Polycyclic aromatic hydrocarbon in urban soils of an ... · Polycyclic aromatic hydrocarbon in...

Solid Earth 9 669ndash682 2018httpsdoiorg105194se-9-669-2018copy Author(s) 2018 This work is distributed underthe Creative Commons Attribution 30 License

Polycyclic aromatic hydrocarbon in urban soils of an EasternEuropean megalopolis distribution source identificationand cancer risk evaluationGeorge Shamilishvily1 Evgeny Abakumov1 and Dmitriy Gabov2

1St Petersburg State University Dept of Applied Ecology St Petersburg Russia2Institute of Biology Komi Scientific Centre Russian Academy of Sciences Syktyvkar Russia

Correspondence George Shamilishvily (george199207gmailcom)

Received 27 May 2017 ndash Discussion started 16 August 2017Revised 17 March 2018 ndash Accepted 16 April 2018 ndash Published 23 May 2018

Abstract This study explores qualitative and quantitativecomposition of 15 priority polycyclic aromatic hydrocarbons(PAHs) in urban soils of some parkland residential and in-dustrial areas of the large industrial centre of Saint Petersburg(Russian Federation) in Eastern Europe The aim of the studywas to test the hypothesis on the PAH loading differencesamong urban territories with different land use scenariosBenzo(a)pyrene toxic equivalency factors (TEFs) were usedto calculate BaPeq in order to evaluate carcinogenic risk ofsoil contamination with PAHs Results of the study demon-strated that soils within residential and industrial areas arecharacterized by common loads of PAHs generally attributedto high traffic activity in the city Considerable levels of soilcontamination with PAHs were noted Total PAH concentra-tions ranged from 033 to 810 mg kgminus1 A larger portion ofhigh-molecular-weight PAHs along with determined molec-ular ratios suggest the predominance of pyrogenic sourcesmainly attributed to combustion of gasoline diesel and oilPetrogenic sources of PAHs have a significant portion anddefine the predominance of low-molecular-weight PAHs as-sociated with petroleum such as phenanthrene Derived con-centrations of seven carcinogenic PAHs as well as calculatedBaPeq were multiple times higher than reported in a numberof other studies The obtained BaPeq concentrations of thesum of 15 PAHs ranged from 005 to 139 mg kgminus1 A vastmajority of examined samples showed concentrations abovethe safe value of 06 mg kgminus1 (CCME 2010) However es-timated incremental lifetime risks posed to the populationthrough distinct routes of exposure were in an acceptablerange One-way ANOVA results showed significant differ-ences in total PAHs and the sum of seven carcinogenic PAH

concentrations as well as in levels of FLU PHE FLT PYRBaA CHR BbF BaP and BPE among parkland residentialand industrial land uses suggesting the influence of the landuse factor

1 Introduction

There is a huge variety of toxic organic compounds but inenvironment control practices around the world evaluationof contaminated areas is often based on priority listed pol-lutants This list includes for example polycyclic aromatichydrocarbons (PAHs) which are ubiquitous organic pollu-tants in the environment (Wilcke 2000) PAHs are a largegroup of aromatic organic compounds consisting of severalhundred individual homologues and isomers containingat least two condensed aromatic rings Their input to theenvironment has both natural and anthropogenic originsNatural sources include releases from vegetation fires dia-genetic processes and volcanic exhalations (ATSDR 1995Wilcke 2000) In turn anthropogenic PAHs occur frompyrolytic processes especially incomplete combustion oforganics during industrial activities domestic heating wasteincineration transportation and power generation (ATSDR1995 Wilcke 2000) It is believed that by far most PAHs arereleased into the environment by anthropogenic combustionof wood and fossil fuels (Wilcke 2000) Soil contaminationwith PAHs is even noted in such remote places as Antarcticabasically near the polar stations However the origin ofPAHs in Antarctic soils is questioned considering that itcould have both natural sources for example decomposition

Published by Copernicus Publications on behalf of the European Geosciences Union

670 G Shamilishvily et al Polycyclic aromatic hydrocarbon in urban soils of an Eastern European megalopolis

of organic matter and anthropogenic sources such as fuelcombustion oil spills and long-range transport of solidatmospheric particles containing PAH mixtures (Abakumovet al 2014 2015) Detection of some individual PAHsis of the most environmental importance because of theestablished carcinogenic mutagenic and teratogenic ef-fects on living organisms and in humans particularly (Yu2002 Guo et al 2013) There have been 16 PAHs listedas priority contaminants by both the US EnvironmentalProtection Agency (US EPA) and the European Union (EU)Among them seven compounds ie benzo(a)anthracenechrysene benzo(a)pyrene benzo(b)fluoranthenebenzo(k)fluoranthene dibenz(ah)anthracene andindeno(123-cd)pyrene are considered to be probablehuman carcinogens (US EPA 2002) In Canada the USAand some European countries regulation of soil contamina-tion is based on developed soil quality criteria for selectedPAHs or their sum Only a few countries have establishedcomprehensive soil guideline values for particular land useat least for the sum of priority PAHs (67ndash16) Generally theexisting soil critical values provide only human health-risk-based approaches and do not consider protection of otherecological receptors In turn the US EPA has developedecological soil screening levels (Eco-SSLs) for PAHswhich are derived separately for four groups of ecologicalreceptors plants soil invertebrates birds and animalsHowever these screening levels are intended to evaluate anunacceptable ecological risk to terrestrial receptors they arenot designed to be used as clean-up levels For this purposethe US EPA adopted the human-health-based preliminaryremediation goals for soil using estimates of different routesof exposure In contrast to this the Russian Federationhas not yet developed soil guideline values at least for thesum of priority PAHs normalization is provided only forsoil contamination with benzo(a)pyrene without distinctionfor particular land use Furthermore no threshold valuesare provided for other POPs (polychlorinated biphenylschlororganic pesticides benzene toluene ethylbenzene andxylenes) A summary of soil guideline values for PAHs set insome countries is presented in Table S1 in the SupplementThus studies on soil contamination with PAHs are of theutmost importance as they provide information that canbe further used to delineate special contaminated sitesexhibiting a high risk of human exposure Thousands ofreports about PAH concentrations sources and health riskassessments in urban and semiurban areas from all over theworld were published in recent years (Yunker et al 2002Liu et al 2010 Wang et al 2013) Elevated levels of PAHsin urban soils were reported in Houston USA (Hwang etal 2002) Beijing China (Tang et al 2005) Glasgow UKTurin Italy (Morillo et al 2007) and Esbjerg Denmark(Essumang et al 2011)

St Petersburg is the largest industrial and transport centrein the north-western region of Russia and is of great inter-est from the viewpoint of environmental concern The eco-

logical status of such a large centre reflects the whole rangeof socioeconomic problems resulting in the decline of hu-man health under the influence of various chemical physicaland biological factors The ecological situation in the city isdetermined by the emissions from more than a thousand in-dustrial enterprises a large railway junction a seaport andthe large motor vehicle fleet ndash 1 670 794 cars and 207 975trucks as of 2014 (Belousova et al 2015) All this transportis served by a huge number of petrol stations and transportcompanies currently in St Petersburg there are 27 fuel oper-ators and 397 petrol stations Industrial enterprises of the cityinclude high-capacity resource- and power-consuming eco-logically dangerous works According to the data collectedfrom the automatic air monitoring system of the city in 2014total emissions into the air from both the stationary sourcesand vehicles has reached 513 200 t of chemicals in 2014 in-cluding 16 903 t of hydrocarbons (CHx) 3000 t of black car-bon (BC) and 47 900 t of volatile organic compounds (VOCs)(Belousova et al 2015) The amount of emissions per capitais 1359 kg yrminus1 per unit area ndash 4345 t kmminus2 (Belousova etal 2015) At the same time 919 of emissions are at-tributed to transport activity Industrial and transport emis-sions along with inputs from petroleum products are themajor source of soil contamination with PAHs in urban ar-eas No systematic survey of soil contamination with prior-ity PAHs has been conducted yet in St Petersburg exceptfor benzo(a)pyrene (Gorky and Petrova 2012) Consideringthis fact and environmental aspects of the territory describedabove St Petersburg affords an excellent location to studygeochemical cycles of PAHs

Therefore this study aims to test the hypothesis on thePAH load differences among urban territories with differentland use scenarios The results of this study would contributeto the knowledge about PAH distribution in urban soils ofthe Eastern European region and may be used by decisionmakers during land management

Objectives of the study were to (1) explore qualitative andquantitative composition of 15 priority PAHs in urban soils insome parkland residential and industrial areas of St Peters-burg (2) compare with existing data on the PAH distributionin urban soils (3) distinguish between PAH sources usingPAH molecular ratios and (4) evaluate cancer risks (CRs) as-sociated with soil contamination with PAHs within selectedareas

2 Materials and methods

21 Study site description

Choice of the study area namely the Primorsky Vasileostro-vsky and Kirovsky administrative districts of St Petersburgwas made in the order of increasing location density of po-tential stationary sources of contamination with PAHs pop-ulation density and traffic activity Detailed characteristics

Solid Earth 9 669ndash682 2018 wwwsolid-earthnet96692018

G Shamilishvily et al Polycyclic aromatic hydrocarbon in urban soils of an Eastern European megalopolis 671

Table 1 Description of the study area

Characteristics Units Primorsky Vasileostrovsky KirovskyDistrict District District

S km2 10987 171 4710Population ndash 534 646 211 048 334 746Industries units 250 350 70Number of potential contamination sources with petroleum products units 14 7 10Density of potential contamination sources units per km2 013 041 021CHx emissions from stationary sources in 2014 thousand tons 0556 0034 0708VOC emissions from stationary sources in 2014 thousand tons 0153 0099 0545BC emissions from stationary sources in 2014 thousand tons 0237 0037 0174

about each chosen area are given in Table 1 Certain recre-ational residential and industrial land use scenarios withineach chosen district were included in the study Informationon the land use scenario of each chosen area was obtainedusing the online map service ldquoRegional Geoinformation Sys-tem (RGIS)rdquo developed with the support of the committeefor land resources and land management of St Petersburg(Fig 1) Potential sources of PAH contamination affectingPAH levels in soil here are high traffic activity (western high-way and Primorsky prospect) steel and chemical industries(Kirovsky engineering plant Baltic Shipyard plant varnishfactory Kronos SPb and thermal power stations (North-WestThermal Power Plant)

Climate is moderately continental and significantly af-fected by the Baltic Sea Annual amount of atmospheric pre-cipitates varies from 565 to 635 mm The territory repre-sents an almost flat plain with altitudes below 20 m abovethe sea level (Neva lowland) Natural soil formation usuallyoccurs on ancient lake-marine littoral sands sandy loams andloams (less) depleted in calcium (Gagarina et al 2008) Ur-ban soils are formed on the bulk deposits ranging from 09to 4 m of thickness (Dashko et al 2011) Soils are stronglydisturbed by anthropogenic activities (buried sealed andorcontaminated) with small relatively intact islands in natu-ral and seminatural areas to the north north-west and north-east of the city An example of natural soils in St Peters-burg are Albeluvisols which are widespread in suburb ter-ritories of the Leningradsky region Soils of the historicalcentre are presented by anthropogenic soil-like formationscalled urbanozems (Stroganova et al 1992) or urbiquaz-izems (Shishov et al 2004) in national soil classificationsystems and generally characterized by light grain size andmodified soil profiles with abundant inclusions of anthro-pogenic artefacts in the form of debris domestic wastes andremains of communications They also have a neutral to alka-line pH high humus nitrogen and phosphorus content hu-mate and fulvic-humate types of humus and traces of chem-ical contamination (Rusakov et al 2005 Matinyan et al2005 Ufimtseva et al 2011) Investigated urban soils were

classified as Technosols according to the World ReferenceBase for Soil Resources (Micheacuteli et al 2006)

22 Sampling strategy and procedure

Sampling was conducted in September 2013 at nine urbansites in dry and clear weather conditions according to inter-national standard protocol ISO 10381-1 (2002) and nationalsampling standard GOST 174402-84 (1984) Soil sampleswere taken from the 0 to 20 cm topsoil layer A total of 135grab soil samples were collected diagonally from 25 m2 sam-pling plots Single samples were combined into 27 compos-ite samples of 07 kg each Location of the sampling siteswas defined according to proximity to residential areas andpotential pollution sources (Fig 1a b c)

Sampling strategy responds to the study objectives and isaimed at providing comprehensive characterization of the se-lected sites suspected to be contaminated with PAHs

Quantity of sampling sites ranged between two and fiveper each zone The description of sampling sites providinginformation on location proximity to potential sources ofcontamination population density road traffic and dominat-ing wind direction is given in Table S3 in the Supplement Allthe sampling plots were located near highways with differenttraffic rates with a distance of no further than 200 m Dis-tance among sampling plots ranged between 100 and 200 mTotal quantity of sampling plots was 34 The sampling depthwas common among all sites and matched a topsoil layer of0ndash20 cm Depth of sampling is a function of exposure routes(eg soil ingestion dermal contact with soil and dust in-halation of contaminated dust inhalation of volatile com-pounds) Five single initial samples of 005 kg each collecteddiagonally from 25 m2 sampling plots were combined intoone grab sample of 01ndash02 kg packed in a dark glass flaskmarked transported to the laboratory and stored at +4 CA total of 135 grab soil samples were collected Grab sam-ples were combined into 27 composite samples of 07 kgeach The sampling scheme represents both the purposiveand judgment sampling techniques delineating sample lo-cations that were assumed to be representative of the wholesite and most contaminated Instruments for sample deriva-

wwwsolid-earthnet96692018 Solid Earth 9 669ndash682 2018

Figure 1 Location of the sampling sites

tion included a stainless steel scoop and knife prewashedwith acetone The representativeness of collected sampleswas provided through mixing and taking an average sampleusing a quartering method

Collected samples were packed in labelled sterile plasticbags kept in cool conditions and transported to the labo-ratory Once in the laboratory soil samples were dispersedon the sterile glass plates and air-dried at room temperaturefor 5 days Then they were cleaned of the organic and in-organic debris ground in a laboratory vibrating cup millsieved through a 025 mm caprone sieve and finally storedin the dark glass containers prewashed with acetone untilanalysis This technique enables the prevention of cross-contamination as well as losses of PAHs due to environmen-tal factors (Berset et al 1999)

23 HPLC PAH source identification and riskevaluation

A total of 15 PAHs were analysed including naph-thalene (NAP) acenaphthene (ANA) fluorene (FLU)phenanthrene (PHE) anthracene (ANT) fluoranthene(FLT) pyrene (PYR) benzo(a)anthracene (BaA) chrysene(CHR) benzo(b)fluoranthene (BbF) benzo(k)fluoranthene(BkF) benzo(a)pyrene (BaP) dibenz(ah)anthracene(DBA)benzo(ghi)perylene (BPE) and indeno(123-cd)pyrene(IPY)

PAH content in samples was determined on the basis of USEPA method 8310 (1996a) national standard method PND F161222362-09 (2009) and the method of Gabov (20072008) Extraction of the PAHs was carried out at room tem-perature with methylene chloride (high purity grade) andultrasonic treatment via a Branson 5510 ultrasonic bath(USA power 469 W working frequency 42 kHz) follow-ing the US EPA method 3550b (1996b) Solvent removal(evaporation) was carried out with KudernandashDanish con-centrator (Supelco) PAH fractions were purified by con-secutive chromatography in columns filled with aluminumoxide (Brockmann activity grade 2ndash3 Neva Reaktiv) andsilica gel (Fluka) according to the US EPA purificationmethod 3660c (1996c) The purity was controlled by theabsence of peaks in the blank chromatogram A standardmixture of 15 PAHs (Supelco) with the concentrations ofeach component in the range of 100ndash2000 microg cmminus3 wasused to prepare the standard PAH solutions Qualitative andquantitative determination of PAHs in soils was carried outwith reverse-phase high-performance liquid chromatography(HPLC) in gradient mode with spectrofluorometric detec-tion via the rdquoLYuMAHROMrdquo chromatograph (Lumex Rus-sia) Chromatography was performed at 30 C on a columnSupelcosiltrade LC-PAH n5 microm (25 cmtimes 21 mm) The mo-bile phase was provided with an acetonitrilendashwater gradientSamples of 10 microL volume were injected using the injection

valve Individual PAHs were identified by the time of re-tention and comparison of fluorescence spectra of the com-ponents coming from the column with spectra of the stan-dard PAHs Quantitative analysis of PAHs was performedusing an external standard method For the quality assur-ance purposes Standard Reference Materialsreg 1944 NewYorkNew Jersey waterway sediment (National Institute ofStandards and Technologies (NIST) USA) containing a mix-ture of 15 PAHs was subjected to the procedure describedabove The error of measuring the PAHs (benz[a]pyrene) inthe soils was 35 in the range of 5ndash40 ng gminus1 and 25 inthe range of 40ndash2000 ng gminus1 with a confidence probability ofP = 095

PAH molecular markers and ratios were used to de-termine PAH sources (Yunker et al 2002 Hwang et al2003 Wang et al 2015 2017) The sum of combustionPAHs (combPAH15PAH) was used as the tracer of py-rogenic sources The combPAH15PAH marker indicatesthe portion of the sum of combustion-specific compoundsin total PAH content which are fluoranthene pyrenechrysene benzo(a)anthracene benzo(k)fluoranthenebenzo(b)fluoranthene benzo(a)pyrene benzo(ghi)peryleneand indeno(123-cd)pyrene (Prahl and Carpenter 1983)Applied PAH molecular markers and ratios as well as theirranges are given in Table S2 in the Supplement

Since BaP is the most studied PAH the carcinogenic po-tential of other PAHs is generally assessed referring it tothat of BaP (toxicity equivalence factors TEFs in a similarway to the toxic equivalents (TEQs) used in the evaluationof the toxicity of dioxins and furans The benzo[a]pyrenepotency equivalence approach is a major approach used bythe US EPA (1993 1999) California EPA (OEHHA 1992)Netherlands (Verbruggen et al 2001) UK (Duggan andStrehlow 1995) or provinces of British Columbia and On-tario for example for assessing the human health risks ofPAH-containing mixtures

Site-specific incremental lifetime CR was calculated in de-rived soil samples taken from areas with different land usesby application of the risk exposure model for chemicals ofthe Risk Assessment Information System (RAIS) This cal-culation estimates a theoretical excess CR expressed as theproportion of a population that may be affected by a carcino-gen during a lifetime of exposure The CRs via ingestiondermal contact and inhalation of soil particles as well totalCR were estimated using the following Eqs (1) (2) and (3)(US EPA 2004)

CRing =Csoiltimes IRsoiltimesEFtimesEDtimesCF

BWtimesATtimesCSFo (1)

where CRing is the cancer risk (unitless) through ingestionof soil particles Csoil is the total BaPeq concentrations ofsoil PAHs IRsoil is the soil ingestion rate (mg dminus1) EF isthe exposure frequency (d yrminus1) ED is the exposure duration(years) CF is the conversion factor of 10minus6 mg kgminus1 BW

is body weight (kg) AT is the average life span (d) CSFois oral (ingestion) cancer slope factor ((mg kgminus1 dminus1)minus1)CSFo = 73 (mg kgminus1 dminus1)minus1 for BaP (US EPA 2004)

CRderm =CsoiltimesSAtimesAFsoiltimesABStimesEFtimesEDtimesCF

BWtimesAT

timesCSFo

GIABS (2)

where CRderm is the cancer risk (unitless) for the dermalcontact pathway SA is the exposed surface area of the skin(cm2) AFsoil is the dermal adherence factor (mg cmminus2) ABSis the absorption factor (unitless) and GIABS is the fractionof contaminant absorbed in the gastrointestinal tract (unit-less)

CRinh =Csoiltimes IRairtimesEFtimesED

PEFtimesBWtimesATtimesCSFi (3)

where CRinh is the cancer risk (unitless) for the inhalationpathway IRair is the inhalation rate (m3 dminus1) CSFi is theinhalation cancer slope factor ((mg kgminus1 dminus1)minus1) and CSFiis obtained from the inhalation unit risk (IUR (microg mminus3)minus1)of BaP according to the recommended method by theUS EPA (2013) PEF is the soil particle emission factor(m3 kgminus1) The total incremental lifetime carcinogenic risk(TILCR) was calculated by summing the CRs for childrenand adults Evaluation of CRs in industrial areas was pro-vided only for adults (composite workers) as the dominatinggroup of population Due to differences in activities physi-ology (body weight skin surface lung volume) and habitsadults and children are exposed to PAHs through differentroutes and on different scales For example children are lessvulnerable to dermal contact with dust and ash particles con-taining PAHs due to the smaller skin surface which leadsto smaller CRs (Wang et al 2015) This paper provides re-sults of CR evaluation only for the sum of adults and childrenwithout separation for individual groups

24 Soil property analysis and statistical treatment

Total organic carbon (TOC) was determined using a LecoCHN628 elemental analyser (USA combustion temperature1030 C oxygen boost time 28 s) Inorganic carbonates wereremoved before analysis by in situ acidification of the groundsamples with 1 M hydrochloric acid in order to avoid uncer-tainty in TOC determination Clay content was determinedwith a Shimadzu SALD-2201 laser diffractometer (Japan)All measurements were carried out in triplicate All measure-ments were converted to an absolutely dry sample

Statistical treatment of the data was carried out with STA-TISTICA 100 software One-way ANOVA was applied inorder to test statistical significance of differences among ob-tained data The essence of the method is based on estimationof the significance of the average differences among three or

more independent groups of data combined by one feature(factor) The null hypothesis of the average equality is testedduring the analysis suggesting the provisions on the equal-ity or inequality of variances In case of rejection of the nullhypothesis basic analysis is not applicable If the variancesare equal the f -test Fisher criterion is used for evaluationof intergroup and intergroup variability If f statistics ex-ceed the critical value the null hypothesis is rejected consid-ering inequality of averages A post hoc test (Fisherrsquos leastsignificant difference) was used to provide detailed evalua-tion of average differences among analysed groups of dataA feature of the post hoc test is application of intra-groupmean squares for the assessment of any pair averages Dif-ferences were considered to be significant at the 95 con-fidence level All calculations were carried out via STATIS-TICA 100 software PAH concentrations were analysed atleast in triplicate Calculated mean concentrations were pro-vided with standard deviations (aplusmn b)

3 Results and discussion

31 PAH concentrations in studied soils

Data on analysed properties of the studied soils are presentedin Table 2 Measured TOC concentrations in studied sam-ples ranged between 382 and 641 with a median value of480 Numerous studies suggested that soil organic matter(SOM) content plays an important role in retention of PAHin soil (Chung and Alexander 2002) In simple terms thehigher SOM concentrations are then the higher the amountof PAH that can be absorbed (Wilcke 2000) Entering thesoil from the atmosphere PAHs are preferentially sorbed toaggregate surfaces (Wilcke 1996) The close association ofPAHs with SOM results in differentiation of organic con-taminant pools among particle size fractions (Guggenbergeret al 1996) A significant increase in PAH concentrationsin finer fractions is shown in a number of studies (Wilcke1996) Clay content in studied soils ranges between 187and 850 Correlation coefficients were calculated in thepresent study in order to reveal the relationship between lev-els of PAH in soil and analysed soil parameters A strongpositive correlation was found between the sum of 15 PAHin soil and clay content (r = 091 n= 27 p = 095) how-ever no correlation of total PAH and TOC concentrations insoil was detected

The levels of 15 individual PAH compounds analysed insoils are shown in Table 3 The sum of 15 PAHs and thesum of seven compounds included in the group of proba-ble human carcinogens (B2) by the US EPA (1993) are ad-ditionally given Total PAH concentrations in studied soilswere found to range from traces to 806 mg kgminus1 (sum of15 priority PAHs hereafter referred to as 15 PAH) The vastmajority of samples were characterized by concentrations ofmore than 1 mg kgminus1 which is set as a guide level for to-

tal PAH content in soil by a number of countries The high-est 15 PAH levels were observed in soil samples collectedfrom residential and industrial sites reaching an average of419 and 401 mg kgminus1 respectively with a maximal value of806 mg kgminus1 for an industrial site in Kirovsky district (here-after ndash KD) Concentrations found in parkland areas weresubstantially lower than those of residential and industrial ar-eas with an average value of 108 mg kgminus1

Distribution of the sum of the seven carcinogenic PAHs(7 PAH) in soils of the studied urban sites is generally char-acterized by the same pattern as the total PAH content insoils The highest 7 PAH levels were measured in soil sam-ples taken from residential sites (194 mg kgminus1) with an ab-solute value of 347 mg kgminus1 in Technosol of a KD residen-tial area The 7 PAH levels in parkland areas corresponds tothe distribution of 15 PAH All sampling sites were locatedin a proximity of less than 250 m to the highways (Korable-stroiteley street Stachek prospect Optikov prospect uni-versity embankment Bolshoi prospect in Vasilievsky Ostrovand others) showing heavy traffic The portion of 7 PAH tothe 15 PAH in all tested samples ranged between 41 and46 which evidently shows that the soils may represent aconsiderable health risk for humans

The sum of PAHs is mostly dominated by heavy-molecular-weight PAHs with four to five rings The portionof four-ringed PAH compounds in the soils of residentialand industrial sites accounts for 50 of the sum decreasingto 34 in parkland soils Five-ringed PAHs including suchcompounds as BaP BbF BkF and DBA contribute up to 31 of the sum of PAH insignificantly varying among studied ar-eas The rest is accounted for by the six-ringed (10ndash14 )and low-molecular-weight PAHs with two or three rings instructure (11ndash17 )

The pie chart illustrating composition of PAH mixturesin soils is depicted in Fig 2 The obvious equality inPAH distribution patterns in all studied sites clearly indi-cates the common source of PAHs Pyrene and fluoran-thene (four-ring PAHs) are the most abundant compoundsin the examined samples and account for 16ndash18 of 15PAH The following predominant compounds are five-ringPAHs benzo(b)fluoranthene (10ndash11 ) and benzo(a)pyrene(8ndash11 ) The rest is represented by lighter-weight PAHs(two- to three-ring PAHs) and is generally dominated byphenanthrene (6ndash9 ) Domination of four- and five-ringPAHs mainly PYR FLT BbF and BaP in studied soils isindicative of elevated diesel fuel consumption activity in thearea Estimated diesel consumption in St Petersburg reaches38 of the total fuel use for transportation (Belousova et al2015) As is known the emission rate of heavyweight PAHfraction during diesel combustion is several times higher thanthat during gasoline combustion (Marr et al 1999)

The data obtained are nearly consistent with data fromLodygin et al (2008) exploring PAH levels (sum of 11 PAHs)in soils of Vasilrsquoyevskiy Island in St Petersburg) The mainanthropogenic impact on soils of residential areas of the is-

Table 2 Physicochemical properties of the studied soils

District Land use Soil name Munsell colour TOC Ntot Clay pH

(WRB) chart index

Parkland Mollic Technosol 25 YR 41 410plusmn 001 035plusmn 006 583plusmn 021 652Primorsky Residential Urbic Technosol 25 YR 41 382plusmn 003 041plusmn 008 743plusmn 006 734

Industrial Urbic Technosol 10 YR 41 549plusmn 002 023plusmn 004 850plusmn 010 715

Parkland Mollic Technosol 25 YR 41 539plusmn 001 028plusmn 007 73plusmn 020 704Vasileostrovsky Residential Urbic Technosol 25 YR 41 641plusmn 002 033plusmn 005 187plusmn 012 745

Parkland Mollic Technosol 25 YR 41 419plusmn 003 032plusmn 009 75plusmn 010 684Kirovsky Residential Urbic Technosol 5 YR 71 480plusmn 003 030plusmn 005 327plusmn 015 712

Table 3 Mean PAH concentrations in soils of St Petersburg (mg kgminus1)

Compound Parkland (n= 9) Residential (n= 9) Industrial (n= 9) P One-way

MeanplusmnSD Max Min MeanplusmnSD Max Min MeanplusmnSD Max Min ANOVA(α = 005)

NAP 006plusmn 008 028 003 005plusmn 002 007 000 009plusmn 007 021 000 042ANA 002plusmn 006 018 000 000 001 000 001 003 000 ndashFLU 010plusmn 006 023 005 017plusmn 011 040 003 017plusmn 011 031 006 004PHE 016plusmn 013 045 005 026plusmn 017 047 003 036plusmn 022 065 007 004ANT 006plusmn 011 037 001 004plusmn 004 011 000 005plusmn 003 009 001 087FLT 018plusmn 007 035 009 069plusmn 052 149 004 072plusmn 048 150 011 002PYR 018plusmn 008 035 009 074plusmn 055 167 004 070plusmn 046 150 016 002BaA 019plusmn 017 053 004 035plusmn 026 064 002 030plusmn 020 067 007 005CHR 015plusmn 014 044 001 031plusmn 024 069 002 028plusmn 018 054 007 005BbF 023plusmn 021 069 005 046plusmn 030 084 002 041plusmn 030 100 010 004BkF 015plusmn 017 056 002 019plusmn 014 036 001 016plusmn 011 033 004 082BaP 022plusmn 022 070 004 043plusmn 032 087 002 034plusmn 023 073 007 004DBA 003plusmn 006 018 000 002plusmn 001 004 000 002plusmn 003 008 000 093BPE 017plusmn 014 046 004 029plusmn 021 052 001 027plusmn 020 069 006 005IPY 012plusmn 015 049 000 017plusmn 017 045 001 015plusmn 013 038 000 076sum

15 PAH 202plusmn 150 478 058 417plusmn 291 810 033 402plusmn 261 806 086 004sum7 PAHlowast 108plusmn 104 318 021 194plusmn 136 347 010 166plusmn 113 320 036 005

NAP ndash naphthalene ANA ndash acenaphthene FLU ndash fluorene PHE ndash phenanthrene ANT ndash anthracene FLT ndash fluoranthene PYR ndash pyrene BaA ndashbenzo(a)anthracene CHR ndash chrysene BbF ndash benzo(b)fluoranthene BkF ndash benzo(k)fluoranthene BaP ndash benzo(a)pyrene DBA ndash dibenz(ah)anthracene BPEndash benzo(ghi)perylene IPY ndash indeno(123-cd) pyrenelowast Carcinogenic PAHs chrysene benzo(a)anthracene benzo(b)fluoranthene benzo(k)fluoranthene benzo(a)pyrene indeno(123-cd) pyrene anddibenz(ah)anthracene

land was exerted by light polyarens including two- to four-ring substances (as stated by the author) the portion of whichin the total content of PAHs was more than 50 Maximumconcentrations of PAHs were detected in soils along high-ways with intense traffic and considerable emissions of com-bustion gases The reported total PAH content ranged from0197 to 820 mg kgminus1 between different land utilizationtypes The described distribution patterns of individual PAHsare similar to those of this study the most abundant are four-to five-ring PAHs particularly pyrene (17 ) fluoranthene(17 ) benzo(ghi)perylene (13 ) benzo(b)fluoranthene

(12 ) and benzo(a)pyrene (12 ) Several samples were no-ticed to exhibit higher contents of heavy polyarens of naturalorigin as both of the samples were represented by fresh or-ganic material (peat) which is used as amendment in soilsof residential areas and roadsides Thus the findings of theabove-mentioned study suggest that spatial distribution ofPAHs is mainly dictated by the closeness to highways andby the artificial input of peat material in the urban soils

There is still a lack of information about PAH concen-trations in the soils of St Petersburg thus the data on thepollutant distribution in water sediments obtained from en-

Figure 2 Composition of PAH mixtures in studied soil

vironmental monitoring systems may be applied in discus-sion for evaluation of the PAH loads Comparative PAH lev-els were detected in bottom sediments in different parts ofNeva Bay (Gulf of Finland) and along the Niva River wa-terway Reported total PAH concentrations ranged between001 and 145 mg kgminus1 (HELCOM 2014) Benzo(a)pyrenewas detected in 96 of sediment samples taken with an av-erage concentration of 009 mg kgminus1

Total PAH concentrations in soils of urban and industrialsites from a number of investigations set in other countriesare summarized in Table 4 In general terms the predomi-nance of three- to five-ring PAHs is noted which is mainlyattributed to the influence of anthropogenic activities on thestudied territories

32 Determination of the PAH sources and statistics

While a domination of high-molecular-weight PAH fractionindicates a combustion origin (pyrogenic) enrichment oflow-molecular-weight PAHs is common in fresh fuels (pet-rogenic) (Budzinski et al 1997) Special molecular markersand ratios proposed by Yunker et al (2002) and a total com-bustion PAH index reported by Hwang et al (2003) wereapplied for PAH source apportionment Obtained meaningsof applied PAH molecular ratios are listed in Table 5Applied markers allow us to distinguish between pyrogenicand petrogenic as well as traffic and non-traffic sources ofPAHs namely ANT (ANT+PHE) FLT (FLT+PYR)

Figure 3 PAH source apportionment

BaA (BaA+CHR) IPY (IPY+BPE) CombPAH 15PAH and BaP BPE Calculated ratios for samples takenfrom residential and industrial areas exhibited numbers thatpoint to a domination of pyrogenically formed PAHs Thecross plots of the PAH ratios are depicted in Fig 3

Several markers are indicative of certain combus-tion sources of PAHs pointing to gasoline dieselcrude oil or grass coal and wood combustion ori-gins namely FLT (FLT+PYR) BaA (BaA+CHR)IPY (IPY+BPE) and BaP BPE The calculatedFLT (FLT+PYR) (049ndash051) IPY (IPY+BPE) (030ndash

Table 4 Reported total concentrations of PAHs in urban soils (mg kgminus1 dry weight) from a number of studies

Location Study area Concentrationssum

PAH Reference(mg kgminus1 dw)

Houston TX USA Urbansuburban 02ndash22 23 Hwang et al (2002)Mexico City Mexico Urbanindustrial 020ndash110 17 Hwang et al (2003)Beijing China Urban 022ndash2782 16 Tang et al (2005)New Orleans USA Urban 373 (median) 16 Mielke et al (2001)Tarragona County Urbanresidential 011ndash100 16 Nadal et al (2004)Catalonia Spain industrialSwiss soil monitoring Urban parkland 005ndash062 16 Bucheli et al (2004)system (NABO) Switzerland semiurbanTallinn Estonia Urban 220plusmn 140 12 Trapido (1999)Linz Austria Industrial 145 (median) 18 Weiss et al (1994)Tokushima Japan Urban 061 13 Yang et al (2002)Shanghai China Main urban 013ndash865008ndash722 26 16 Wang et al (2013)El-Tebbin Egypt Urbanindustrial 005ndash556 16 Havelcovaacute et al (2014)Phoenix Arizona USA Urban (highways) 006ndash1012 20 Marusenko et al (2011)

Table 5 PAH ratios in studied soils

Ratio Parkland Indicated source Residential Indicated source Industrial Indicated source(origin) (origin) (origin)

ANT (ANT+PHE) 019 Pyrogenic 009 Petrogenic 012 PyrogenicFLT (FLT+PYR) 051 Grass coal and 049 Gasoline diesel and 050 Gasoline diesel and

wood combustion crude oil combustion crude oil combustionBaA (BaA+CHR) 058 Grass coal and 052 Grass coal and 051 Grass coal and

wood combustion wood combustion wood combustionIPY (IPY+BPE) 030 Liquid fossil 040 Liquid fossil 034 Liquid fossil

fuel combustion fuel combustion fuel combustionBaP BPE 120 Traffic sources 164 Traffic sources 131 Traffic sourcesCombPAH

sumPAH 079 Combustion- 080 Combustion- 081 Combustion-

dominated source dominated source dominated source

40) and BaP BPE (120ndash164) values point to a dominationof gasoline diesel and oil combustion However obtainedvalues of FLT (FLT+PYR) and BaA (BaA+CHR) ra-tios suggested that coal and wood combustion have a certainrole in PAH origination as well It is important to note thatthe shift of heavy- and low-molecular-weight PAH ratiostowards the heavy ones cannot be explained by only theanthropogenic factor the degradation of lighter PAHs dueto environmental factors such as photolysis under direct sunrays in the topsoil layers or thermal degradation biologicaluptake and biodegradation may play a significant role aswell (Wild and Jones 1995 Johnsen 2005 Choi et al2010) These processes are predetermined by physical andchemical properties of the lighter fraction PAHs such as lowmolecular weight high vapour pressure and high volatilityrate (Mackay and Hickie 2000) Volatilization proved toplay the most significant role in the global degradation ofthe two- and three-ringed PAHs especially Park et al (1990)reported that approximately 30 loss of naphthalene ac-counts for volatilization while for the remaining compounds

this process was insignificant Heavy-weight PAHs iefour- to six-ring compounds have low solubility in waterlow volatility and a strong affinity to particulates (BC andSOM fine fractions) and are less accessible for biologicaluptake and degradation and thus are more persistent in theenvironment (Johnsen 2005 Haritash 2009) It has beenproven that PAHs may form non-extractable [14C]PAHresidues in soil under the stimulation of microbial activitywhich obviously leads to unexpectedly lower results whileanalyzing the concentrations of naphthalene anthracenepyrene and benzo(a)pyrene in soil samples (Eschenbach etal 1998)

Obtained probabilities for one-way ANOVA revealed nostatistically significant differences of total PAH concentra-tions in soils among different land uses (Plt005) Probabil-ities for ANOVA are given in Table 3

The differences in levels of individual PAH compoundswere tested using a post hoc Fisherrsquos least significant dif-ference test The results showed significant differences ofFLU PHE FLT PYR BaA CHR BbF BaP and BPE con-

centrations among parkland residential and industrial areas(p = 002minus005) The tested hypothesis suggested that PAHlevels in urban soil may differ among areas with differentland utilization types in the following order industrial res-idential parkland The results of the study proved the argu-ment of the influence of the land use factor on the differ-ence of PAH levels in urban soils between studied sites Theland use factor is intensively expressed in distribution of thedominant individual PAHs particularly BaP PHE FLT andPYR These compounds are known to be a part of the PAHmixtures isolated from the exhaust gases and industrial emis-sions (Rehwagen et al 2005) Thus it is not too surprisingthat elevated levels of these pollutants are expected primarilyin industrial and transport areas along with surrounding ar-eas where maximum input of BC from air pollution sourcesis noted PHE representing low-molecular-weight PAH isa thermodynamically stable tri-aromatic compound arisingfrom petroleum-hydrocarbon-based releases Distribution ofthis contaminant follows the scheme of potential sources ofcontamination with petroleum product allocation (Fig 4)

33 Health risk evaluation of PAHs in soils

Health risks associated with soil contamination from PAHswas assessed using the benzo(a)pyrene total potency equiva-lents approach (BaPeq) The BaPeq for a soil sample is simplycalculated by multiplying the concentration of each PAH inthe sample by its benzo(a)pyrene TEF given in Table 6

The calculated BaPeq on the average concentration of15 PAH (here and after referred to as BaPeq-15 PAH) var-ied between 044 and 066 mg kgminus1 of dry soil The highestBaPeq-15PAH mean concentrations were found in residen-tial and industrial areas 066 and 055 mg kgminus1 respectivelyParkland areas are characterized by lower but still consid-erable levels of BaPeq-15 PAH (mean 044 mg kgminus1) Notethat one single sample taken from Kirovsky parkland ex-hibited a total BaPeq concentration of 184 mg kgminus1 (ThePark of 9th January) which evidently shows that parklandland uses are subjected to a high load of PAHs as well asother land uses Obtained values are several times higherthan reported total PAH carcinogenic potencies in a num-ber of studies (BaPeq of total PAHs) 002 mg kgminus1 in soilsof Viseu and 023 mg kgminus1 in Lisbon Portugal (Cachada etal 2012) Nadal et al (2004) reported BaPeq concentrationsvarying between 002 and 012 mg kgminus1 in soils of Tarrag-ona Province Spain 018 mg kgminus1 in soils of Beijing and024 mg kgminus1 in Shanghai China (Liu et al 2010 Wang etal 2013)

Finally obtained BaP total potency equivalents of PAHswere compared with soil quality guideline values for di-rect contact with contaminated soil with respect to partic-ular land use (CCME 2010) setting out the safe level of06 mg kgminus1BaPeq (for each land use) The reported BaPeqof the 15 PAH concentrations was above the safe level of06 mg kgminus1 Exposure to these soils through direct contact

Figure 4 Scale of potential sources of contamination withpetroleum products (units per square kilometre) with PHE distri-bution plots

probably poses a significant risk to human health from car-cinogenic effects of PAHs even in urban parklands Ob-tained values of BaPeq were further used to calculate the in-dex of incremental lifetime cancer risk (ILCR) This methodprovides quantitative evaluation of the human exposure toPAHs through various exposure scenarios including inges-tion dermal contact and inhalation of different age and gen-der groups

The acceptable level of ILCR is set at 10minus6ndash10minus4 by theUS EPA (US EPA 2001) Risks below 10minus6 do not requirefurther action while risks above 10minus4 are considered con-cerning and require additional action to reduce the expo-sure and resulting risk (US EPA 2004) Calculated valuesof TILCR are summarized in Table 7

All estimated TILCRs were within the acceptable range(10minus6ndash10minus4) The TILCRs for different exposure pathwaysdecreased in the following order ingestion gt dermal con-tact gt inhalation for both children and adults The greatestTILCR value was estimated for soil ingestion in the caseof residential land use (425times 10minus5) followed by industrialland use (841times 10minus6) Soil ingestion is considered to be themost significant route of exposure in residential areas partic-ularly for children since they are more naturally active thanother age groups which leads to greater CR caused by soilingestion (Wang et al 2015) The estimated TILCRs causedby dermal contact with soil and inhalation for both the chil-dren and adult groups were smaller than those caused by in-gestion of soil particles ranging from 10minus6 to 10minus12 Theapplied RAIS model does not provide an estimation of CRfor youths though this age group is supposed to be morevulnerable for dermal contact with contaminated soil whichaccounts for 325 of the exposure followed by the CRs for

Table 6 PAH concentrations in urban soils expressed in BaPeq mg kgminus1

Compound Parkland Residential Industrial TEFlowast

MeantimesTEF MaxtimesTEF MintimesTEF MeantimesTEF MaxtimesTEF MintimesTEF MeantimesTEF MaxtimesTEF MintimesTEF

NAP 000006 000028 000003 000005 000007 000 000009 000021 000 0001ANA 000002 000018 000 000 000001 000 000 000003 000 0001FLU 00001 000023 000005 000017 00004 000003 000017 000031 000006 0001PHE 000016 000045 000005 000026 000047 000003 000036 000065 000007 0001ANT 00006 00037 00001 00004 00011 000 00005 00009 00001 001FLT 000018 000035 000009 000069 000149 000004 000072 00015 000011 0001PYR 000018 000035 000009 000074 000167 000004 00007 00015 000016 0001BaA 0019 0053 0004 0035 0064 0002 003 0067 0007 010CHR 00015 00044 00001 00031 00069 00002 00028 00054 00007 001BbF 0023 0069 0005 0046 0084 0002 0041 010 001 010BkF 0015 00560 0002 0019 0036 0001 0016 0033 0004 010BaP 022 07 004 043 087 002 034 073 007 100DBA 015 090 000 010 020 000 010 040 000 500BPE 00017 00046 00004 00029 00052 00001 00027 00069 00006 001IPY 0012 0049 000 0017 0045 0001 0015 0038 000 010sum

15 PAH 04435 184154 005191 065531 131631 002644 055004 13854 00928sum7 PAHlowast 04405 18314 00511 06501 13059 00262 05448 13734 00917

lowastValues of the toxic equivalency factors proposed by Nisbet and Lagoy (1992)

Table 7 Calculated TILCRs based on different routes of exposure and land use scenarios (sum of children and adults)

Land use scenario Total incremental lifetime cancer risk (unitless)

Route of exposure Ingestion Dermal Inhalation Total risk

Parkland 616times 10minus7 171times 10minus7 205times 10minus12 777times 10minus7

Residential 424times 10minus5 124times 10minus6 283times 10minus8 436times 10minus5

Industrial (composite worker) 841times 10minus6 ndash 198times 10minus7 861times 10minus6

children and adults accounting for 276 and 218 respec-tively suggesting that dermal contact could be a significantexposure pathway for youths compared to children and adults(Wang et al 2015) Exposure route related to dermal contactwith soil in industrial areas was not assessed considering thatskin of the workers is not exposed

4 Conclusions

Results of the study demonstrated that soils within stud-ied urban areas are characterized by common levels of to-tal PAHs generally attributed to high traffic density of thecity Considerable levels of soil contamination with PAHswere noted The common tendency in PAH distribution pat-terns between investigated sites clearly indicates the com-mon source of PAHs in urban soils A larger portion of high-molecular-weight PAHs along with determined molecular ra-tios suggest the predominance of pyrogenic sources mainlyattributed to combustion of gasoline diesel and oil Petro-genic sources of PAHs also have a significant portion defin-ing the predominance of low-molecular-weight PAHs asso-ciated with petroleum such as phenanthrene Derived con-centrations of seven carcinogenic PAHs as well as calculated

BaP total potency equivalents were multiple times higherthan reported in a number of other studies indicating a sig-nificant risk for human health in the case of direct contactHowever application of the RAIS CR evaluation module re-vealed that incremental lifetime risks posed to the populationare under the acceptable range (10minus4ndash10minus6 and lower) One-way ANOVA results showed significant differences in lev-els of 15 PAHs 7 PAHs FLU PHE FLT PYR BaA CHRBbF BaP and BPE among parkland residential and indus-trial land uses suggesting the influence of land use factor ondistribution of PAHs in soils of the city Further study with anapplication of complex statistical methods such as principalcomponent analysis which would contribute to precision ofPAH sources allocation is needed

Data availability Data can be accessed at httpsdrivegooglecomopenid=18UCcZNp0_qzXHpXsW-O3jKYqPidiozbX(Shamilishvily et al 2018)

The Supplement related to this article is available onlineat httpsdoiorg105194se-9-669-2018-supplement

Competing interests The authors declare that they have no conflictof interest

Acknowledgements Saint Petersburg University grant no1371512014 and Saint Petersburg State University Internal Grantfor the Modernization of Scientific Equipment no 1405412017

Edited by Martine van der PloegReviewed by four anonymous referees

References

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Abakumov E V Parnikoza I Y Lupachev A V Lodygin ED Gabov D N and Kunakh V A Content of polycyclic aro-matic hydrocarbons in soils of Antarcti stations regions Gigienai saniataria 94 20ndash25 2015

ATSDR Polycyclic Aromatic Hydrocarbons Agency for ToxicSubstances and Disease Registry available at httpswwwatsdrcdcgovtoxprofilestpaspid=122amptid=25 (last access 24 Au-gust 2015) 1995

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Belousova V A Berezin I K Golovina N M Grigoriev AS Gromyko M O Guchinsky V A Dvinyanina O V Za-vyalov D V Zaporozhets A I Ipatova S V KaretnikovaT V Kerenkov G A Kovaleva T V Konstantinova O VKorobeinikova M A Krapivko N A Kruglov F V Kru-toy D M Kryakova E O Kuptsova N M Kurnosov D VLyakhovnenko S F Menrsquoshova Yu A Miloslavskaya Yu GMorozova I A Mozhsenikova N B Pakudina V N Par-fenova A V Romanova T V Rublevsky V V RutkovskiyA M Rybakova YuV Savenkova G B Sergeeva N ASerebritsky I A Silina I V Smirnov NA Strakhov M AStukkei G A Suchkova L I Titorenko A A Fomina LB Frumin G T Khmylev I V Shpakova E N Shulga LV and Shundrina Yu A Report on the environmental sit-uation in St Petersburg in 2014 The Committee for NatureUse Environmental Protection and Ecological Safety of St Pe-tersburg St Petersburg Russia httpgovspbrustaticwritableckeditoruploads20150619doklad_2014_SWipmNUpdf lastaccess 11 September 2015

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Choi H G Moon H B Choi M Yu J and Kim S S Musselwatch program for organic contaminants along the Korean coast2001ndash2007 Environ Monit Assess 169 473ndash474 2010

Chung N and Alexander M Differences in sequestration andbioavailability of organic compounds aged in dissimilar soilsEnviron Sci Technol 32 855ndash860 1998

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Eschenbach A Wienberg R and Mahro B Fate and stability ofnonextractable residues of [14C]PAH in contaminated soils un-der environmental stress conditions Environ Sci Technol 322585ndash2590 1998

Essumang D K Kowalski K and Sogaard E G Levels distri-bution and source characterization of polycyclic aromatic hydro-carbons (PAHs) in topsoils and roadside soils in Esbjerg Den-mark Bull Environ Contam Toxicol 86 438ndash443 2011

Gabov D N Beznosikov V A and Kondratenko B M Poly-cyclic aromatic hydrocarbons in background podzolic and gleyicpeat-podzolic soils Eurasian Soil Sci+ 40 256ndash264 2007

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GOST 174402-84 Nature protection Soils Methods for sam-pling and preparation of soils for chemical bacteriologicalhelmintological analysis Moscow 8 pp 1984 (in Russian)

Guo W He M C Yang Z F Zhang H Y Lin C Y andTian Z J The distribution sources and toxicity risks of poly-cyclic aromatic hydrocarbons and n-alkanes in riverine and es-tuarine core sediments from Daliao River watershed EnvironEarth Sci 68 2015ndash2024 2013

Haritash A K and Kaushik C P Biodegradation aspects ofpolycyclic aromatic hydrocarbons (PAHs) a review J HazardMater 169 1ndash15 2009

Havelcovaacute M Melegy A and Rapant S Geochemical distribu-tion of polycyclic aromatic hydrocarbons in soils and sedimentsof El-Tabbin Egypt Chemosphere 95 63ndash74 2014

HELCOM BASE project 2012ndash2014 Preparation of biodiver-sity and hazardous substances indicators with targets thatreflect good environmental status for HELCOM (including theHELCOM CORESET project) and improvement of Russiancapacity to participate in operationalization of those indicatorshttphelcomfiListsPublicationsINDICATORS_Russian20capacity20to20participate20in20operationalization20of20CORESET20indicatorspdf (last access June 2016)2014

Hwang S and Cutright T J Biodegradability of aged pyrene andphenanthrene in a natural soil Chemosphere 47 891ndash899 2002

Hwang H M Wade T L and Sericano J L Concentrationsand source characterization of polycyclic aromatic hydrocarbonsin pine needles from Korea Mexico and United States AtmosEnviron 37 2259ndash2267 2003

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Johnsen A R Wick L Y and Harms H Principles of microbialPAH-degradation in soil Environ Pollut 133 710ndash84 2005

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Liu S Xia X Yang L Shen M and Liu R Polycyclic aro-matic hydrocarbons in urban soils of different land uses in Bei-jing China distribution sources and their correlation with thecityrsquos urbanization history J Hazard Mater 177 1085ndash10922010

Lodygin E D Chukov S N Beznosikov V A and Gabov D NPolycyclic aromatic hydrocarbons in soils of Vasilievsky Island(St Petersburg) Eurasian Soil Sci+ 41 1321ndash1326 2008

Mackay D and Hickie B Mass balance model of source appor-tionment transport 482 and fate of PAHs in Lac Saint LouisQuebec Chemosphere 41 681ndash692 2000

Marr L C Kirchstetter T W Harley R A Miguel A H Her-ing S V and Hammond S K Characterization of polycyclicaromatic hydrocarbons in motor vehicle fuels and exhaust emis-sions Environ Sci Technol 33 3091ndash3099 1999

Marusenko Y Herckes P and Hall S J Distribution of poly-cyclic aromatic hydrocarbons in soils of an arid urban ecosystemWater Air Soil Poll 219 473ndash487 2011

Micheacuteli E Schad P Spaargaren O Dent D and NachtergaeleF World reference base for soil resources 2006 a frameworkfor international classification correlation and communication(FAO) IUSS Working Group WRB World reference base forsoil resources World Soil Resources Reports No 103 FAORome 143 pp 2006

Mielke H W Wang G Gonzales C R Le B Quach V N andMielke P W PAH and metal mixtures in New Orleans soils andsediments Sci Total Environ 281 217ndash227 2001

Morillo E Romero A S Maqueda C Madrid L Ajmone-Marsan F Grcman H and Villaverde J Soil pollution by

PAHs in urban soils a comparison of three European cities JEnviron Monit 9 1001ndash1008 2007

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OEHHA (Office of Environmental Health Hazard Assessment) Ex-pedited Cancer Potency Factors and Proposed Regulatory Lev-els for Certain Proposition 65 Carcinogens Air Resources Boardand OEHHA California EPA Sacramento CA USA 45 pp1992

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PND F 161222362-09 Quantitative chemical analysis of soilMethods of measurement of the mass fraction of polycyclic aro-matic hydrocarbons in soil sediments sewage sludge and indus-trial wastes by HPLC Moscow Russia 23 pp 2009 (in Rus-sian)

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Rehwagen M Muumlller A Massolo L Herbarth O and RoncoA Polycyclic aromatic hydrocarbons associated with particlesin ambient air from urban and industrial areas Sci Total Envi-ron 348 199ndash210 2005

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Shamilishvily G Abakumov E and Gabov D Polycyclicaromatic hydrocarbon in urban soils of an Eastern Euro-pean megalopolis distribution source identification and cancerrisk evaluation available at httpsdrivegooglecomopenid=18UCcZNp0_qzXHpXsW-O3jKYqPidiozbX last access 8 May2018

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Ufimtseva M D Terekhina N V and Abakumov E V Fiziko-khimicheskayakharakteristikaurbanozemovtsentralrsquonogoraionaSankt-Peterburga Vestnik Sankt-Peterburgskogouniversiteta 785ndash97 2011 (in Russian)

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tions (NSCEP) of the US Environmental Protection AgencyWashington DC Office of Health and Environmental As-sessment available at httpnepisepagovExeZyPURLcgiDockey=30002TUAtxt (last access 20 April 2015 1993

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US EPA Method 3550b Ultrasonic extraction in Test Methodsfor Evaluating Solid Waste PhysicalChemical Methods ThirdEdition Final Update 3-A National Service Center for Environ-mental Publications (NSCEP) of the US Environmental Protec-tion Agency Washington DC Office of Health and Environmen-tal Assessment Revision 2 availabel at httpnepisepagovExeZyPURLcgiDockey=50000U6Etxt (last access 20 April2015) 1996b

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Wang C Wu S Zhou S Wang H Li B Chen H and Shi Y Polycyclic aromatic hydrocarbons in soils from urban to ruralareas in Nanjing concentration source spatial distribution andpotential human health risk Sci Tot Environ 527 375ndash3832015

Wang C Wu S Zhou S Shi Y and Song J Characteristicsand Source Identification of Polycyclic Aromatic Hydrocarbons(PAHs) in Urban Soils A Review Pedosphere 27 17ndash26 2017

Weiss P Riss A Gschmeidler E and Schentz H Investigationof heavy metal PAH PCB patterns and PCDDF profiles of soilsamples from an industrialized urban area (Linz Upper Austria)with multivariate statistical methods Chemosphere 29 2223ndash2236 1994

Wilcke W Zech W and Kobža J PAH-pools in soils along aPAH-deposition gradient Environ Pollut 92 307ndash313 1996

Wilcke W Synopsis polycyclic aromatic hydrocarbons (PAHs) insoil ndash a review J Plant Nutr Soil Sci 163 229ndash248 2000

Wild S R and Jones K C Polynuclear aromatic hydrocarbons inthe United Kingdom environment a preliminary source inven-tory and budget Environ Pollut 88 91ndash108 1995

Yang H H Lai S O Hsieh L T Hsueh H J and Chi T WProfiles of PAH emission from steel and iron industries Chemo-sphere 48 1061ndash1074 2002

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Abstract
Introduction
Materials and methods
- Study site description
- Sampling strategy and procedure
- HPLC PAH source identification and risk evaluation
- Soil property analysis and statistical treatment
- - Results and discussion
  - - PAH concentrations in studied soils
    - Determination of the PAH sources and statistics
    - Health risk evaluation of PAHs in soils
    - - Conclusions
      - Data availability
      - Competing interests
      - Acknowledgements
      - References

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of organic matter and anthropogenic sources such as fuelcombustion oil spills and long-range transport of solidatmospheric particles containing PAH mixtures (Abakumovet al 2014 2015) Detection of some individual PAHsis of the most environmental importance because of theestablished carcinogenic mutagenic and teratogenic ef-fects on living organisms and in humans particularly (Yu2002 Guo et al 2013) There have been 16 PAHs listedas priority contaminants by both the US EnvironmentalProtection Agency (US EPA) and the European Union (EU)Among them seven compounds ie benzo(a)anthracenechrysene benzo(a)pyrene benzo(b)fluoranthenebenzo(k)fluoranthene dibenz(ah)anthracene andindeno(123-cd)pyrene are considered to be probablehuman carcinogens (US EPA 2002) In Canada the USAand some European countries regulation of soil contamina-tion is based on developed soil quality criteria for selectedPAHs or their sum Only a few countries have establishedcomprehensive soil guideline values for particular land useat least for the sum of priority PAHs (67ndash16) Generally theexisting soil critical values provide only human health-risk-based approaches and do not consider protection of otherecological receptors In turn the US EPA has developedecological soil screening levels (Eco-SSLs) for PAHswhich are derived separately for four groups of ecologicalreceptors plants soil invertebrates birds and animalsHowever these screening levels are intended to evaluate anunacceptable ecological risk to terrestrial receptors they arenot designed to be used as clean-up levels For this purposethe US EPA adopted the human-health-based preliminaryremediation goals for soil using estimates of different routesof exposure In contrast to this the Russian Federationhas not yet developed soil guideline values at least for thesum of priority PAHs normalization is provided only forsoil contamination with benzo(a)pyrene without distinctionfor particular land use Furthermore no threshold valuesare provided for other POPs (polychlorinated biphenylschlororganic pesticides benzene toluene ethylbenzene andxylenes) A summary of soil guideline values for PAHs set insome countries is presented in Table S1 in the SupplementThus studies on soil contamination with PAHs are of theutmost importance as they provide information that canbe further used to delineate special contaminated sitesexhibiting a high risk of human exposure Thousands ofreports about PAH concentrations sources and health riskassessments in urban and semiurban areas from all over theworld were published in recent years (Yunker et al 2002Liu et al 2010 Wang et al 2013) Elevated levels of PAHsin urban soils were reported in Houston USA (Hwang etal 2002) Beijing China (Tang et al 2005) Glasgow UKTurin Italy (Morillo et al 2007) and Esbjerg Denmark(Essumang et al 2011)

St Petersburg is the largest industrial and transport centrein the north-western region of Russia and is of great inter-est from the viewpoint of environmental concern The eco-

logical status of such a large centre reflects the whole rangeof socioeconomic problems resulting in the decline of hu-man health under the influence of various chemical physicaland biological factors The ecological situation in the city isdetermined by the emissions from more than a thousand in-dustrial enterprises a large railway junction a seaport andthe large motor vehicle fleet ndash 1 670 794 cars and 207 975trucks as of 2014 (Belousova et al 2015) All this transportis served by a huge number of petrol stations and transportcompanies currently in St Petersburg there are 27 fuel oper-ators and 397 petrol stations Industrial enterprises of the cityinclude high-capacity resource- and power-consuming eco-logically dangerous works According to the data collectedfrom the automatic air monitoring system of the city in 2014total emissions into the air from both the stationary sourcesand vehicles has reached 513 200 t of chemicals in 2014 in-cluding 16 903 t of hydrocarbons (CHx) 3000 t of black car-bon (BC) and 47 900 t of volatile organic compounds (VOCs)(Belousova et al 2015) The amount of emissions per capitais 1359 kg yrminus1 per unit area ndash 4345 t kmminus2 (Belousova etal 2015) At the same time 919 of emissions are at-tributed to transport activity Industrial and transport emis-sions along with inputs from petroleum products are themajor source of soil contamination with PAHs in urban ar-eas No systematic survey of soil contamination with prior-ity PAHs has been conducted yet in St Petersburg exceptfor benzo(a)pyrene (Gorky and Petrova 2012) Consideringthis fact and environmental aspects of the territory describedabove St Petersburg affords an excellent location to studygeochemical cycles of PAHs

Therefore this study aims to test the hypothesis on thePAH load differences among urban territories with differentland use scenarios The results of this study would contributeto the knowledge about PAH distribution in urban soils ofthe Eastern European region and may be used by decisionmakers during land management

Objectives of the study were to (1) explore qualitative andquantitative composition of 15 priority PAHs in urban soils insome parkland residential and industrial areas of St Peters-burg (2) compare with existing data on the PAH distributionin urban soils (3) distinguish between PAH sources usingPAH molecular ratios and (4) evaluate cancer risks (CRs) as-sociated with soil contamination with PAHs within selectedareas

2 Materials and methods

21 Study site description

Choice of the study area namely the Primorsky Vasileostro-vsky and Kirovsky administrative districts of St Petersburgwas made in the order of increasing location density of po-tential stationary sources of contamination with PAHs pop-ulation density and traffic activity Detailed characteristics

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4 Conclusions

References

Abstract
Introduction
    - - Conclusions
      - Data availability
      - Acknowledgements
      - References

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4 Conclusions

References

Abstract
Introduction
    - - Conclusions
      - Data availability
      - Acknowledgements
      - References

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BWtimesAT

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4 Conclusions

References

Abstract
Introduction
    - - Conclusions
      - Data availability
      - Acknowledgements
      - References

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BWtimesAT

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(WRB) chart index

4 Conclusions

References

Abstract
Introduction
    - - Conclusions
      - Data availability
      - Acknowledgements
      - References

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(WRB) chart index

4 Conclusions

References

Abstract
Introduction
    - - Conclusions
      - Data availability
      - Acknowledgements
      - References

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(WRB) chart index

4 Conclusions

References

Abstract
Introduction
    - - Conclusions
      - Data availability
      - Acknowledgements
      - References

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4 Conclusions

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Abstract
Introduction
    - - Conclusions
      - Data availability
      - Acknowledgements
      - References

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4 Conclusions

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Abstract
Introduction
    - - Conclusions
      - Data availability
      - Acknowledgements
      - References

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4 Conclusions

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Abstract
Introduction
    - - Conclusions
      - Data availability
      - Acknowledgements
      - References

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4 Conclusions

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Introduction
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      - Data availability
      - Acknowledgements
      - References

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References

Abstract
Introduction
    - - Conclusions
      - Data availability
      - Acknowledgements
      - References

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Abstract
Introduction
    - - Conclusions
      - Data availability
      - Acknowledgements
      - References

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Abstract
Introduction
    - - Conclusions
      - Data availability
      - Acknowledgements
      - References

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