the concentration of mild-extracted polycyclic aromatic hydrocarbons in sewage sludges

JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH

Part A—Toxic/Hazardous Substances & Environmental Engineering

Vol. A39, Nos. 11–12, pp. 2799–2815, 2004

The Concentration of Mild-Extracted Polycyclic

Aromatic Hydrocarbons in Sewage Sludges

Patryk Oleszczuk* and Stanisbaw Baran

Institute of Soil Science and Environmental Management,

Agriculture University, Poland

ABSTRACT

The present study evaluates the content of the mild-solvent extracted fraction of

the polycyclic aromatic hydrocarbons. Ten compounds from the US EPA list

(phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene, chryzene,

benzo[b]fluoranthene, benzo[a]pyrene, benzo[ghi]perylene oraz indeno[1,2,3-

cd]pyrene) were chosen. The compounds were extracted with n-butanol from

11 sewage sludges that differed both in the total PAH content and in their

physicochemical properties. On the basis of the results obtained, the influence of

the properties of the PAH and some properties of selected sludge on the content

of the mild-solvent extracted fractions of these compounds was determined.

The content of the fraction extracted with n-butanol within the total of 10 PAHs

ranged from 12.5 to 83.2% (mean 40.1%) depending on the type of sludge.

Similarly, as in the case of the total of the 10 PAHs, significant differences in the

content of PAHs extracted with n-butanol were also noted for the individual

compounds studied. In the case of most individual PAHs their mean share did

not differ statistically in relation to the PAH type and was close to 40%.

An evaluation of the relation between the share of the fraction extracted with

n-butanol from the different types of sludge and the properties of the PAHs

showed that statistically, there existed significant (P< 0.05) correlations between

log Koc (in the case of one sewage sludge) and between the nitrogen content,

*Correspondence: Patryk Oleszczuk, Institute of Soil Science and Environmental

Management, University of Agriculture, Lublin, Poland; E-mail: [email protected].

2799

DOI: 10.1081/LESA-200033835 1093-4529 (Print); 1532-4117 (Online)

Copyright & 2004 by Marcel Dekker, Inc. www.dekker.com

ORDER REPRINTS

the ratio of C/N, cations Mg2þ and Kþ (in the case of a few PAHs). A clear and

significant relation was found between the content of and the share of the fraction

of n-butanol extracted and the PAH fraction present in the sewage sludge pore

water (determined on the basis of an equilibrium partition model).

Key Words: Polycyclic aromatic hydrocarbons; Sewage sludges; Organic

contaminants; Bioavailability; Mild extraction.

INTRODUCTION

Polyaromatic hydrocarbons (PAHs) are listed as priority pollutants by the USEPA.[1] Some are toxic, mutagenic, and carcinogenic to humans[2] and are known topersist in the environment. The presence of PAH’s can be found in numerouselements within the natural environment (water, soil, sediments),[3–5] however, ithas been evaluated[6] that the main PAHs sink is the soil. One source of PAHs’ insoil is sewage sludge[7,8] resulting from a considerable PAH content in this typeof waste.[9–13]

As has been shown,[14] directly after sewage sludge has been introduced into thesoil, in the case of some PAHs there are quite significant disproportions between thecontent of these compounds forecast (as calculated theoretically) and their actualcontent as determined in soil fertilized with sewage sludge. Losses can be explainedby the biodegradation phenomenon, leaching, evaporation, and photodegradation.Evaluation of the bioavailable PAH fraction in sewage sludge could then be the basisfor the evaluation of the potential possibility of their quick degradation in the initialperiod after their introduction. In the literature, there are descriptions of the variousmethods used for the determination of the bioavailable fraction of polycyclicaromatic hydrocarbons. In order to evaluate the content of the bioavailableforms, the following methods have been proposed: supercritical-fluid extraction(SFE),[15–17] the application of passive samplers (tenax, semi-permeable membranedevices, octadecyl-modified silica disks),[18–22] persulphate oxidation,[23] the multi-column system,[24] the nonexhaustive cyclodextrin-based extraction technique[25] andselective chemical extractants.[22,26–28] Researchers from Cornell University[26,28]

using the mild-solvent extraction procedure with n-butanol achieved very goodresults in the prediction of the bioavailable PAH fraction in the soils.

In the studies presented, the content of mild-solvent extracted PAHs wasevaluated in sewage sludge. Evaluated were the extent of the influences of theamount of organic matter on the PAH fraction extracted with this method, theextent of the influence of the properties of the other types of sludge (pH, cationexchange capacity, the total of the exchangeable bases, the degree of the basesaturation, the total amount of nitrogen, ratio TOC/Nt, available forms of P and K,cations—Ca2þ, Mg2þ, Kþ, Naþ) and the properties of the PAHs themselves(molecular weight, solubility in water, log Koc, log Kow, Henry’s constant, molecularconnectivity index, and molecular surface area) on the scope of this process.The results obtained are the basis for further studies on the evaluation of the contentof the bioavailable PAH fraction in the various types of sewage sludge as well as inthose soils fertilized with sewage sludge and compost.

2800 Oleszczuk and Baran

ORDER REPRINTS

MATERIALS AND METHODS

Polycyclic Aromatic Hydrocarbons Analysis

The total content of PAHs was determined by a method described in more detailin Refs.[5,29,30] Sewage sludge samples (3 g) were extracted with dichloromethane(2� 40mL) in an ultrasonic bath (Sonic-3, Polsonic, Poland); the extract was thencentrifuged and purified by the solid phase extraction method in octadecyl C18

microcolumns (JT Baker-Mallinckrodt, Germany). A Spherisorb-PAH (SchambeckSFD GmbH, Germany) was used for PAH separation. The mobile phase(acetonitrile:water, 82:18, v/v) flow was set to 1mL/min. Detection was carriedout at 254 nm. The column was installed in a thermostated oven at 31�C (LCO 101,ECOM, Czech Republic). Recoveries for the total procedures (sample preparation,extraction, and SPE) ranged between 72 and 83% for individual PAHs.

Mild-solvent extraction was carried out by the extraction of samples of sewagesludge (10 g) with 30mL n-butanol; after which, the extracts were centrifuged andthe PAH content was determined in the residue after extraction in accordance withthe methodology described above. The differences between the total PAH content(as determined in the dichloromethane) and the residue (after extraction withn-butanol) was determined as an n-butanol fraction.

All reported concentrations of PAHs (total and n-butanol fractions) areexpressed on a dry-weight basis of sewage sludge (determined by drying thesewage sludge for 24 h at 105�C) and are the average of triplicate extractions.

Evaluation of PAH Concentrations in Sewage Sludge Water Phase

In the literature[31,32] the bioavailable fraction is often defined as the pollutantspresent mainly in the pore water. The concentration of investigated PAHs in thesewage sludge pore water phase was evaluated on the basis of an equilibriumpartition model[31,33]:

PAHwp ¼ PAHtot=ðKoc � focÞ ð1Þ

wherePAHwp—concentration of PAHs in the sewage sludge water phase (mg/L);PAHtot—concentration of PAHs in the sewage sludge (mg/kg);foc—fraction of sewage sludge organic carbon (kg/kg);Koc—water–carbon partition coefficient (L/kg).

Properties of Sewage Sludges

The physical–chemical properties of the soils studied were determined bymethods generally used in chemical-soil laboratories. pH was measured potention-metrically in 1M KCl after 24 h in the liquid/soil ratio of 10, the total of theexchangeable bases (TEB) and cation exchange capacity (CEC) were measured in

Concentration of Mild-Extracted Polycyclic Aromatic Hydrocarbons 2801

ORDER REPRINTS

the 0.1N HCl extraction[34] with calculating the degree of the base saturation (BS).The total amount of nitrogen (Nt) was determined by the Kjeldahl method[35]

without the application of Dewarda’s alloy (Cu–Al–Zn alloy-reducer of nitrites andnitrates), and it constituted the sum of organic and ammonium nitrogen. Availablepotassium and phosphorus forms were determined by the method of Egner et al.[36]

Cations (Ca2þ, Mg2þ, Naþ, and Kþ) were determined by Pallman methods in 1NNH4Cl.

[37]

Statistical Evaluation

The relationships between n-butanol fraction of polycyclic aromatic hydro-carbons and properties of sewage sludges (Table 1) and PAHs (Table 2) weredetermined by correlation analysis with Statistica 5.0. Significance was set at�p< 0.05. Statistically significant differences between the results were evaluated onthe basis of standard deviation determinations and analysis of variance method(ANOVA). Data with normal distribution were analyzed by the t-test forindependent samples (P< 0.05).

RESULTS AND DISCUSSION

The Total Content of PAHs

The total content of polycyclic aromatic hydrocarbons in the sewage sludgestudied varied greatly. The total content of the 10 PAHs ranged from 3012.0 to27954.8 mg/kg d.m. (Fig. 1). In the sewage sludges studied, fluoranthene and

Table 1. The physicochemical properties of sewage sludges used in the experiment.

Sewage

sludge pH TOC Nt Ca2þ Mg2þ Kþ Naþ CEC TEB BS P K

B-40 12.4 169.8 22.4 530.8 183.4 22.9 65.6 803 820 97.9 4.6 0.8

W-100 6.4 227.0 23.0 329.4 200.3 31.3 22.2 583 608 96.0 35.4 3.2

K-100 5.8 228.6 40.6 675.5 410.8 64.2 45.5 1196 1222 97.9 28.0 8.4

L-110 6.5 220.8 44.8 701.9 445.8 67.9 57.4 1273 1295 98.3 25.1 3.0

T-140 5.6 207.0 40.6 530.9 699.4 61.5 40.7 1333 1363 97.8 35.7 3.5

D-170 6.6 240.6 28.0 839.8 130.9 17.5 17.6 1006 1020 98.6 18.2 3.2

P-180 6.9 230.4 35.0 541.3 594.5 47.9 35.6 1219 1234 98.8 22.1 2.2

J-190 6.6 177.0 39.2 241.5 174.7 49.8 24.9 491 513 95.7 18.2 3.2

R-200 7.2 253.2 36.4 411.4 200.9 66.5 45.7 725 746 97.2 24.1 2.5

S-230 5.6 222.6 28.0 1057.0 297.1 18.8 34.3 1407 1425 98.7 12.3 1.2

R-250 6.9 184.2 19.7 295.7 804.4 89.0 34.5 1223 1241 98.6 25.8 5.6

pH-in KCl; TOC—total organic carbon content (g/kg); Nt—the total amount of nitrogen

(g/kg); CEC—cation exchange capacity (mmol/kg), TAB—the total of the exchangeable bases

(mmol/kg), BS—the degree of the base saturation (%); P and K—available forms of

phosphorous and potassium (mg/kg); cations—Mg2þ, Ca2þ, Naþ, Kþ (mmol/kg).


ORDER REPRINTS

benzo[b]fluoranthene predominated, and in few cases, significant amounts of pyrene

and benzo[a]anthracene (>14%) were observed. Taking into consideration the PAH

content related to the number of rings, the widest group were 4-rings compounds

where the content in the different types of sewage sludges studied exceeded 50%.

Some authors attempt to identify the source of PAH in order to determine PAH the

origin based on the presence of individual compounds from this group or

Table 2. The physicochemical properties of PAHs.a

PAHs MW S logKow

log Koc

Hs1� MSAmin max mean

Phen 178 1.1 4.57 4.10 6.70 5.40 3.24 4.815 198.0

Ant 178 0.05 4.54 4.20 6.90 5.55 3.96 4.809 202.2

Fluo 202 0.13 5.22 4.60 6.70 5.65 0.92 1.220 218.6

Pyr 202 0.26 5.18 4.60 6.80 5.70 1.04 5.559 213.5

BaA 228 0.002 5.61 4.50 6.70 5.60 0.58 6.226 —

Ch 228 0.011 5.91 4.90 7.80 6.35 0.065 6.226 240.2

BbF 252 0.0038 6.60 5.70 7.50 6.60 — 6.976 —

BaP 252 0.0008 6.04 6.30 8.50 7.40 0.046 6.976 225.6

BghiP 276 0.0006 7.10 6.20 9.20 7.70 0.075 7.720 266.9

Ind 276 0.062 7.10 6.60 9.20 7.90 — 7.720 —

aData from Refs. [14,21,60–63]

MW—molecular weight; S—water solubility; log Kow—octanol water partitioning coefficient;

log Koc—organic carbon–water partitioning coefficient, Hs—Henry constant; 1�—molecular

connectivity index; MSA—molecular surface area.

B-40 W -100 K-100 L-110 T-140 D-170 P-180 J-190 R-200 S-230 R-250

Sewage sludges

0

4000

8000

12000

16000

20000

24000

28000

32000

PA

H c

onte

nt [µ

g/kg

]

Total PAHs contentMild-extracted solvent PAHs content

Figure 1. The mild-extracted solvent and total PAHs content in investigated sewage sludges.


ORDER REPRINTS

determining relations between the individual PAHs. The above method is usedmainly for soils[38] and sediments.[4,39,40] In the case of sewage sludge, the mostrepresentative seems to be the method proposed by Budzinski et al.[39] Further to thismethod, it is assumed that the value of the coefficient phenantrene/anthracene (Fen/Ant)>10 indicates that the source of the origin of PAHs are the processes to whichcrude oil is subjected, whereas the value of the phenantrene/anthracene coefficientlower than 10, points to the predominance of pyrolytic processes. In the case of thefluoranthene/pyrene coefficient, it is assumed that values higher than 1 are related topyrolytic processes, mainly coal burning.

The values of coefficients: phenantrene/anthracene and fluoranthene/pyrene inthe sewage sludge samples studied showed that the main share of PAHs in mostsewage sludge samples was related to pyrolytic processes. Only in the case of onesewage sludge sample (R-250) was the value of the fluoranthene/pyrene coefficientabove 1. At the same time, the highest value of the phenanthrene/anthracenecoefficient was found in this sample. On the basis of the above data, it can beassumed that discharges from the fuel industry could have contributed to thepollution of sewage sludge with PAHs. It would also confirm the high contributionof benzo[ghi]perylene when compared to other sludges studied as suggested byPerez et al.[11]

Potentially Bioavailable Content of PAHs

As can be seen in the data presented in Fig. 1, only in the case of one sludge(W-100) were the differences between the total PAH content and the content ofPAHs extracted with n-butanol found to be insignificant. In much of the sewagesludge, these differences were markedly higher and for more than half of the sewagesludge studied they exceeded 50%. Figure 2 presents the contribution of then-butanol fraction in the total PAH content in relation to the number of rings.The contribution of 4 and 5-rings PAHs extracted with n-butanol in relation to thetotal content of the compounds studied was characterized by a low relativelystandard deviation (RSD), i.e., 36.9 and 38.0%, respectively, whereas for theremaining PAHs groups (3 and 6-rings) the RSD values exceeded 50%.

Figure 3 presents the mean and the maximum contribution of the n-butanolfraction of the individual PAHs noted in the total content of these compounds. Inthe case of most PAHs, their mean share did not differ significantly, statisticallyspeaking, from the PAH type and was often close to 40%. Only in the case of thepyrene, did the mean share of the n-butanol fraction exhibit a clearly higher valuethan that of the remaining compounds at a level of about 55%. The lowest meanvalue was noted for chrysene (>30%) (Table 3).

On the other hand, the statistical analysis carried out did not show any clearinfluence of the properties of PAH and the properties of the various types of sludgeon the share of the fraction of the n-butanol extracted. Statistically significantrelations (P� 0.05) were only obtained between the nitrogen content and the share ofthe n-butanol fraction of benzo[b]fluorantene (�0.662), 5-rings PAHs (�0.696), andthe sum of the 10 compounds determined (�0.608). However, correlationsconcerning the same groups but characterized by a reverse direction of the influence


ORDER REPRINTS

were also found for the C/N ratio (0.633; 0.725; 0.632). The remaining statisticallysignificant relations observed concerned Ca2þ cations (anthracene �0.608; fluor-anthene �0.687; indeno[1,2,3-cd]pyrene �0.611) and Kþ (benzo[a]anthracene�0.622; the total of the 10 PAHs�0.607 and 4-rings PAHs�0.699). As observedwith the Nt, they took on negative values.

Phen Ant Fluo Pyr BaA Ch BbF BaP BghiP Ind

PAHs

0

10

20

30

40

50

60

70

80

90

100

Con

trib

utio

n [%

]

Mean contribution of n-butanol fractionMaximum contribution of n-butanol fraction

Figure 3. Mean and maximum contribution of individual PAHs extracted by n-butanol.

Figure 2. Contribution of PAHs extracted by n-butanol in relation to number of rings.


ORDER REPRINTS

Table

3.

Totalandn-butanolextracted

contentofindividualPAHsin

investigatedsewagesludges.

PAHscontent(mg/kg)

Sew

agesludges

Phen

Ant

Fluo

Pyr

BaA

Ch

BbF

BaP

BghiP

Ind

B-40

Total

548�10

153�13

1470�10

1058�14

818�8

282�8

725�12

430�12

83�9

188�11

n-But

309�12

127�10

589�11

696�10

508�12

50�10

488�11

272�9

30�9

114�12

W-100

Total

648�8

546�7

478�16

223�15

45�24

479�31

241�11

594�5

545�5

632�4

n-But

576�13

522�15

311�13

223�10

345�12

409�9

134�11

445�11

486�9

575�10

K-100

Total

1144�12

333�7

3602�8

2070�11

1621�10

1046�13

3639�9

1602�9

668�11

1045�12

n-But

656�11

139�9

2617�9

1�14

416�12

156�9

659�10

1073�10

163�12

688�10

L-110

Total

253�9

80�11

1240�8

n.d.

560�12

553�12

392�9

247�11

109�9

177�13

n-But

26�10

14�12

342�10

n.d.

246�13

184�12

5�10

137�12

11�10

113�13

T-140

Total

245�8

46�6

678�11

574�13

176�14

120�8

628�12

297�9

99�10

150�11

n-But

33�12

5�9

18�9

482�13

74�12

41�9

183�11

6�11

10�12

24�9

D-170

Total

405�9

147�11

2315�8

2169�12

1078�13

917�11

2529�12

437�10

169�9

305�13

n-But

113�8

n.d.

793�10

1042�9

282�10

500�13

1625�8

n.d.

n.d.

59�9

P-180

Total

764�10

239�12

3469�11

2752�9

1420�8

847�13

3019�10

661�12

473�11

331�11

n-But

n.d.

12�11

951�9

1824�13

n.d.

n.d.

1517�10

279�10

373�12

120�12

J-190

Total

1149�9

318�12

5400�11

5051�9

2579�8

1869�12

7573�10

1786�9

835�13

1396�10

n-But

544�11

113�12

2457�10

2520�12

1024�9

n.d.

2729�12

798�10

n.d.

628�12

R-200

Total

1052�9

426�14

2827�8

n.d.

613�11

414�9

3512�9

370�13

261�10

316�14

n-But

811�9

277�13

1278�10

n.d.

n.d.

7�12

2524�8

257�13

198�11

262�13

S-230

Total

432�9

284�13

2271�13

1253�10

1493�8

866�10

2480�12

655�12

484�10

414�10

n-But

280�12

203�11

1539�14

663�11

1172�8

568�9

1663�12

384�14

223�9

225�11

R-250

Total

725�13

101�10

409�9

1904�11

802�12

760�14

289�10

376�13

61�9

139�11

n-But

322�11

111�12

416�11

840�9

36�9

113�12

122�12

189�11

16�10

n.d.

Total—

PAHsextracted

bydichloromethane;

n-But—

PAHsextracted

n-butanol;Phen—

phenantherene;

Ant—

anthracene;

Fluo—

fluoranthene;

Pyr—

pyrene,

BaA—

benzo[a]anthracene;

Ch—

chryzene;

BbF—

benzo[b]fluoranthene;

BaP—

benzo[a]pyrene,

BghiP—

benzo[ghi]perylene;

Ind—

indeno[1,2,3-cd]pyrene;�—

relativestandard

deviation(n¼3,%

).


ORDER REPRINTS

It is difficult to relate the results obtained to the data presented by other authors.

The existing information concerns mainly those soils polluted with PAHs.[41–48] The

studies carried out so far show that the soil’s properties—such as the content of

organic matter,[41,43,45] the nanoporosity and hydrophobicity of the matrix,[49] as well

as the cation exchange capacity (CEC),[45]—play an important role in the

bioavailability of pollutants for the soil’s microorganisms and invertebrates.

Chung and Alexander[45] obtained a clear relationship between the content of

organic matter and the percentages of phenanthrene not extracted by n-butanol from

the soil. Nam et al.[41] found also that the amount of the phenanthrene fraction

extracted with n-butanol increased markedly with the decrease in the content of

organic carbon in the soil. The above observation points to the important role of the

organic fraction both in sequestering and in the bioavailability of phenanthrene. In

the present study, no significant statistic relations between TOC and n-butanol

fraction were noted, however there was a significant statistical relationship (0.603;

P� 0.05) between benzo[a]pyrene and the residue after the extraction of n-butanol.

It is surprising that in the present study, the share of n-butanol fraction in the various

types of sludge with a relatively low content of organic matter (J-190, R-250)

(Table 1), and in the case of most PAHs—as well as their sum total—was markedly

lower than in sludge with about a 20% higher content of organic carbon (W-100,

R-200, S-230) (Table 1). The above points to the existence of factors other than

organic matter, which determine the content of the bioavailable PAH fraction.

Significant correlations between the residue after the extraction of n-butanol and

CEC, TEB, and BS were also found in the case of chrysene (�0.651;�0.645;�0.803;

P� 0.05, respectively). A similarly high correlation but with a positive value,

however, was also observed by Chung and Alexander[45] in the case of phenanthrene.

Moreover, these last authors showed also that there exist high relations between the

content of TOC and CEC. In the present study, no such relation was noted which

could explain the opposite of the relation between CEC and PAHs as observed in the

studies by Chung and Alexander.[45]

The lack of relations between the content of the n-butanol PAH fraction and the

sewage sludge properties, even though it was noted in the case of the soils, could be

related to the properties of the sewage sludge matrix. Sewage sludge is characterized

by the clearly higher values of almost all the physico–chemical properties studied

(in some cases they were even several times higher); hence their influence on the PAH

desorption processes could be different than for soils. Other pollutant levels some

several degrees higher, both with respect to their amounts and diversification, were

found in the sludge. Some of them (for example surfactants), frequently noted in the

various types of sewage sludge,[50,51] can significantly increase the bioavailability and

desorption of the PAHs.[52,53]

Studies carried out by some other authors on PAH bioavailability and

sequestration showed that such factors as the concentration of contaminants,[42]

the wetting and drying of the soil,[47,48] soil moisture,[54] slurring,[52] the presence of

other PAHs[44,52] and the length of time that the soil and the pollutant are in

contact,[55] can also influence the scope of the above process along with the

properties of the soil mentioned above. All the factors enumerated above can also

influence the process of the bioavailability of pollutants in sewage sludge. A precise


ORDER REPRINTS

determination of the influence of the factors enumerated requires model studies to be

initially conducted on the technological line of the sewage treatment plant.Relations between the percentage content of the bioavailability of the PAH

fraction (in n-butanol) and the residue after the extraction of n-butanol were

evaluated with the following PAH properties (Table 2): Henry’s constant (Hs) related

to volatilisation ability,[56] water solubility (S) related to bio-availability,[57] the

octanol–water partition coefficient (logKow), the organic carbon–water partition

coefficient (log Koc), the first-order molecular connectivity index (1�) and the

molecular surface area (MSA) related to soil sorption affinity.[58–60] In the case of

one sludge only (S-230) was any statistically significant relation noted between the

share of the n-butanol fraction and log Koc (�0.674). These results suggest that

the properties tested were poorly correlated with the n-butanol fraction of PAHs.

It could be suspected that in the above process, the properties may be more

descriptive of bioavailability. Similar relationships between the PAH properties

studied and PAH bioavailability and sequestration were observed by Kottler and

Alexander.[61]

The content of the PAH fraction present in the sewage sludge pore water

(calculated according to Eq. (1) ranged from 0.00081 to 0.00385% for the sum of the

compounds studied. Much lower values were noted for individual PAHs (Table 4).

Interesting results were obtained during the evaluation of the relationships between

the content of PAHs extracted with n-butanol (Table 3) and content of PAHs

evaluated in pore water of sewage sludge. High and significant relationships were

observed both in the case of the content and percentage PAH share of the forms

selected (Fig. 4). In the case of the sum of the compounds studied, their respective

values were: 0.859 and 0.881 for the content and percentage share. In the case of

some individual PAH forms, high and statistically significant differences were also

noted. Only chrysene and benzo[ghi]perylene (for the content) and pyrene (for the

percentage share) were the exceptions in this case, no statistically significant relations

being noticed for them. The results obtained showed that the n-butanol fraction is

connected to a high degree with the PAH content determined in the sewage sludge

pore water. In order to discover the mechanisms responsible for the phenomena

observed, it is necessary to carry out additional studies, however, the information

presented above clearly shows that the PAH content in the sewage sludge pore water

can, indirectly, have a significant influence on the sequestration and bioavailability

of the pollutants.When analyzing the relations between the PAH content in sewage sludge pore

water and water solubility (S), it was found that in 5 types of sludge (K-100, D-170,

J-190, R-200, R-250) this property was significantly (>0.694, P� 0.05) statistically

correlated with the PAH fraction share potentially present in sewage sludge pore

water. Among the sludge types enumerated, two (J-190 and R-250) drew the

attention of the researchers earlier since despite the low content of organic matter,

they were characterized by the low content of the n-butanol fraction. The above

observation could mean that water solubility in the case of these sludge types

(decreased by the low content of the factors increasing solubility) limited the

bioavailability of the pollutants in them more than did the content of the organic

carbon.


ORDER REPRINTS

Table

4.

TheconcentrationofPAHsin

sewagesludgepore

watercalculatedonthebasisofanequilibrium

partitionmodel

(1).

PAHsa

B-40

W-100

K-100

L-110

T-140

D-170

P-180

J-190

R-200

S-230

R-250

Phen

0.012838

0.011364

0.019920

0.004569

0.004715

0.006702

0.013192

0.025849

0.016543

0.007730

0.015670

Ant

0.002541

0.006779

0.004101

0.001025

0.000621

0.001724

0.002920

0.005057

0.004736

0.003595

0.001614

Fluo

0.019382

0.004714

0.035274

0.012568

0.007329

0.021538

0.033706

0.068299

0.024997

0.022836

0.004971

Pyr

0.012426

0.001960

0.018070

0.000000

0.005535

0.017986

0.023829

0.056932

0.000000

0.011230

0.020622

BaA

0.012104

0.004980

0.017812

0.006366

0.002132

0.011253

0.015480

0.036604

0.006084

0.016841

0.010929

Ch

0.000741

0.000943

0.002044

0.001119

0.000258

0.001702

0.001641

0.004717

0.000731

0.001737

0.001842

BbF

0.001072

0.000267

0.003998

0.000446

0.000762

0.002640

0.003291

0.010746

0.003484

0.002798

0.000393

BaP

0.000101

0.000104

0.000279

0.000045

0.000057

0.000072

0.000114

0.000402

0.000058

0.000117

0.000081

BghiP

0.000010

0.000048

0.000058

0.000010

0.000010

0.000014

0.000041

0.000094

0.000021

0.000043

0.000007

Ind

0.000014

0.000035

0.000058

0.000010

0.000009

0.000016

0.000018

0.000099

0.000016

0.000023

0.000010

PAHssum

0.061228

0.031194

0.101614

0.026158

0.021429

0.063648

0.094233

0.208798

0.056670

0.066952

0.056140

aDescriptionofPAHsin

Table

3.


ORDER REPRINTS

CONCLUSION

The issue presented in this study is relatively poorly described in the literature onthe subject, and the explanation of the relationships observed requires a series ofexaminations. The results obtained showed that the contribution of the PAHsfraction extracted with n-butanol in the total PAH content varies widely.The contribution of the n-butanol extracted fraction ranging from 0 to 100%could prove that the scope of degradation of the pollutants described in the soils

0 2000 4000 6000 8000 10000 12000

Content of PAHs in n-butanol fraction [µg/kg]

0

0.05

0.1

0.15

0.2

0.25

Con

tent

of P

AH

s in

sew

age

slud

ge p

ore

wat

er [µ

g/L]

0 20 40 60 80

Contribution of PAHs in n-butanol fraction [%]

0

0.001

0.002

0.003

0.004

0.005

Con

trib

utio

n of

PA

Hs

in s

ewag

esl

udge

por

e w

ater

[%]

A

B

Figure 4. Correlation between n-butanol extracted PAHs and PAHs in sewage sludge-pore

water. A—content [mg/kg]; B—contribution [%].


ORDER REPRINTS

fertilized with sludge can vary considerably. The high discrepancies in the content of

the n-butanol fraction as well as the unclear relations between this fraction and PAH

properties and the properties of the various types of sewage sludge studied showed

that the amount of this fraction (as well as its scope) depend on other factors which

need further studies for clarification. The PAH content in sewage sludge pore water

in which a significant relation to the n-butanol fraction has been established could

be used as an example here.At the present stage of research, it is also important to determine to what degree

the bioavailability established on the basis of the above described examinations also

holds true for the bioavailability of these pollutants after fertilization of the soil

with sewage sludge.

ACKNOWLEDGMENTS

Financial support from the State Committee for Scientific Research (MNiI,

Warsaw). Project no. KBN 3 P06S 042 25 is gratefully acknowledged. P. Oleszczuk

is granted by the Foundation for Polish Science

REFERENCES

1. Keith, L.H.; Telliard, W.A. Priority pollutants I—a perspective view. Environ.

Sci. Technol. 1979, 13, 416–423.2. Cerniglia, C.E. Biodegradation of polycyclic aromatic hydrocarbons. Curr.

Opinion Biotechnol. 1993, 4, 331–338.3. Maliszewska-Kordybach, B. Persistent organic contaminants in the environ-

ment: PAHs as a case study. Bioavailability of Organic Xenobiotics in the

Environment; Kluwer Academic Publishers: Netherlands, 1999; pp. 3–34.4. Baran, S.; Oleszczuk, P.; Lesiuk, A.; Baranowska, E. Trace metals and polycyclic

aromatic hydrocarbons in surface sediment samples from the Narew river

(Poland). Pol. J. Environ. Stud. 2002, 11, 299–305.5. Baran, S.; Bielinska, E.J.; Oleszczuk, P. Enzymatic activity in an airfield soil

polluted with polycyclic aromatic hydrocarbons (PAH). Geoderma 2004, 118,

221–232.6. Wild, S.R.; Jones, K.C. Polynuclear aromatic hydrocarbons in the United

Kingdom environment: a preliminary source inventory and budget. Environ.

Pollut. 1995, 88, 91–108.7. Smith, K.E.C.; Green, M.; Thomas, G.O.; Jones, K.C. The behaviour of sewage

sludge derived PAHs on pasture. Environ. Sci. Technol. 2001, 35, 2141–2150.8. Baran, S.; Oleszczuk, P. Changes in the content of polycyclic aromatic

hydrocarbons (PAHs) in light soil fertilised with sewage sludge. J. Environ.

Sci. Health A 2003, 38, 793–805.9. Bodzek, D.; Janoszka, B.; Dobosz, C.; Warzecha, L.; Bodzek, M. Determination

of polycyclic aromatic compounds and heavy metals in sludges from biological

sewage treatment plants. J. Chromatogr. A 1997, 774, 177–192.


ORDER REPRINTS

10. Lazzari, L.; Sperni, L.; Salizzato, M.; Pavoni, B. Gas chromatographicdetermination of organic micropollutants in samples of sewage sludge andcompost: behaviour of PCB and PAH during composting. Chemosphere 1999,38, 1925–1935.

11. Perez, S.; Farre, M.; Garcia, M.J.; Barcelo, D. Occurence of polycyclicaromatic hydrocarbons in sewage sludge and their contribution to its toxicityin the ToxAlert 100 bioassay. Chemosphere 2001, 45, 705–712.

12. Stevens, J.L.; Northcott, G.L.; Stern, G.A.; Tomy, G.; Jones, K.C. PAHs,PCBs, PCNs, organochlorine pesticides, synthetic musks and polychlorinatedn-alkanes in UK sewage sludge: survey results and implications. Environ. Sci.Technol. 2003, 37, 462–467.

13. Baran, S.; Oleszczuk, P. The concentration of polycyclic aromatic hydro-carbons in sewage sludge in relation to the amount and origin of sewagepurified. Pol. J. Environ. Stud. 2003, 12, 523–529.

14. Oleszczuk, P.; Baran, S. Preliminary investigation for forecasting the content ofpolycyclic aromatic hydrocarbons after soil fertilization with sewage sludge.Pol. J. Environ. Stud. 2004, 13, 253–260.

15. Loibner, A.P.; Holzer, M.; Gartner, M.; Szolar, O.H.J.; Braun, R. The use ofsequential supercritical fluid extraction for bioavailability investigations ofPAH in soil. Die Bodenkultur 2000, 51, 225–233.

16. Hawthorne, S.B.; Grabanski, C.B. Correlating selective supercritical fluidextraction with bioremediation behavior of PAHs in a field treatment plot.Environ. Sci. Technol. 2000, 34, 4103–4110.

17. Szolar, O.H.J.; Rost, H.; Braun, R.; Loibner, A.P. Assessment of(Bio)Availability of PAHs in Soil Using Sequential Supercritical FluidExtraction (SSFE), Proceedings of the First European BioremediationConference, Technical University: Chania, 2001.

18. Cornelissen, G.; Rigterink, H.; Ferdinandy, M.M.A.; van Noort, P.C.M.Rapidly desorbing fractions of PAHs in contaminated sediments as a predictorof the extent of bioremediation. Environ. Sci. Technol. 1998, 32, 966–970.

19. Akkanen, J.; Penttinen, S.; Haitzer, M.; Kukkonen, J.V.K. Bioavailability ofatrazine, pyrene and benzo[a]pyrene in European river waters. Chemosphere2001, 45, 453–462.

20. Richardson, B.J.; Zheng, G.J.; Tse, E.S.C.; de Luca-Abbott, S.B.; Siu, S.Y.M.;Lam, P.K.S. A comparison of polycyclic aromatic hydrocarbon and petroleumhydrocarbon uptake by mussels (Perna viridis) and semi-permeable membranedevices (SPMDs) in Hong Kong coastal waters. Environ. Pollut. 2003, 122,223–227.

21. Krauss, M.; Wilcke, W. Biomimetic extraction of PAHs and PCBs from soilwith octadecyl-modified silica disks to predict their availability to earthworms.Environ. Sci. Technol. 2001, 35, 3931–3935.

22. Tang, J.; Liste, H.H.; Alexander, M. Chemical assays of availability toearthworms of polycyclic aromatic hydrocarbons in soil. Chemosphere 2002,48, 35–42.

23. Cuypers, C.; Grotenhuis, T.; Joziasse, J.; Rulkens, W. Rapid persulfateoxidation predicts PAH bioavailability in soils and sediments. Environ. Sci.Technol. 2000, 34, 2057–2063.


ORDER REPRINTS

24. Zhao, X.; Voice, T.C. Assessment of bioavailability using a multicolumn

system. Environ. Sci. Technol. 2000, 34, 1506–1512.25. Reid, B.J.; Stokes, J.D.; Jones, K.C.; Semple, K.T. Nonexhaustive

cyclodextrin-based extraction technique for the evaluation of PAH bioavail-

ability. Environ. Sci. Technol. 2000, 34, 3174–3179.26. Kelsey, J.W.; Kottler, B.D.; Alexander, M. Selective chemical extractants to

predict bioavailability of soil-aged organic chemicals. Environ. Sci. Technol.

1997, 31, 214–217.27. Macleaod, C.J.A.; Semple, K.T. Sequential extraction of low concentrations of

pyrene and formation of non-extractable residues in sterile and non-sterile soils.

Soil Biol. Biochem. 2003, 35, 1443–1450.28. Liste, H.H.; Alexander, M. Butanol extraction to predict bioavailability of

PAHs in soil. Chemosphere 2002, 46, 1011–1017.29. Oleszczuk, P.; Baran, S. Optimization of ultrasonic extraction of polycyclic

aromatic hydrocarbons from sewage sludge samples. Chem. Anal. 2003, 48,

211–221.30. Oleszczuk, P.; Baran, S. Application of solid-phase extraction to determination

of polycyclic aromatic hydrocarbons in sewage sludge. J. Hazard. Matter. 2004,

(In press).31. Swartz, R.C.; Schults, D.W.; Ozretich, R.J.; Lamberson, J.O.; Cole, F.A.;

DeWitt, T.H.; Redmond, M.S.; Ferraro, S.P. �PAH: a model to predict the

toxicity of polynuclear aromatic hydrocarbon mixtures in field-collected

sediments. Environ. Toxicol. Chem. 1995, 11, 1977–1987.32. Sijm, D.; Kraaij, R.; Belfroid, A. Bioavailability in soil and sediment: exposure

different organisms and approaches to study it. Environ. Pollut. 2000, 108,

113–119.33. Sverdrup, L.E. Toxicity of Tar Constituents in Terrestrial Ecosystem. Effects of

Eight Polycyclic Aromatic Compounds on Terrestrial Plants, Soil Invertebrates

and Microorganisms. Ph.D. thesis, Faculty of Mathematics and Natural

Sciences, University of Oslo, 2001.34. Misztal, M.; Smal, H.; Wojcikowska-Kapusta, A. Lithosphere and Its

Protection; Wyd. AR: Lublin, 1997.35. van Reeuwijk, L.P. Procedures for Soil Analysis; ISRIC: Wageningen, 1995.36. Egner, H.; Riehm, H.; Domingo, W.R. Untersuchungen uber die chemische

Bodenanalyse als Grundlage fur die Beurteilung des Nahrstoffzustandes der

Boden: II. Chemische Extraktionsmethoden zur Phosphor-und Kalium

bestimmung. Kungl. Lantbrukshogskolans Annaler 1960, 26, 45–61.37. Drozd, J.; Licznar, M.; Licznar, S.E.; Weber, J. In Soil Science with Mineralogy

and Petrography Elements; Wyd, A.R., Ed.; Wrocbaw: Poland, 1998.38. Jones, K.C.; Stratford, J.A.; Waterhouse, K.S.; Furlong, E.T.; Giger, W.;

Hites, R.A.; Schaffner, C.; Johnston, A.E. Increases in the polynuclear

aromatic hydrocarbon content of an agricultural soil over the last century.

Environ. Sci. Technol. 1989, 23, 95–101.39. Budzinski, H.; Jones, I.; Bellocq, J.; Pierard, C.; Garrigues, P. Evaluation of

sediment contamination by polycyclic aromatic hydrocarbons in the Gironde

estuary. Mar. Chem. 1997, 58, 85–97.


ORDER REPRINTS

40. Gschwend, P.M.; Hites, R.A. Fluxes of the polycyclic aromatic compounds to

marine and lacustrine sediments in the northeastern United States. Geochim.

Cosmochim. Acta 1981, 45, 2359–2367.41. Nam, K.; Chung, N.; Alexander, M. Relationship between organic matter

content of soil and the sequestration of phenanthrene. Environ. Sci. Technol.

1998, 32, 3785–3788.42. Chung, N.; Alexander, M. Effect of concentration on sequestration and

bioavailability of two polycyclic aromatic hydrocarbons. Environ. Sci. Technol.

1999, 33, 3605–3608.43. White, J.C.; Hunter, M.; Nam, K.; Pignatello, J.J.; Alexander, M. Correlation

between biological and physical availabilities of phenanthrene in soils and soil

humin in aging experiments. Environ. Toxicol. Chem. 1999, 18, 1720–1727.44. White, J.C.; Hunter, M.; Pignatello, J.J.; Alexander, M. Increase in bioavail-

ability of aged phenanthrene in soils by competitive displacement with pyrene.

Environ. Toxicol. Chem. 1999, 18, 1728–1732.45. Chung, N.; Alexander, M. Effect of soil properties on bioavailability and

extractability of phenanthrene and atrazine sequestered in soil. Chemosphere

2002, 48, 109–115.46. Chung, N.; Alexander, M. Differences in sequestration and bioavailability of

organic compounds aged in dissimilar soils. Environ. Sci. Technol. 1998, 32,

855–860.47. White, J.C.; Quinones-Rivera, A.; Alexander, M. Effect of wetting and drying

on the bioavailability of organic compounds sequestered in soil. Environ.

Toxicol. Chem. 1998, 17, 2378–2382.48. White, J.C.; Kelsey, J.W.; Hatzinger, P.B.; Alexander, M. Factors affecting

sequestration and bioavailability of phenanthrene in soils. Environ. Toxicol.

Chem. 1997, 16, 2040–2045.49. Nam, K.; Alexander, M. Role of nanoporosity and hydrophobicity in

sequestration and bioavailability: tests with model solids. Environ. Sci.

Technol. 1998, 32, 71–74.50. Hesselsoe, M.; Jensen, D.; Skals, K.; Olesen, T.; Moldrup, P.; Roslev, P.;

Mortensen, G.K.; Henriksen, K. Degradation of 4-nonylphenol in homo-

geneous and nonhomogeneous mixtures of soil and sewage sludge. Environ.

Sci. Technol. 2001, 35, 3695–3700.51. Petrovic, M.; Barcelo, D. Determination of anionic and nonionic surfactants,

their degradation products, and endocrine-disrupting compounds in sewage

sludge by liquid chromatography/mass spectrometry. Anal. Chem. 2000, 72,

4560–4567.52. White, J.C.; Alexander, M.; Pignatello, J.J. Enhancing the bioavailability of

organic conmpounds sequestrered in soil and aquifer solids. Environ. Toxicol.

Chem. 1999, 18, 182–187.53. Guha, S.; Jaffe, P.R.; Peters, C.A. Bioavailability of mixtures of PAHs

partitioned into the micellar phase of a non-ionic surfactant. Environ. Sci.

Technol. 1998, 32, 2317–2324.54. Kottler, B.D.; White, J.C.; Kelsey, J.W. Influence of soil moisture on the

sequestration of organic compounds in soil. Chemosphere 2001, 42, 893–898.


ORDER REPRINTS

55. Macleod, C.J.A.; Semple, K.T. Influence of contact time on extractability and

degradation of pyrene in soils. Environ. Sci. Technol. 2000, 34, 4952–4957.56. Beck, A.J.; Johnson, D.L.; Jones, K.C. The form and bioavailability of non-

ionic organic chemicals in sewage sludge-amended agricultural soils. Sci. Total

Environ. 1996, 185, 125–149.57. Wild, S.R.; Berrow, M.L.; Jones, K.C. The persistence of polynuclear aromatic

hydrocarbons (PAHs) in sewage sludge amended agricultural soils. Environ.

Pollut. 1991, 72, 141–157.58. Karickhoff, S.W.; Brown, D.S.; Scott, T.A. Sorption of hydrophobic pollutants

on natural sediments. Water Res. 1979, 13, 241–248.59. Reid, B.J.; Jones, K.C.; Semple, K.T. Bioavailability of persistent organic

pollutants in soils and sediments—a perspective on mechanisms, consequences

and assessment. Environ. Pollut. 2000, 108, 103–112.60. Maliszewska-Kordybach, B. The relationship between the properties of PAHs

and the rate of their disappearance form soils. Environ. Toxicol. Chem. 1998,

66, 47–52.61. Kottler, B.D.; Alexander, M. Relationship of properties of polycyclic aromatic

hydrocarbons to sequestration in soil. Environ. Pollut. 2001, 113, 293–298.62. Krauss, M.; Wilcke, W. Predicting soil–water partitioning of polycyclic

aromatic hydrocarbons and polychlorinated biphenyls by desorption with

methanol-water mixtures at different temperatures. Environ. Sci. Technol.

2001, 35, 2319–2325.63. Mackay, D.; Shiu, W.Y.; Ma, K.C. Illustrated Handbook of Physical-Chemical

Properties and Environmental Fate for Organic Chemicals. Polynuclear Aromatic

Hydrocarbons, Polychlorinated Dibenzodioxins and Dibenzofurans; Lewis

Publishers: Boca Raton, FL, 1992; Vol II.

Received March 22, 2004


the concentration of mild-extracted polycyclic aromatic hydrocarbons in sewage sludges

Documents