueira, R.C.L., Silva, L.R.N., Figueiredo, A.M.G., Cunha, I.I.L., 1998. Goiania, ten yearslater. Instrumental Analysis by Gamma Spectrometry of Low Level Cs-137 inMarine Samples, vol. 7. IAEA, Vienna. 327329.

Figueira, R.C.L., Martins, C.C., Montone, R.C., Figueiredo, A.M.G., Tessler, M.G.,Mahiques, M.M., Cunha, I.I.L., 2005. Pb-210, Ra-226 and Cs-137 levels andsedimentation rate in Admiralty bay, Antarctic Peninsula, 1st Internationalnuclear chemistry Congress. Kusadasi, 289290.

Figueiredo Jr., A.G., Brehme, I., 2000. Amostragem Geolo gica na Pesquisa Mineral.Brazilian Journal of Geophysics 18, 269280.

Ghosh, U., Zimmerman, J.R., Luthy, R.G., 2003. PCB and PAH speciation amongparticle types in contaminated harbour sediments and effects on PAHbioavailability. Environmental Science and Technology 37, 22092217.

Godoy, J.M., Schuch, L.A., Nordemann, D.J.R., Reis, V.R.G., Ramalho, M., Recio, J.C.,Brito, R.R.A., Olech, M.A., 1998. 137Cs, 226, 228 Ra, 210Pb and 40 K concentrations inAntarctic soil, sediment and selected moss and lichen samples. Journal of Environmental Radioactivity 41, 3345.

Gomez-Rico, M.F., Font, R., Aracil, I., Fullana, A., 2007. Analysis of organic pollutantsin sewage sludges from the Valencian Community (Spain). Archives of Envi-ronmental Contamination and Toxicology 52, 306316.

Headland, K., 1989. Chronological List of Antarctic Expeditions and Related Events.Cambridge University Press, Cambridge, 730 pp.

Headland, K., Keagep, L., 1985. Activities on the king George island Group, southShetland islands, Antarctica. Polar Record 22, 475484.

Jia, G., Testa, C., Desideri, D., Guerra, F., Meli, M.A., Roselli, C., Belli, M.E., 1999. Soilconcentration, vertical distribution and inventory of plutonium, 241Am, 90Sr and137Cs in the marche region of central Italy. Health Physics 77, 5261.

Kennicutt II, M.C., McDonald, T.J., Denoux, G.J., McDonald, S.J., 1992. Hydrocarbonscontamination on the Antarctic Peninsula. I. Arthur Harbor subtidal sediments.Marine Pollution Bulletin 24, 499506.

Kim, M., Kennicutt II, M.C., Qian, Y., 2006. Molecular and stable carbon isotopiccharacterization of PAH contaminants at McMurdo Station, Antarctica. MarinePollution Bulletin 52, 15851590.

Klanova , J., Matykiewiczova , N., Macka, Z., Prosek, P., Laska, K., Klan, P., 2008.Persistent organic pollutants in soils and sediments from James Ross Island,Antarctica. Environmental Pollution 152, 416423.

Lazzari, L., Sperni, L., Bertin, P., Pavoni, B., 2000. Correlation between inorganic(heavy metals) and organic (PCBs and PAHs) micropollutant concentrationsduring sewage sludge composting processes. Chemosphere 41, 427435.

Leal, M.A., Joppert, M., Licnio, M.V., Evangelista, H., Maldonado, J., Da lia, K.C.,Lima, C., Barros-Leite, C.V., Correa, S.M., Medeiros, G., Cunha, K.D., 2008.Atmospheric impacts due to anthropogenic activities in remote areas: the Casestudy of Admiralty Bay/King George Island/Antarctic Peninsula. Water, Air, andSoil Pollution 188, 6780.

Mackenzie, A.B., 2000. Environmental Radioactivity: experience from the 20thcentury trends and issues for the 21st century. The Science of the TotalEnvironmental 249, 313329.

Martins, C.C., Venkatesan, M.I., Montone, R.C., 2002. Sterols and linear alkylben-

zenes in marine sediments from Admiralty Bay, Antarctica. Antarctic Science 14,244252.Martins, C.C., Bcego, M.C., Taniguchi, S., Montone, R.C., 2004. Aliphatic and poly-

cyclic aromatic hydrocarbons in surface sediments in Admiralty bay, kingGeorge island, Antarctica. Antarctic Science 16, 117122.

Medeiros, P.M., B cego, M.C., 2004. Investigation of natural and anthropogenichydrocarbon inputs in sediments using geochemical markers. I. Santos, SPBrazil. Marine Pollution Bulletin 49, 761769.

Montone, R.C., Taniguchi, S., Boian, C., Weber, R.R., 2005. PCBs and chlorinatedpesticides (DDTs, HCHs and HCB) in the atmosphere of the southwest Atlanticand Antarctic oceans. Marine Pollution Bulletin 50, 778786.

Ohsaki, Y., Matsueda, T., Ohno, K., 1995. Levels of coplanar PCBs, PCDDs and PCDFsin y ashes and pond sediments. International Journal of EnvironmentalAnalytical Chemistry 59, 2532.

Oleszczuk, P., 2008. Forms of polycyclic aromatic hydrocarbon in the formation of sewage sludge toxicity to Heterocypris incongruens . Science of the Total Envi-ronment 404, 94102.

Oros, D.R., Ross, J.R., 2004. Polycyclic aromatic hydrocarbons in San FranciscoEstuary sediments. Marine Chemistry 86, 169184.

Pelletier, E., Delille, D., Delille, B., 2004. Crude oil bioremediation in sub-Antarcticintertidal sediments: chemistry and toxicity of oiled residues. Marine Envi-ronment Research 57, 311327.

Pereira, K.C.D., Evangelista, H., Pereira, E.B., Simo es, J.C., Johnson, E., Melo, L.R., 2004.Transport of crustal microparticles from Chilean Patagonia to the AntarcticPeninsula by SEM-EDS analysis. Tellus, Serie B 56, 262275.

Pereira, E.B., Evangelista, H., Pereira, K.C.D., Cavalcanti, I.F.A., Setzer, A.W., 2006.Apportionment of black carbon in the south Shetland islands, AntarcticPeninsula. Journal of Geophysical Research 111, D03303.

Rakusa-Suszczewski, S., 1980. Environmental conditions and the functioning of Admiralty Bay (South Shetlands Islands) as part of near shore Antarcticecosystem. Polish Polar Research 1, 1127.

Rose, N.L., 1990. A method for the extraction of carbonaceous particles from lakesediment. Journal of Paleolimnology 3, 4553.

Rose, N.L., 1994. A note on further renements to a procedure for the extraction of carbonaceous y-ash particles from sediments. Journal of Paleolimnology 11,201204.

Rose, N.L., 2008. Quality control in the analysis of lake sediments for spheroidalcarbonaceous particles. Limnology and Oceanography: Methods 6, 172179.

http://https//www.comnap.aqhttp://https//www.comnap.aqhttp://https//www.comnap.aqhttp://https//www.comnap.aq


9/9

Rose, N.L., Monteith, D.T., 2005. Temporal trends in spheroidal carbonaceousparticle deposition derived from annual sediment traps and lake sedimentcores and their relationship with non-marine sulphate. Environmental Pollu-tion 137, 151163.

Rose, N.L., Rippey, B., 2002. The Historical Record of PAH, PCB, trace metal and yash particle deposition at the remote lake in north-west Scotland. Environ-mental Pollution 117, 121132.

Rose, N.L., Harlock, S., Appleby, P.G., Battarbee, R.W., 1995. Dating of recent lakesediments in the United Kingdom and Ireland using spheroidal carbonaceousparticle (SCP) concentration proles. The Holocene 5, 328335.

Rose, N.L., Harlock, S., Appleby, P.G., 1999. The spatial and temporal distributions of spheroidal carbonaceous y-ash particles (SCP) in the sediment records of European mountain lakes. Water, Air, and Soil Pollution 113, 132.

Santos, I.R., Silva Filho, E.V., Schaefer, C.E.G.R., Albuquerque Filho, M.R., Campos, L.S.,2005. Heavy metals contamination in coastal sediments and soils near theBrazilian Antarctic Station, King George Island. Marine Pollution Bulletin 50,185194.

Santos, I.R., Silva-Filho, E.V., Schaefer, C., Sella, S.M., Silva, C.A., Gomes, V.,Passos, M.J.A.C.R., Ngan, P.V., 2006. Baseline mercury and zinc concentrations interrestrial and coastal organisms of Admiralty Bay, Antarctica. EnvironmentalPollution 140, 304311.

Santos, I.R., Favaro, D.I.T., Schaefer, C.E.G.R., Silva-Filho, E.V., 2007. Sedimentgeochemistry in coastal maritime Antarctica (Admiralty Bay, King GeorgeIsland): evidence from rare earths and other elements. Marine Chemistry 107,464474.

Seigneur, C., Abeck, H., Chia, G., Reinhard, M., Bloom, N.S., Prestbo, E., Saxena, P.,2005. Mercury adsorption to elemental carbon (soot) particles and atmsophericparticulate matter. Atmospheric Environment 32, 26492657.

Setzer, A., Roma o, M., 2008. Atena o Pesquisador: Caiu a temperatura nos u lti-mos 11 anos em Ferraz. Proceedings of XVI Simposio Brasileiro sobre Pesquisa Antartica . 78.

Stevens, H., 1997. The Last Battalion and German Arctic, Antarctic and Andean Bases.The German Research Project, Gorman, California.

UNEP (United Nations Environment Programme),1992. Determination of PetroleumHydrocarbons in Sediments. Reference Methods for Marine Pollution Studies,vol. 20. UNEP, Nairobi, Kenya, 97 pp.

Villar, P., Callejo n, M., Alonso, E., Jimenez, J.C., Guiraum, A., 2006. Temporal evolu-tion of polycyclic aromatic hydrocarbons (PAHs) in sludge from wastewatertreatment plants: comparison between PAHs and heavy metals. Chemosphere64, 535541.

Waterhouse, E.J., 2001. Ross sea Region: a State of the environment report for theRoss Sea Region of Antarctica. New Zealand Antarctic Institute, Christchurch,New Zealand.

Wolff, E.W., Suttie, E.D., Peel, D.A., 1999. Antarctic snow record of cadmium, copper,and zinc content during the twentieth century. Atmospheric Environment 33,15351541.

Yang, H., Rose, N.L., 2003. Distribution of mercury in six lake sediment cores acrossthe U.K. Science of the Total Environment 304, 391404.

Yang, Z., Feng, J., Niu, J., Shen, Z., 2008. Release of polycyclic aromatic hydrocarbonsfrom Yangtze River sediment cores during periods of simulated resuspension.Environmental Pollution 155, 366374.

Yoon, H.I., Park, B.K., Kim, Y., Kim, D., 2000. Glaciomarine sedimentation and itspaleoceanographic implications along the fjordmargins in the South ShetlandIslands, Antarctica during the last 6000 years. Palaeogeography, Palae-oclimatology, Palaeoecology 157, 189211.

Young, L.Y., Cerniglia, E., 1995. Microbial Transformation and Degradation of ToxicOrganic Chemicals. Wiley-Liss, Inc, New York.

Yunker, M.B., Macdonald, R.W., 2004. Alkane and PAH depositional history, sourcesand uxes in sediments from Fraser River basin and Strait of Georgia, Canada.Organic Geochemistry 34, 14291454.

Yunker, M.B., Macdonald, R.W., Vingarzan,R., Mitchell, R.H., Goyette, D., Sylvestre,S.,2002. PAHs in the Fraser River basin: a critical appraisal of PAH ratios asindicators of PAH source and composition. Organic Geochemistry 33, 489515.

Zuo, Z., Eisma, D., Berger, G.W., 1991. Determination of sediment accumulation andmixing rates in the Gulf of Lions, Mediterranean Sea. Oceanologica Acta 14,253262.


env pol trends haps sources antartica

Documents