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Accumulation and risk assessment of polycyclic aromatic hydrocarbons (PAHs) in soils around oil slud


Environ Earth Sci DOI 10.1007/s12665-011-0960-9

ORIGINAL ARTICLE

Accumulation and risk assessment of polycyclic aromatic hydrocarbons (PAHs) in soils around oil sludge in Zhongyuan oil ?eld, China
Shaoping Kuang ? Zhanchao Wu ? Laishi Zhao

Received: 10 December 2009 / Accepted: 7 February 2011 ? Springer-Verlag 2011

Abstract In this paper, the contents of polycyclic aromatic hydrocarbons (PAHs) in soil samples around three different oily sludge plants in winter were analyzed by high performance liquid chromatography (HPLC) and the pollution degree with PAHs in soil samples was determined. Soil samples were collected from the agricultural soil around three different oily sludge plants (the Third Wenming Plant, the Third Mazhai Plant, and the Fourth Wener Plant) along with the leeway in Zhongyuan oil ?eld. The distances from collected sample sites to oily sludge plants are 10, 20, 50, 100, 200, and 500 m, respectively. The results show that the contents of PAHs in soil samples decrease dramatically with the increase of the distance from the oily sludge, and that the PAHs with 2–4 rings are major pollutants in the oily sludge and soil samples. The main factors, which in?uenced the distribution of PAHs are discussed. Based on Nemero Index P, the classi?cation evaluation shows that the soils around the oily sludge are heavily polluted in winter. The health risk assessment and ecological risk assessment of the soils around the oily sludge in Zhongyuan oil ?eld in winter are analyzed.

Keywords Contamination ? Soil ? PAHs ? Health risk assessment ? Ecological risk assessment

Introduction In recent years, concern about persistent organic pollutants (POPs) has considerably increased (Nadal et al. 2004). One of the most common representatives of POPs in nature environment are polycyclic aromatic hydrocarbons (PAHs), which represent signi?cant threat to the ecosystem and especially to people due to their widespread distribution in the environment and potential toxicity to organisms. For example, many of the PAHs with four or more rings are carcinogenic and mutagenic because of their metabolic transformation capability. Consequently, PAHs are among the priority pollutant list of the Environmental Protection Agency (EPA, USA). Many countries including China also place several of PAHs into black list or gray list of priority pollutants (Maria et al. 2006; Patryk and Stanislaw 2005; Baran et al. 2004). Polycyclic aromatic hydrocarbons originate mainly from anthropogenic sources such as combustion of fossil fuels and direct release of oil and its products (http://www. chem.unep.ch/gmn/default.htm). Owing to the rapid demand for oil during the last two decades, air, water, and soil have been signi?cantly polluted (Jiang et al. 2005). Sources, environmental behaviors, ecological effect, and remediation of PAHs in air and water have been presented by many authors (Qiao et al. 2006; Ge et al. 2005; Doick et al. 2005; Hafner et al. 2005; Duan et al. 2005; Kannan et al. 2005; Li et al. 2004; Tao et al. 2004; Zhu et al. 2004; Tian et al. 2003; Jia 1999). However, there are few reports about the degree of pollution involving PAHs in agricultural soil around oil ?elds (Ling et al. 2005, 2006;

S. Kuang ? Z. Wu Qingdao University of Science and Technology, Qingdao 266042, China S. Kuang (&) ? Z. Wu ? L. Zhao (&) State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074, China e-mail: kuang1009@126.com S. Kuang ? Z. Wu Key Laboratory of Biogeology and Environmental Geology of Ministry of Education, China University of Geosciences, Wuhan 430074, China

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Zhan et al. 2006; Zhang et al. 2005; Ding et al. 2004; Tao et al. 2003; Zhan and Zhou 2003; Liste and Alexander 2000; Menzies et al. 1992). It is of particular signi?cance to determine the degree of contamination involving PAHs in soils around oil ?elds as PAHs can easily enter the sediment. In this paper, the distribution of PAHs in agricultural soil around the Zhongyuan oil ?eld was analyzed to carry out the pollution treatment and reasonable distribution of the agricultural products in this region pertinently. The main factors, which in?uenced the distribution of PAHs were also discussed. Nemero Index P determined the pollution level in the soil adjacent to the oily sludge that was used for environmental health risk analysis. The results will provide theoretical basis for proper utilization and scienti?c management of oily sludge in Zhongyuan oil ?eld.

particles. They were placed in a polyvinyl chloride bag and stored at room temperature after sieving. Instruments High performance liquid chromatography (HPLC, Shimadzu, Japan) with a ?uorescence detector and VP-ODS column (Serial No. 9122504, 150L 9 4.6) was used for determination of PAHs. The ultrasonic washer (KQ5200, Kun Shan in China) was used for the extraction of PAHs. The rotary evaporator (Shen Sheng SENCO-R, China) and the thermostat water bath (Shen Sheng W201B, China) were used for the concentration of PAH liquors. Low-speed tabletop centrifuge (TDL-40B, Shanghai) was used for separating PAH samples. A water-cycling, multipurpose vacuum pump (SHB-III, Zheng Zhou in China) and a quick mixer (Chang Zhou, China) were used in this study. Reagents Dichloromethane, cyclohexane, and methanol were of analytical grade. Acetonitrile was of chromatographic grade. Silica gel (dikma, the diameter was from 0.15 to 0.074 mm) was reactivated at 130°C for 16 h immediately prior to use. Anhydrous sodium sulphate was heated at 500°C in a furnace for 2 h prior to use and stored in a sealed desiccator. The standards of 16 PAHs were from Supelco Company (USA). Analytical procedure The extraction, concentration, and puri?cation of PAHs A 5.00 g sample was put into a 100 mL centrifuge bottle. Then 20.00 mL of dichloromethane was added. The centrifuge bottle was kept in the ultrasonic washer at 40°C for 2 h and then transferred into a centrifugal vacuum pump of 2,000 r/min for 5 min. 10.00 mL of supernatant was moved into an egg yard type bottle, and all the solvent was evaporated by rotary evaporator at 40°C. Afterwards, the resulting residue was dissolved in 2.00 mL of cyclohexane. 0.50 mL of the obtained solution was put in the mini silica column packed with 1.00 g of silica gel. The column was eluted with methylene chloride/hexane (1:1, v/v), and the eluate was discarded with 1.00 mL. The second fraction containing PAHs was collected with 2.00 mL, and blown drying by nitrogen. The residue was redissolved in 1.00 mL of acetonitrile and stored at 4°C. Determination of PAHs HPLC equipped with ?uorescence detector and VP-ODS column was used. The acetonitrile–water (90:10, v/v)

Samples and experiments Samples collection The oily sludge samples were collected from fresh oily sludge and air-dried oily sludge of the Third Wenming Plant of oily sludge (3W), the Third Mazhai Plant of oily sludge (3M) and the Fourth Wener Plant of oily sludge (4W) in Zhongyuan oil ?eld on December 4 and 8, 2008, respectively. According to the local monsoon feature, the soil samples were collected from the agricultural soil (topsoil 5–10 cm) along with the leeway, which are distant from the oily sludge 10, 20, 50, 100, 200, and 500 m, respectively. There were no factories or residents in the sampling areas. The details of sampling sites are listed in Table 1. Samples treatment The collected samples were air-dried in the shade; the samples were ground according to the order of distance from farthest to nearest, and sieved into 60-mesh size
Table 1 Sampling sites Sample 3M-1 3M-2 3M-3 3M-4 3M-5 3M-6 3M-7 3M-8 Sample 3W-1 3W-2 3W-3 3W-4 3W-5 3W-6 3W-7 3W-8 Sample 4W-1 4W-2 4W-3 4W-4 4W-5 4W-6 4W-7 4W-8 Type Fresh oil sludge Dried oil sludge Soil Soil Soil Soil Soil Soil Distance (m) – – 10 20 50 100 200 500

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solution was used as the mobile phase. The ?ow rate was 0.50 mL/min and the column temperature was at 30°C. A sample preconcentration liquid and a mixed certi?cate liquid of the same volume were extracted separately, and the samples were determined by the external standard method. Quality control The retention time of PAHs standard compound was used to analyze and compare in qualitative analyses and the determination of PAHs external standard method was used in quantitative analyses. The recovery of known samples was (87.74 ± 8.05)%. In addition, principal component analyses were conducted with SPSS 11.0 software. Categories and contents of PAHs in samples are illustrated in Tables 2, 3, 4.

Distribution characteristics of PAHs in soil samples As given in Tables 2, 3, 4, all 16 PAHs from the soil samples were detected. Figure 1 shows the relations between the distances and the contents of PAHs in the soil samples. As seen, the contents of PAHs in soil samples dramatically decreased as the distance from the oily sludge increased. The contents of PAHs in soil samples in 3M, 3W

and 4W were 499.9–2,241.3, 483.0–2,408.8 and 434.5–1,822.0 ng/g, respectively (Kuang et al. 2008). According to the PAHs’ content in soil, the order of pollution degree in soil near the three plants was 3W [ 3M [ 4W, which was consistent with the order of the PAHs contents in oily sludge from the three plants. Tables 2, 3, 4 show that naphthalene, acenaphthene, ?uorene, phenanthrene and pyrene were characteristic PAH factors in the soil samples of 3M and 3W, whereas, naphthalene, acenaphthene, ?uorene and phenanthrene were characteristic PAH factors in the soil samples of 4W. In the soil samples of 3M, 3W and 4W, mass fractions of the characteristic factors of PAHs were 72.4, 72.8 and 74.2%, respectively. Concentrations ranges of individual PAHs compounds in the tested soils in winter are listed in Table 5. From Table 5, it can be seen that the concentrations ratios (Cmax/ Cmin) of 16 PAHs in the 18 soil samples range from 2.83 to 39.4. The ratio order is: Bgp [ I1P [ Chy [ Daa [ Pyr [ Ant [ Ane [ Flu [ Any [ BaAn [ BaP [ Fla [ Phe [ Bkf [ Nap [ Bbf. This result indicates that the pollution degree is signi?cantly different between individual soil samples. As the distance to oily sludge increases, content of each PAHs component decreases. The farther the distance from the oily sludge, the lighter the pollution level.

Table 2 Contents of PAHs of oily sludge samples and peripheral soil samples from 3M Compound NaP Any Ane Flu Phe Ant Fla Pyr BaAn Chy Bbf Bkf BaP I1P Daa BgP RPAHs Fla/Pyr 3M-1 886.6 482.3 644.3 712.1 456.8 46.5 31.5 77.3 70.5 96.8 29.9 46.2 57.5 19.6 13.0 20.0 3,690.9 0.408 3M-2 461.4 274.5 386.1 451.4 289.6 35.3 23.6 66.8 57.0 73.5 26.0 40.8 48.1 10.0 10.6 17.5 2,272.2 0.353 3M-3 612.9 103.5 143.5 189.4 403.2 98.3 96.5 175.5 113.3 120.9 31.4 33.9 19.9 25.3 31.2 42.6 2,241.3 0.550 3M-4 600.1 62.3 118.6 149.8 309.6 81.0 82.8 140.3 96.8 98.3 13.5 31.6 18.3 24.5 27.0 33.7 1,888.2 0.590 3M-5 602.4 51.0 89.7 121.7 256.8 56.3 71.4 86.3 75.8 61.1 14.3 24.7 15.2 11.6 14.7 15.1 1,568.1 0.827 3M-6 485.4 32.3 33.5 41.8 209.6 45.8 66.1 35.3 57.8 23.8 14.3 17.0 5.94 2.41 3.25 5.12 1,079.4 1.87 3M-7 360.1 19.5 24.2 30.2 87.2 29.3 22.8 9.75 24.0 6.15 12.7 12.4 4.06 1.28 1.30 1.33 646.3 2.34 3M-8 275.4 11.4 13.3 23.0 95.2 9.00 12.2 9.75 12.0 5.64 11.9 12.4 5.40 0.96 1.16 1.16 499.9 1.25

Content Unit of PAHs in oily sludge: *103 ng/g; Content Unit of PAHs in soil: ng/g PAHs: NaP naphthalene, Any acenaphthylene, Ane acenaphthene, Flu ?uorene, Phe phenanthrene, Ant anthracene, Fla ?uoranthene, Pyr pyrene, BaAn benzo(a)anthracene, Chy chrysene, Bbf benzo[b]?uoranthene, Bkf benzo[k]?uoranthene, BaP benzo[a]pyrene, I1P indeno(1, 2, 3-cd)pyrene, Daa dibenzo (a, h) anthracene, BgP benzo(g,h,i)perylene

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Environ Earth Sci Table 3 Contents of PAHs of oily sludge samples and peripheral soil samples from 3W Compound NaP Any Ane Flu Phe Ant Fla Pyr BaAn Chy Bbf Bkf BaP I1P Daa BgP RPAHs Fla/Pyr 3W-1 1,048.6 546.0 678.5 812.9 527.2 58.5 38.8 73.4 68.3 90.3 26.0 47.8 53.6 17.2 11.4 13.5 4,112.0 0.529 3W-2 527.4 318.0 391.6 504.7 328.8 39.0 25.1 57.0 58.5 65.4 23.6 40.1 44.2 6.66 8.77 10.3 2,449.1 0.440 3W-3 693.9 117.0 160.7 228.2 445.6 102.8 108.7 164.3 110.3 101.9 27.5 34.7 21.5 29.3 28.7 33.7 2,408.8 0.662 3W-4 675.1 65.3 130.3 180.7 324.0 84.8 93.5 130.5 98.3 91.7 18.9 33.1 19.1 27.7 26.2 30.5 2,029.7 0.716 3W-5 531.1 48.8 85.0 91.4 243.2 53.3 69.2 90.0 81.0 63.2 18.2 22.4 12.8 13.2 11.4 17.5 1,451.7 0.769 3W-6 503.4 31.5 32.8 53.3 183.2 44.3 65.4 36.8 54.8 21.6 15.0 15.4 8.92 1.44 2.92 4.55 1,075.3 1.78 3W-7 363.9 21.0 23.4 33.1 105.6 31.5 24.3 11.3 25.5 7.03 13.5 13.9 5.55 1.04 1.28 1.16 683.1 2.15 3W-8 267.1 10.4 12.5 20.9 89.6 8.25 12.9 10.5 12.8 7.03 13.5 10.0 4.30 0.96 1.19 1.08 483.0 1.23

Table 4 Contents of PAHs of oily sludge samples and peripheral soil samples from 4W Compound NaP Any Ane Flu Phe Ant Fla Pyr BaAn Chy Bbf Bkf BaP I1P Daa BgP RPAHs Fla/Pyr 4W-1 787.6 506.3 612.3 643.7 308.0 36.8 22.8 54.8 43.5 60.3 22.1 24.7 40.3 6.66 5.97 7.70 3,183.5 0.416 4W-2 444.9 279.8 356.5 419.8 191.2 27.0 16.7 43.5 36.8 46.5 18.2 18.5 37.1 4.09 5.47 6.73 1,953.8 0.384 4W-3 573.9 99.8 156.8 195.1 340.8 60.8 62.3 119.3 49.5 65.4 25.2 23.1 15.2 11.6 14.7 8.51 1,822.0 0.522 4W-4 545.4 56.3 122.5 143.3 233.6 50.3 60.0 102.8 32.3 49.4 14.3 17.7 12.8 10.0 13.9 4.07 1,468.7 0.584 4W-5 503.4 46.5 75.7 84.2 172.0 36.0 41.0 39.0 26.3 33.3 13.5 12.4 7.90 6.90 3.09 2.70 1,103.9 1.05 4W-6 456.1 30.0 29.6 43.9 121.6 24.0 23.6 17.3 18.0 18.0 13.5 11.6 2.18 1.12 1.36 1.16 813.0 1.36 4W-7 333.9 17.3 20.3 26.6 69.6 9.48 12.2 9.12 11.3 6.30 11.1 10.0 3.83 0.96 1.28 1.08 544.4 1.34 4W-8 240.9 12.0 14.0 18.7 71.2 6.03 13.7 10.5 12.0 4.26 11.9 11.6 4.06 1.12 1.36 1.16 434.5 1.30

Now, many researchers have made use of the concentration ratios of Fla/Pyr as a standard to determine the sources of PAHs. Sicre et al. (1987) have indicated that PAHs are mainly from fossil fuel combustion when Fla/Pyr ratio is [1, and PAHs are mainly from oil products when Fla/Pyr ratio is\1. From Tables 2, 3, 4, it can be found that the Fla/Pyr ratios in the 18 soil samples increase with the

distance to oily sludge increasing. These phenomena show that the in?uence of oil source diminishes as the distance to oily sludge increases. The Fla/Pyr ratios became [1 at distance up to 100 m from oily sludge for soil samples of 3M and 3W, while the distance was 50 m for soil sample of 4W. The results indicate that combustion sources become major sources of PAHs in soil when the distance from the

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3000 2500

2000 1500 1000 500 0
3M 3W 4W

1

10

100

1000

S(m)
Fig. 1 The relations between the distances and contents of PAHs in soil samples

oily sludge is up to a certain value. Through analyzing distribution characteristics of PAHs and Fla/Pyr ratios in soil samples, oil sources are major sources of PAHs in soil close to oily sludge. With the distance to oily sludge increasing, the in?uence of oil sources decreases gradually, while the in?uence of combustion sources increases gradually. Oil sources and combustion sources become the corporate sources of PAHs in soil when the distance from oily sludge is up to a certain value.

human and the average absorption rate. This standard has been used to evaluate pollution levels in west Europe. Such pollution levels of PAHs in soils are given in Table 6. According to such standard, classi?cation results of the PAHs pollution in soils of Zhongyuan oil ?eld in winter are listed in Table 7. As seen, the pollution level of PAHs in soils around Zhongyuan oil ?eld was correlative with the distance from oily sludge plants, which indicated that the pollution level of PAHs in soils dramatically decreased with the increase of the distance from oily sludge plants. The soil samples of 3M-3, 3M-4, 3M-5, 3M-6, 3W-3, 3W4, 3W-5, 3W-6, 4W-3, 4W-4, and 4W-5 showed heavy contamination, whereas the soil samples of 3M-7, 3W-7, and 4W-6 showed medium contamination. Moreover, the soil samples of 3M-8, 3W-8, 4W-7, and 4W-8 showed light contamination. In all the soil samples from Zhongyuan oil ?eld in winter, heavily contaminated samples, mediumcontaminated samples, and lightly contaminated samples accounted for 61.1, 16.7 and 22.2%, respectively. The pollution degree of soils in 4W was lower than that of soils in 3M and 3W, which was ascribed to the content of PAHs in 4W oil sludge lower than that of 3M and 3W oil sludge. The health risk assessment in soils of Zhongyuan oil ?eld in winter According to the health risk assessment, different PAHs have different toxicities. It is unreasonable to evaluate human exposure dose by simply adding the concentration of these compounds. In fact, toxicity equivalent factors (TEF) of different composition should be combined to calculate equivalent concentration. Table 8 shows the TEF for 16 priority control PAHs given by Nisbet and LaGoy (1992), which was calculated by the equivalent concentrations (BaPep) of the reference object (BaP). Based on such parameters, BaP equivalent concentrations of PAHs in the soil samples in winter are given in Table 9. Figure 2 shows that the distribution of BaP equivalent concentrations of PAHs in the soil samples in winter are basically identical with the gross distribution of PAHs. In

The pollution degree of PAHs and ecological risk assessment in soils around Zhongyuan oil ?eld The pollution degree evaluation of PAHs in soils around Zhongyuan oil ?eld in winter Many researches have shown that the total content of the environment priority control of 16 typical PAHs were usually chosen to evaluate their pollution level. Maliszewska (1996) proposed that the pollution degree of PAHs in soils could be divided into four grades, viz., not contaminated, light contaminated, medium contaminated, and heavily contaminated, based on the content determination range of PAHs in soils, the evaluation of exposure risk to

Table 5 Concentration of individual PAHs compounds in the tested soils (ng/g) in winter Compounds NaP Any Ane Flu Phe Ant Fla Pyr Concentration range 240.9–693.9 10.4–117 12.5–160.7 18.7–228.2 71.2–445.6 6.03–102.8 12.2–108.7 9.12–175.5 Cmax/Cmin 2.88 11.3 12.9 12.2 6.26 17.0 8.91 19.2 Compounds BaAn Chy Bbf Bkf BaP I1P Daa BgP Concentration range 11.3–113.3 4.26–120.9 11.1–31.4 10.0–34.7 2.18–21.5 0.96–29.3 1.16–31.2 1.08–42.6 Cmax/Cmin 10.0 28.4 2.83 3.47 9.86 30.5 26.9 39.4

Total PAHs (ng/g)

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Environ Earth Sci Table 6 Pollution levels of PAHs in soils ng/g Pollution levels of PAHs in soils (K) Concentration ranges of PAHs in soils Not contaminated \200 Light contaminated 200–600 Medium contaminated 600–1,000 Heavily contaminated [1,000

Table 7 Evaluating results of the PAHs pollution in soils of Zhongyuan oil ?eld in winter Soils 3M-3 3M-4 3M-5 3M-6 3M-7 3M-8 K Heavily contaminated Heavily contaminated Heavily contaminated Heavily contaminated Medium contaminated Light contaminated Soils 3W-3 3W-4 3W-5 3W-6 3W-7 3W-8 K Heavily contaminated Heavily contaminated Heavily contaminated Heavily contaminated Medium contaminated Light contaminated Soils 4W-3 4W-4 4W-5 4W-6 4W-7 4W-8 K Heavily contaminated Heavily contaminated Heavily contaminated Medium contaminated Light contaminated Light contaminated

Table 8 The toxic equivalency factors (TEF) for 16 PAHs PAHs NaP Any Ane Flu TEF 0.001 0.001 0.001 0.001 PAHs Phe Ant Fla Pyr TEF 0.001 0.01 0.001 0.001 PAHs BaAn Chy Bbf Bkf TEF 0.1 0.01 0.1 0.1 PAHs BaP I1P Daa BgP TEF 1 0.1 1 0.01

addition, it can reach a maximum value near the oil-sludgesampling site, and a minimum value in the farthest oilsludge-sampling site, which mainly results from the fact that the distribution of PAHs in different samples was comparatively close. Contribution rates of different rings PAHs on BaP equivalent concentrations in the soil samples in winter are given in Fig. 3. The contribution of different rings PAHs on BaP equivalent concentrations and on PAHs measured total quantity was signi?cantly different. This phenomenon was mainly caused by the differences between TEF. As TEF value was very low, contribution rates of 2–3 rings PAHs, which originally occupied a large proportion in the concentration of total PAHs on BaP equivalent concentrations, were very little. When TEF value was very high, contribution rates of 5-ring PAHs, which originally occupied a small proportion in the concentration of total PAHs on BaP equivalent concentrations, were very large. Ecological risk assessment of PAHs in soils around Zhongyuan oil ?eld in winter In this paper, the standard of PAHs in farmland soils in Canada is used to assess ecological risk since the allowable PAHs residues in farmland soils of China have not been established. Although the weather in winter of Canada is cooler than that of China, and therefore has in?uence on

distribution, dispersion, volatilization, and degradation of PAHs, they cannot play decisive roles in a fundamental sense. According to the standard of PAHs in farmland soils in Canada, the prohibitive contents of naphthalene, phenanthrene, pyrene, Benz[a]anthracene, benzo[a]pyrene, benzo [b]?uoranthene, benzo[k]?uorathene, dibenzo[a, h]anthrace and indeno[1, 2, 3-cd]pyre were 100 ng/g (Annokkee 1990). The ranges of this classi?cation values (\0.7, 0.7–1, 1–2, 2–3, [3) for ‘not contaminated’, ‘warning’, ‘light contaminated’, ‘medium contaminated’ and ‘heavily contaminated’ samples, respectively, were derived from Nemero Index P. Nemero Index P evaluated 9 PAH residues from all 18 sampling points. Table 10 illustrates the marker of P in soil samples. Around 3M soil samples in winter, the range of Nemero Index P values was 1.98–4.49, which was correlative with the distance from oily sludge plants. Such result suggested that the Nemero Index P values increased with the increasing of the distance from oily sludge plants. The minimum value of 1.98 appeared at the 3M-8 sampling point and the maximum value of 4.49 appeared at 3M-3 sampling point. The soil samples of 3M-3, 3M-4, 3M-5 and 3M-6 were heavily contaminated and the soil samples of 3M-7 were medium contaminated. The soil samples of 3M-8 were light contaminated. The variation characteristics of Nemero Index P values around 3W and 4W soil samples were consistent with P of 3M soils. The range of Nemero Index P values was 1.92–5.06 and 1.72–4.16 around 3W and 4W soil samples, respectively. For 3W soil samples, the minimum P value of 1.92 appeared at the 3W-8 sampling site and the maximum p value of 5.06 appeared at 3W-3 sampling site. For 4W soil samples, the minimum value of 1.72 appeared at the 4W-8 sampling site and the maximum value of 4.16 appeared at 4W-3 sampling site. The soil samples of 3W-3, 3W-4, 3W-5, 3W-6, 4W-3, 4W-4, 4W-5 and 4W-6 were heavily contaminated. The soil samples of 3W-7 and 4W-7

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Table 9 BaP equivalent concentrations of PAHs in soil samples in winter (ng/g) 3M-5 0.6024 0.051 0.0897 0.1217 0.2568 0.563 0.0714 0.0863 7.58 0.611 1.43 2.47 15.2 1.16 14.7 0.151 0.0512 0.0133 0.0116 0.337 0.305 3.25 1.3 1.16 28.7 26.2 0.241 0.128 0.096 2.93 2.77 1.32 11.4 0.175 5.94 4.06 5.4 21.5 19.1 12.8 1.7 1.24 1.24 3.47 3.31 2.24 1.43 1.27 1.19 2.75 1.89 1.82 1.5 1.54 8.92 0.144 2.92 0.0455 5.78 0.238 2.4 0.0615 1.2 0.0564 11.03 1.019 9.83 0.917 8.1 0.632 5.48 0.216 0.0353 0.00975 0.00975 0.1643 0.1305 0.09 0.0368 0.0661 0.0228 0.0122 0.1087 0.0935 0.0692 0.0654 0.458 0.293 0.09 1.028 0.848 0.533 0.443 0.315 0.2096 0.0872 0.0952 0.4456 0.324 0.2432 0.1832 0.1056 0.0896 0.0825 0.0243 0.0129 0.0113 0.0105 2.55 1.28 0.0703 0.0703 1.35 1.39 5.55 0.104 1.28 1.35 1 4.3 0.096 1.19 0.0116 0.0108 0.0418 0.0302 0.023 0.2282 0.1807 0.0914 0.0533 0.0331 0.0209 0.0335 0.0242 0.0133 0.1607 0.1303 0.085 0.0328 0.0234 0.0125 0.1568 0.1951 0.3408 0.608 0.0623 0.1193 4.95 0.654 2.52 2.31 15.2 1.16 14.7 0.0851 0.0323 0.0195 0.0114 0.117 0.0653 0.0488 0.0315 0.021 0.0104 0.0998 0.4854 0.3601 0.2754 0.6939 0.6751 0.5311 0.5034 0.3639 0.2671 0.5739 3M-6 3M-7 3M-8 3W-3 3W-4 3W-5 3W-6 3W-7 3W-8 4W-3 4W-4 0.5454 0.0563 0.1225 0.1433 0.2336 0.503 0.06 0.1028 3.23 0.494 1.43 1.77 12.8 1 13.9 0.0407 4W-5 4W-6 4W-7 0.5034 0.4561 0.3339 0.0465 0.03 0.0173 0.0757 0.0296 0.0203 0.0842 0.0439 0.0266 0.172 0.36 0.041 0.039 2.63 0.333 1.35 1.24 7.9 0.69 3.09 0.027 0.1216 0.0696 0.24 0.0948 0.0236 0.0122 1.8 0.18 1.35 1.16 2.18 0.112 1.36 1.13 0.063 1.11 1 3.83 0.096 1.28 0.0116 0.0108 4W-8 0.2409 0.012 0.014 0.0187 0.0712 0.0603 0.0137 0.0173 0.00912 0.0105 1.2 0.0426 1.19 1.16 4.06 0.112 1.36 0.0116

Components 3M-3

3M-4

NaP

0.6129

0.6001

Any

0.1035

0.0623

Ane

0.1435

0.1186

Flu

0.1894

0.1498

Phe

0.4032

0.3096

Ant

0.983

0.81

Fla

0.0965

0.0828

Pyr

0.1755

0.1403

BaAn Chy

11.33 1.209

9.68 0.983

Bbf

3.14

1.35

Bkf

3.39

3.16

BaP

19.9

18.3

I1P

2.53

2.45

Daa

31.2

27

BgP

0.426

0.337

RPAHs

75.8325 65.5335 45.1443 19.9922 11.3196

10.88425 74.6824 66.7694 40.1787 22.1149 13.2035 9.8035 43.7351 36.4316 18.5818 9.1157 9.10362 9.5775

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Environ Earth Sci Fig. 2 The distribution of BaP equivalent concentrations of PAHs in soil samples in winter
80

BaP equivalent concentrations of PAHs (ng/g)

70

60

50

40

30

20

10

0

3M-3 3M-4 3M-5 3M-6 3M-7 3M-8 3W-3 3W-4 3W-5 3W-6 3W-7 3W-8 4W-3 4W-4 4W-5 4W-6 4W-7 4W-8

samples

100

2 rings

3 rings

4 rings

5 rings

6 rings

80

percentage (%)

60

40

20

0

3M-3 3M-4 3M-5 3M-6 3M-7 3M-8 3W-3 3W-4 3W-5 3W-6 3W-7 3W-8 4W-3 4W-4 4W-5 4W-6 4W-7 4W-8

samples
Fig. 3 Contribution rates of different rings PAHs on BaP equivalent concentrations in winter Table 10 The marker of P in soil samples No. 3M-3 3M-4 3M-5 3M-6 3M-7 3M-8 P 4.49 4.36 4.35 3.50 2.58 1.98 No. 3W-3 3W-4 3W-5 3W-6 3W-7 3W-8 P 5.06 4.90 3.84 3.62 2.61 1.92 No. 4W-3 4W-4 4W-5 4W-6 4W-7 4W-8 P 4.16 3.93 3.61 3.26 2.39 1.72

Conclusion According to the contamination degree of PAHs in soil samples in winter, soils around three different oily sludges in Zhongyuan oil ?eld were heavily polluted. Although the pollution degree of PAHs in different plants (3M, 3W, 4W) is different, the contamination rate has reached 100%. 1. The contents of PAHs in soil samples in 3M, 3W and 4W were 499.9–2,241.3, 483.0–2,408.8 and 434.5– 1,822.0 ng/g, respectively. The order of pollution degree in soil near the three plants was 3W [ 3M [ 4W. Naphthalene, acenaphthene, ?uorene, phenanthrene and pyrene were characteristic factors of PAHs in soil samples of 3M and 3W, whereas, naphthalene, acenaphthene, ?uorene and phenanthrene were characteristic factors of PAHs in soil samples of 4W.

were medium contaminated. For comparison, the soil samples of 3W-8 and 4W-8 were light contaminated. The evaluation results of the marker of P showed that 66.7% of the samples obtained around Zhongyuan oil ?eld in winter were as ‘heavily contaminated’, 16.7% as ‘medium contaminated’, and 16.6% as ‘light contaminated’. Result of classi?cation evaluation presented that the soils around oily sludge was seriously polluted.

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Environ Earth Sci

2.

According to the total content of PAHs in the soil samples, heavily contaminated samples accounted for 61.1%; medium contaminated samples accounted for 16.7% and light contaminated samples accounted for 22.2% in the soil samples of Zhongyuan oil ?eld in winter. The evaluation results of the marker of P showed that 66.7% of the samples obtained around Zhongyuan oil ?eld in winter were as ‘heavily contaminated’, 16.7% as ‘medium contaminated’, and 16.6% as ‘light contaminated’. All the results of classi?cation evaluation presented that soils around oily sludge were seriously polluted.

Due to ubiquity and persistence of PAHs, the PAHs contents are excessive in most soils of petrochemical area, which has done harm to the health of oil workers and ambient residents. Much attention ought to be given to pollution from oily sludge.
Acknowledgments The study is jointly supported by National Natural Science Foundation of China (20977055), Shandong Provincial Natural Science Foundation of China (Y2007E03), State Key Laboratory Foundation of Geological Processes and Mineral Resources (GPMR200924, GPMR201010) and Key Lab Foundation of Biogeology and Environmental Geology of Ministry of Education (No. BGEGF200804). Miss Hong Chen and Mr. Dongya Sun were acknowledged for their kindly help during the research and the submission of the paper.

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