Polycyclic Aromatic Hydrocarbons in Soils from European High Mountain Areas

Polycyclic aromatic hydrocarbons (PAHs) were analyzed in 70 soils distributed in mountain areas such as Montseny (300?C1,700 m), Pyrenees (1,500?C2,900 m), Alps (1,100?C2,500 m), and Tatras (1,400?C1,960 m). Average total PAH concentrations, excluding retene and perylene, were about 400 ng/g in the Pyrenees and 1,300?C1,600 ng/g in the other mountain ranges. No correlations between PAH concentrations and total organic carbon were observed. Retene was the major PAH in the Pyrenean soils of lower altitude. No altitudinal dependence was found between soil PAH concentrations and elevation for the whole dataset. However, in the Tatra soils a statistically significant correlation with altitude was observed involving higher concentrations at higher altitude. This correlation was due to the statistically significant altitudinal dependence of the more volatile PAHs. Another observed altitudinal trend concerned the benz[a]anthracene/(benz[a]anthracene + chrysene + triphenylene) and the benzo[a]pyrene/(benzo[a]pyrene + benzo[e]pyrene) ratios that exhibited a decrease in the more chemically labile compounds, benz[a]anthracene and benzo[a]pyrene, respectively, in the soils located at higher altitude. This observation is consistent with the expected higher photooxidation at higher mountain altitude.     

Input and behavior of polycyclic aromatic hydrocarbons in arable,fallow, and forest soils of the taiga zone (Tver oblast)

Contents of 11 most prevalent polycyclic aromatic hydrocarbons (PAHs) in snow and soils of arable, fallow, and forest areas significantly remote from impact technogenic sources of polyarenes have been examined in the Torzhok district of Tver oblast. From the analysis of snow samples, the volumes and composition of PAHs coming from the atmosphere onto the areas of different land use have been determined. Light hydrocarbons prevail in PAHs. They make up 65–70% of total PAHs; their share in soils reaches almost 95%. An increase in the content of PAHs is revealed in fallow soils compared to arable and afforested areas. A direct relationship is revealed between the lateral distribution of total PAHs and the content of organic carbon. The distribution of total PAHs is surface-accumulative in forest soils, mainly uniform in arable soils, and deepaccumulative in fallow soils. PAH groups characterized by similar radial distributions and ratios between their reserves in snow and soils are distinguished: (1) fluorene and phenanthrene, (2) biphenyl and naphthalene, (3) benzo(a)anthracene, chrysene, perylene, and benzo[a]pyrene, and (4) anthracene and benzo[ghi]pyrene.     

Salix rubens and Salix triandra Species as Phytoremediators of Soil Contaminated with Petroleum-Derived Hydrocarbons

The petroleum industry activities provide potential risks to the environment because they can contaminate ecosystems with different organic compounds in the production chain. Several accidents with transport and handling of petroleum and related products occurred in urban areas with harmful effects to the quality of life and economy. In the 1990s, bioremediation and phytoremediation technologies as economically feasible alternatives to repair the environmental damage were developed. In this study, the potential of the willows Salix rubens and Salix triandra were evaluated with regard to the phytoremediation of soils contaminated with petroleum-derived hydrocarbons (total hydrocarbons and polycyclic aromatic hydrocarbons (PAHs)). The PAHs were quantified by extraction from soils and plants using dichloromethane under ultrasonication. The HPLC analysis was performed with GC/MSD equipment. The total hydrocarbons present in uncontaminated soil were quantified by the sum of animal/vegetable oils and greases and mineral oils and greases according to Standard Methods 5520 (1997). The two willows species S. rubens and S. triandra were resistant during the project development. In the contaminated soil, in which both species were planted, the total hydrocarbons concentration was reduced near 98?%. The PAHs content was remarkably reduced as well. Pyrene showed an initial concentration of 23.06???g?kg^?1, decreasing in most cases to 0.1???g?kg^?1 or to undetectable levels. Chrysene decreased from 126.27???g?kg^?1 to undetectable levels. Benzo[k]fluoranthene and benzo[a]pyrene concentrations had also showed a decrease from 28.44 and 3.82???g?kg^?1, respectively, to undetectable levels.     

Hydrocarbon status of soils under atmospheric pollution from a local industrial source

Contents and compositions of bitumoids, polycyclic aromatic hydrocarbons (PAHs), and free and retained hydrocarbon gases in soils along a transect at different distances from the local industrial source of atmospheric pollution with soot emissions have been studied. The reserves of PAHs progressively decrease when the distance from the source increases. Among the individual PAHs, the most significant decrease is observed for benzo[a]pyrene, tetraphene, pyrene, chrysene, and anthracene. On plowlands, the share of heavy PAHs—benzo[ghi]perylene, benzo[a]pyrene, perylene, etc.—is lower than in the forest soils. In automorphic soils of the park zone adjacent to the industrial zone, the penetration depth of four-, five-, and sixring PAHs from the atmosphere is no more than 25 cm. In soils under natural forest vegetation, heavy PAHs do not penetrate deeper than 5 cm; in tilled soils, their penetration depth coincides with the lower boundary of plow horizons. Analysis of free gases in the soil air revealed hydrocarbons only under forest. From the quantitative and qualitative parameters of the content, reserves, and compositions of different hydrocarbons, the following modification types of hydrocarbon status in the studied soils were revealed: injection, atmosedimentation–injection, atmosedimentation–impact, atmosedimentation–distant, and biogeochemical types.     

Hydrocarbon status of soils in the asphalt deposit area (Samara Bend)

The composition and distribution features of the main components of soil hydrocarbon complex― organic (noncarbonate) carbon, hexane bitumoids, and individual polycyclic aromatic hydrocarbons (PAHs)―in the area of depleted Bakhilovo asphalt deposit (Samara oblast) have been studied. According to their proportions, three genetic types of soil hydrocarbon status are distinguished: (a) emanation–injection type prevailing within the limits of the former production field and characterized by anomalous contents of heavy resinous bitumoids (5000–7000 mg/kg on the average) throughout the soil profile and a high content of PAHs (4–9 mg/kg on the average, 29 mg/kg as the maximum, with the dominance of naphthalene homologues); (b) emanation–biogeochemical type confined to mechanogenically undisturbed soils within and beyond the deposit area, where the emanation component is manifested in soils with heavy texture and higher concentrations and very light composition of bitumoids in the lower parts of the soil profile; and (c) atmosedimentation–biogeochemical type characteristic of conventionally background soils with light texture; benzo[a]pyrene traces are detected among PAHs in the upper soil horizon, which indicates the input of this hydrocarbon with aerosols from the atmosphere; the concentrations of bitumoids and PAHs in parent rocks are lower than in the soils.     

Bioaugmentation and biostimulation effects on PAH dissipation and soil ecotoxicity under controlled conditions

The degradation of spiked anthracene (ANT), pyrene (PYR) and benzo[a]pyrene (B[a]P) in soil (3000 mg ∑ 3 PAHs kg⁻¹ dry soil) was studied in aerobically incubated microcosms for 120 d. The applied treatments aimed at enhancing PAH removal from the heavily contaminated soils are: (i) bioaugmentation by adding aged PAH-contaminated soil (ACS) containing activated indigenous degraders; and (ii) combined bioaugmentation/biostimulation by incorporating sewage sludge compost (SSC) and decaying rice straw (DRS). The adopted treatments produced higher PAH dissipation rates than those observed in unamended PAH-spiked soils, especially for ANT and PYR in the presence of DRS or ACS (>96%). However, B[a]P was the most recalcitrant hydrocarbon to biodegradation. Extracellular enzyme investigation revealed the existence of ligninolytic activities in all soil treatments, including control but no relationship could be found with PAH dissipation. The ecotoxicological assessment indicated that regardless of applied treatment, PAH-spiked soils were chronically lethal to ostracod Heterocypris incongruens and confirmed the sensitivity of the microcrustacean to the concomitant presence of these three hydrocarbons. Lettuce root elongation inhibition was correlated with PAH level but the presence of SSC conferred a strong phytotoxic capacity to PAH-spiked soils. DRS amendment may constitute a cost-effective alternative for hydrocarbon bioremediation as it has impacted positively on soil microbial activity and enhanced PAH removal with no apparent changes in soil physico-chemical properties.     

Polycyclic aromatic hydrocarbons in soils of Moscow

The contents of polycyclic aromatic hydrocarbons (PAHs) in the upper horizons of Moscow soils range up to 1400 mg/kg for individual compounds and up to 10000 mg/kg for their sum. The concentration coefficients of PAHs in the soil vary from 0.7 to 200 depending on individual polyarene properties and land use. The heavy polynuclear structures of technogenic origin have the highest concentration coefficients. The highest accumulation of PAHs is observed for the soils of dumping sites, residential-transport areas, and industrial zones. According to the state sanitary norms set in the Russian Federation for the content of benzo[a]pyrene in soils, more than one-third of the urban soils studied are classified as pure, and about half soils are classified as acceptable.     

Polycyclic aromatic hydrocarbons and polychlorinated biphenyls in urban and semi-urban soils of Havana,Cuba

Purpose

Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in Havana were quantified and analyzed in relation to possible emission sources to assess metropolitan soil contaminations in a highly dynamic, urban environment. The results of this study will serve Cuban legislators as a basis to develop environmental quality standards for organic pollutants in soils.

Materials and methods

Possible emission sources as, e.g., the vicinity to roads or industrial plants and the influence of the land use were related to the organic contaminants concentrations. Therefore, 28 topsoils in the Havana urban and semi-urban area were sampled at agricultural (n?=?12), organoponic (urban gardens in the capital, n?=?8), public park (n?=?7), and remediation (on-site bioremediation of an oil refinery, n?=?1) sites. Their PAH and PCB concentrations were measured with gas chromatography mass spectroscopy and the total organic carbon (TOC) and black carbon (BC) concentrations with the chemo-thermal oxidation.

Results and discussion

The sum of the 16 PAH concentrations ranged from 0.04 mg/kg in agricultural and organoponic soils to up to 72 mg/kg in a public park at about 1.5 km distance from an oil refinery. The lowest sum of the seven PCB congener concentrations was also measured in organoponic soils (0.002 mg/kg) and the highest in an arable patch of land between the rail roads and a main road (0.1 mg/kg). Both, PAH as well as PCB soil concentrations in Havana were almost up to two orders of magnitudes higher compared to a soil monitoring in the neighboring province of Mayabeque, but overall in the typical range of urban soils reported by other studies. The pollutants showed no relationship between TOC and BC except for PAHs with BC. For PAHs, combustion was the main source.

Conclusions

A comparison of the pollutant concentrations with regulatory guidance values (RGV) of other countries revealed PCB concentrations in Havana soils far below these RGV. In contrast, some concentrations of benzo[a]pyrene, the most carcinogenic PAH, in agricultural and park soils in Havana exceeded some RGV. Thus, some public parks pose a risk according to the Canadian quality guidelines when people have direct contact with these soils but not if they were consuming products thereof.

     

Polycyclic aromatic hydrocarbons in green space soils in Shanghai: source,distribution, and risk assessment

Purpose

The purpose of this study is to study the major sources, concentrations, and distributions of polycyclic aromatic hydrocarbons (PAHs) in three different types of green space in Shanghai. In addition, we will quantitatively assess the burden of PAHs in the soil, as well as the potential carcinogenic risk of PAHs in humans. These results will provide valuable information for soil remediation and human health risk management.

Materials and methods

A total of 166 surface soil samples were collected in parks, greenbelts, and woodlands. Soils were extracted using accelerated solvent extraction (ASE). PAHs were analyzed by gas chromatography-mass spectrometry (GC-MS). The positive matrix factorization (PMF) model was used to identify major PAH emission sources and quantitatively assess their contributions to PAHs. The incremental lifetime cancer risk (ILCR) was used to quantify the potential health risk of PAHs.

Results and discussion

The average concentrations of ∑15 PAHs are 227?±?95 ng g^?1, 1632?±?251 ng g^?1, and 1888?±?552 ng g^?1 in the woodland, park, and greenbelt soils, respectively. The PMF results show that biomass (33%), coal (21%), vehicles (17%), natural gas (14%), oil (9%), and coke (7%) are the dominant sources of PAHs in the park soils. Diesel (40%), tire debris (30%), biomass (15%), gasoline (9%), and oil (5%) are the main sources in the greenbelt soils. Biomass (48%), vehicles (37%), and coal (15%) are the main sources in the woodland soils. The ILCRs of adults and children who are exposed to PAHs in soils range from 9.53?×?10^?8~1.42?×?10^?5.

Conclusion

In three types of green space in Shanghai, the dominant PAHs are high–molecular weight (HMW) compounds (≥?4 rings). This may be due to the proximity of the sampling site to emission sources. In addition, low–molecular weight (LMW) PAHs (with 2–3 rings) are relatively unstable, and these compounds are prone to volatilization and degradation. Source identification indicates that biomass combustion is the most dominant PAH source in the park and woodland soils, while vehicles are the dominant PAH source in the greenbelt soils. The ILCRs of adults and children indicate potential health risks, and children have a greater health risk than adults.

     

Characterization and Sources of PAHs and Potentially Toxic Metals in Urban Environments of Sevilla (Southern Spain)

The purpose of this study was to determine the degree of PAH contamination and the association of PAHs with metals in urban soil samples from Sevilla (Spain). Fifteen polycyclic aromatic hydrocarbons-PAHs (naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenzo[a,h]anthracene, benzo[g,h,i]perylene, indeno[1,2,3-c,d]pyrene) and seven metals (Cd, Cr, Cu, Mn, Ni, Pb, Zn) have been evaluated in representative urban soil samples. Forty-one top soils (0–10 cm) under different land use (garden, roadside, riverbank and agricultural allotment) were selected. PAHs from soil samples were extracted by sonication using dichloromethane. The simultaneous quantification of 15 different PAH compounds were carried out by HPLC using multiple wavelength shift in the fluorescence detector. For qualitative analysis a photo diode-array detector was used. Metal (pseudo-total) analysis was carried out by digestion of the soils with aqua regia in microwave oven. The mean concentration of each PAH in urban soils of Sevilla showed a wide range, they are not considered highly contaminated. The results of the sum of 15 PAHs in Sevilla soils are in the range 89.5–4004.2 μg kg^?1, but there seems not to be a correlation between the concentration of PAHs and the land use. Of the 15 PAHs examined, phenanthrene, fluoranthene and pyrene were present at the highest concentrations, being the sum of these PAHs about 40% of the total content. Although metal content were not especially high in most soils, there are significant hints of moderate pollution in some particular spots. Such spots are mainly related with some gardens within the historic quarters of the city. The associations among metals and PAHs content in the soil samples was checked by principal components analysis (PCA). The largest values both for ‘urban’ metals (Pb, Cu and Zn) and for PAHs were mainly found in sites close to the historic quarters of the city in which a heavy traffic of motor vehicles is suffered from years.     

分子标志物参数在识别土壤多环芳烃(PAHs)来源中的应用

土壤中PAHs污染物的成因十分复杂,常见的污染源包括生物质的高温降解产物、石油等化石燃料及其不完全燃烧产物等,其输入方式主要有大气中所含PAHs的干、湿沉降、水体输入、固体废弃物排放等。不同成因的PAHs组成特征有一定差别,并可能具有独特的分子标志物或分子化合物组合特征,由此,可以根据环境介质中PAHs的组成特征判断污染物来源或成因类型。目前,分子标志物特征参数已成为追踪PAHs污染来源的有效手段。介绍了近年来国内外在运用PAHs分子标志物特征参数识别土壤中PAHs污染源方面的主要研究进展、应用潜力及存在的问题。     

Enhanced Mobilization of Field Contaminated Soil-bound PAHs to the Aqueous Phase under Anaerobic Conditions

Although microbially-mediated redox environments can alter the characteristics of soil/sediment organic matter (SOM) and its interactions with persistent hydrophobic organic contaminants (HOCs) bound to soils and sediments, the nature of their effects has not been adequately addressed. In this study, a field soil collected from a manufacturer gas plant site and contaminated historically with creosotes was incubated under aerobic and anoxic/anaerobic conditions along with various amendments (extra carbon and enrichment minerals) for stimulating microbial activities. Anaerobic conditions stimulated significant fractions of bound polycyclic aromatic hydrocarbons (PAHs) encompassing naphthalene through benzo[g,h,i]perylene to be mobilized to the aqueous phase, leaving their aqueous phase concentrations far in excess of solubility (increases in their apparent aqueous phase concentrations by factors as high as 62.8 relative to their initial aqueous phase concentrations). Such effects became more evident for high molecular weight PAHs. Dissolved organic matter exhibiting a high affinity for PAHs was liberated from soils during the anaerobic soil incubations. Feasibility of this concept for field applications was evaluated with a lab-scale continuous flow system composed of an anaerobic soil column followed by an aerobic bioreactor inoculated with PAH-degrading microbes. High quantities of PAHs exceeding their aqueous solubilities were eluted from the anaerobic soil column and those mobilized PAHs were readily bioavailable in the secondary aerobic bioreactor. This study may offer a potential method for cost-effective and performance-efficient ex situ remediation technologies (or in situ if appropriate hydrological control available in the contaminated field site) and risk assessment for the HOC-contaminated soils/sediments.     

某氮肥厂场地土壤PAHs污染特征研究

采用现场采样及室内测试方法对广州某氮肥厂原料车间和油库区土壤中16种优控多环芳烃（PAHs）的含量进行调查研究,分析了EPAHs含量及其组成特征和垂直分布特征,并在此基础上进行了源解析。结果表明,分析样品中∑PAHs范围在10-7795μg·kg,原料车间土壤中的∑PAHs小于油库区土壤中的,菲、芘、荧蒽、并（b）荧蒽、苯并（a）芘为主要污染物;油库土壤0-40cm的样品中16种PAHs均有检出,∑PAHs和单体分布基本一致;原料车间土壤∑PAHs和单体浓度随着地面深度的增加而减少。通过对单组分比值（菲／蒽,荧蒽／芘）的分析可以看出油库区土壤中PAHs来源于石油和燃烧源,而原料车间污染源主要为燃烧源。     

The effect of concentrations and properties of phenanthrene, pyrene, and benzo(a)pyrene on desorption in contaminated soil aged for 1 year

Purpose

The choice and timing of microorganisms added to soils for bioremediation is affected by the dominant bioavailable contaminants in the soil. However, changes to the concentration of bioavailable PAHs in soil are not clear, especially when several PAHs coexist. This study investigated the effects of PAH concentration and chemical properties on desorption in meadow brown soil after a 1-year aging period, which could reflect changes of PAH bioavailability during bioremediation.

Materials and methods

Based on the percentage of different molecular weights in a field investigation, high-level contaminated soil (HCS) and low-level contaminated soil (LCS) were prepared by adding phenanthrene (PHE), pyrene (PYR) and benzo(a)pyrene (BaP) to uncontaminated meadow brown soil. The concentrations of HCS and LCS were 250 mg?kg^?1 (PHE, PYR, and BaP: 100, 100, and 50 mg?kg^?1) and 50 mg?kg^?1 (PHE, PYR, and BaP: 20, 20, and 10 mg?kg^?1) respectively. The soils were aged for 1 year, after which desorption was induced by means of a XAD-2 adsorption technique over a 96-h period.

Results and discussion

The range of the rapidly desorbing fraction (F _rap) for PHE, PYR, and BaP in HCS and LCS was from 1.9 to 27.8 %. In HCS, desorption of PYR was most difficult, and the rate constant of very slow desorption (K _vs) of PYR was 8 orders of magnitude lower than that of BaP, which had similar very slow desorbing fractions (49.8 and 50.5 %, respectively). However, in LCS, desorption of PYR was the easiest; the K_vs of PYR was 8–10 orders of magnitude higher than those of PHE and BaP. In HCS, the time scale for release of 50 % of the PAHs was ranked as BaP?>?PYR?>?PHE, while in LCS this was BaP?>?PHE?>?PYR.

Conclusions

The combined effect of PAH concentrations and properties should be taken into account during desorption. The desorption of PAH did not always decrease with increasing molecular weight, and the desorption of four-ring PAHs might be special. These results are useful for screening biodegrading microbes and determining when they should be added to soils based on the dominant contaminants present during different periods, thus improving the efficiency of soil bioremediation.     

Removal of polycyclic aromatic hydrocarbons from soil amended with biosolid or vermicompost in the presence of earthworms (Eisenia fetida)

Earthworms burrow through the soil thereby accumulating many lipophilic organic pollutants from the surrounding environment, so they could be used to remove polycyclic aromatic hydrocarbons (PAHs) from soil. Sterilized and unsterilized soil was contaminated with phenanthrene (Phen), anthracene (Anth) and benzo[a]pyrene (BaP), with or without added Eisenia fetida and biosolid or vermicompost. Concentrations of PAHs were monitored in soil and earthworms for 70 days. Removal of PAHs increased in soil with earthworms added as 91% of Anth, 16% BaP and 99% Phen was dissipated compared to 42%, 3% and 95% in unamended soil. The microorganisms in the gut of the earthworm contributed to PAHs removal and 100% of Phen, 63% of Anth and 58% of BaP was removed from sterilized soil with E. fetida added. Biosolid and to lesser extent vermicompost accelerated removal of PAHs from soil. Applying earthworms to a contaminated site might be an environmentally friendly way to remove hydrocarbons from soil. However, a limitation might be the cost of the large amounts of earthworms required to remove PAHs from soil and the necessity to supply them with sufficient substrate while maintaining the water content of the soil high enough for their normal functioning.     

Polycyclic aromatic hydrocarbons (PAHs) in rural soils of Dongjiang River Basin: occurrence,source apportionment,and potential human health risk

Purpose

A comprehensive study was conducted to investigate the presence of polycyclic aromatic hydrocarbons (PAHs) in Dongjiang River Basin (DRB) soils and to evaluate their sources and ecological and health risk. In addition, factors affecting the distribution and fate of PAHs in the soils such as emission density, soil organic matter, degradation, etc. were studied.

Materials and methods

Surface soil (0–20 cm) samples from 30 sampling sites in the rural areas of DRB were collected and analyzed for 17 polycyclic aromatic hydrocarbons (16 EPA priority PAHs and perylene). Positive matrix factorization model was used to investigate the source apportionment of these PAHs, and an incremental lifetime cancer risk (ILCR) was used to estimate the integrated lifetime risks of exposure to soil-borne PAHs through direct ingestion, dermal contact, and inhalation collectively.

Results and discussion

The total PAH concentrations in the rural soils in DRB range from 23.5 to 231 μg/kg with a mean concentration of 116 μg/kg. The predominant PAHs in the rural soils were naphthalene, fluoranthene, phenanthrene, and benzo(b)fluoranthene. Cluster analysis was performed to classify the soil PAHs into three clusters, which could be indicative of the soil PAHs with different origins and different properties. Source apportionment results showed that coal, biomass, oil, commercial creosotes, and vehicle contributed 24 %, 24 %, 17 %, 17 %, and 18 % of the total soil PAH burden, respectively. The ILCR results indicated that exposure to these soil-borne PAHs through direct ingestion, dermal contact, and inhalation collectively produces some risk.

Conclusions

PAHs in the soils of the DRB will produce long-term influences on rivers and oceans via soil erosion and river transport. Therefore, PAHs in rural soils of DRB have potential impacts on the water supply and human health risk.     

Distribution of polycyclic aromatic hydrocarbons in particle‐size separates and density fractions of typical agricultural soils in the Yangtze River Delta,east China

Soil organic matter can be divided into different organic carbon (C) pools with different turnover rates. The organic pollutants in soils associated with these organic C pools may have different bioavailability and environmental risks during the decomposition of soil organic matter. We studied the distribution patterns of 15 USEPA priority polycyclic aromatic hydrocarbons (PAHs) in different particle‐size separates (clay, fine silt, coarse silt, fine sand and coarse sand) and density fractions (light and heavy fractions) of nine agricultural topsoils (0–20 cm depth) from a contaminated area in the Yangtze River Delta region of east China. There was a decreasing trend in PAH concentration in particle‐size separates with decreasing particle size. However, the different particle‐size separates had similar PAH composition. The concentration of PAHs in the light fraction ranged from 13 037 to 107 299 μg kg^?1, far higher than in the heavy fraction, which ranged from 222 to 298 μg kg^?1. Although the light fraction accounted for only 0.4–2.3% of the soils, it was associated with 31.5–69.5% of soil PAHs. The organic matter in coarse silt had the strongest capacity for enrichment with PAHs. Combining the distributions of PAHs and the turnover rates of organic matter in different soil fractions, the environmental risks of PAH‐polluted soils may be due mainly to the PAHs associated with sand and the light fraction.     

土壤中苯并[a]芘对白符跳(Folsomia candida)的生态毒性研究

苯并(a)芘（B[a]P）是一种典型的多环芳烃（PAHs）,在油田周边和污灌区土壤中有较高的检出率。在污染土壤生态风险评估和制定土壤生态基准时,常用土壤跳虫作为敏感生态受体,但已有研究表明,目前常用的成虫生长率、死亡率和繁殖率等指标特征往往仅对土壤中高剂量B[a]P产生毒性响应。采用白符跳（Folsomia candida）的生态毒理试验筛选可用于较低剂量B[a]P下新的敏感指标特征,并比较其在两种典型地带性土壤天津潮土和鹰潭红壤之间的敏感性差异。结果表明,幼虫的生长指标最敏感,能对土壤较低浓度B[a]P产生毒性响应,可作为指示土壤B[a]P毒性的指标。四个指标的敏感度依次为：幼虫体长>成虫体长>繁殖数>存活数。B[a]P对白符跳的毒性效应在两种土壤类型间存在显著差异（红壤和潮土中幼虫体长的最低效应浓度（LOEC）值分别为1和500 mg kg^-1）,可能受土壤理化性质,特别是有机质含量和pH的影响,在制定土壤生态基准时需对不同土壤的毒性数据进行归一化校正。     

Ecotoxicological characterization of sediment cores from the western Baltic Sea (Mecklenburg Bight) using GC–MS and in vitro biotests

Background, aim, and scope

The Mecklenburg Bight (Western Baltic Sea) near Luebeck, Germany was historically used to dump industrial waste at sea and, thus, sediments in some regions are highly polluted at present. While earlier studies identified hot spots of chemical pollution, little is known about biological activities and impacts on exposed marine organisms. This study aimed to assess the pollution in the Mecklenburg Bight to determine the degree of contamination with sediment-bound polycyclic aromatic hydrocarbons (PAHs) as well as biological activities.

Materials and methods

Sediment cores with a depth of 30 cm were sampled at a dumping site and at a reference site, sliced in distinct layers, freeze-dried, and processed using the accelerated solvent extraction method. Sediment was characterized measuring total organic carbon (TOC) and soot contents. Concentrations of the 16 EPA-PAHs were determined with chemical analysis (gas chromatography–mass spectroscopy) in each sediment slice and referred to the determined TOC content. Further on, in vitro biotests were applied to determine toxic effects of contaminants in the sediment. The acute neutral red retention assay indicated no specific cytotoxic effects. Arylhydrocarbon receptor (AhR)-mediated activities were measured using the mechanism-specific 7-ethoxyresorufin-O-deethylase induction assay. Both biotests were performed with rainbow trout (Oncorhynchus mykiss) liver cells (RTL-W1). Analyzed compound concentrations and biological activities were given in toxicological equivalent concentrations (chem- and bio-TEQs) to determine shares of analyzed EPA-PAHs to the overall activity.

Results

TOC and soot contents indicated a significant alteration through the sediment core at the dumping site. EPA-PAH concentrations were referred to TOC and indicated elevated concentrations at the dumping site. Maximum PAH concentrations (14 to 16 cm depth; 5.44 µg/g TOC) were 300-fold increased at the dumping site, compared to the reference site (4 to 6 cm depth; 0.017 µg/g TOC). Cytotoxicity as determined in the neutral red retention assay was elevated in some layers at the dumping site (maximum in 4 to 6 cm depth; NR₅₀?=?14 mg/ml), but not correlated with TOC or soot contents. Ah receptor agonist activities were clearly elevated in highly PAH-loaded layers at both sites. At the dumping site, maximum activities were determined reflected by a bio-TEQ of 223,000 pg/g (19 to 22 cm), in contrast to a bio-TEQ of 41,000 pg/g (6 to 8 cm) at the reference site. Further on, shares of EPA-PAHs to the overall activity were determined and contributed >40% at the dumping site and between 4% and 17% at the reference site. Chem-TEQs were found to exceed bio-TEQs in a depth of 11 to 22 cm, indicating the presence of Ah receptor antagonistic or inhibitive compounds.

Discussion

Sediments from the dumping site were determined to be highly contaminated and caused toxic effects in depths that are known to be influenced by dumping activities. In contrast, the reference sediment indicated only near to surface layers to be minor contaminated. In comparison with highly polluted sediments from other marine sites, the contamination of the dumping site could be ranked as elevated. Chem-TEQs exceeding bio-TEQs in a depth of 11 to 22 cm seem to be caused by AhR antagonistic compounds in the dumped material. Furthermore, particle-bound PAH concentrations assessed in this study were discussed against freely dissolved concentrations in interstitial water, as determined in a different study with the same sediment core.

Conclusions

Sediments in the inner Mecklenburg Bight could be shown to be highly contaminated, at least with PAHs, causing articulate increased Ah receptor-mediated activities. Marine organisms may be exposed to these contaminants, in particular when inhabiting the sediment.

Recommendations and perspectives

Further research activities should extend the range of chemically analyzed pollutants and applied biotests and endpoints. Monitoring should close the gap between analytical methods in the laboratory and the field to determine possible impacts on organisms at site.     

Persistent Organic Pollutants in Singapore's Coastal Marine Environment: Part II,Sediments

Polycyclic aromatic hydrocarbons (PAHs) can enter the marine environment from a variety of anthropogenic sources. As some PAHs are known or suspected carcinogens and mutagens, their potential hazard to human health and the natural environment warrants investigation. This is the first reported study on the prevalence and concentration of PAHs in marine sediments from Singapore's coastal environment, and accompanies the report by Basheer et al. (2003) on the measurement of persistent organic pollutants (POPs) in seawater. The concentration of 16 PAH, classified as USEPA priority pollutants were analysed in sediments from 22 sample stations located within the northeastern and southwestern regions of Singapore's marine waters. The total PAH concentration varied between 15.22 μg g^-1 and 82.41 μg g^-1 in the northeastern region and between 13.63 μg g^-1 and 84.92 μg g^-1in the southwestern region. The highest concentration of total PAH i.e. 84.92 μg g^-1 was recorded at a site adjacent to a petrochemical refinery. Among the sixteen individual PAHs, chrysene, indeno[1,2,3-cd]pyrene and benzo[a]anthracene were most prevalent in the sediments. The relatively low kinetic/thermodynamic isomer ratios for PAHs suggest that PAHs of pyrogenic origin are predominant in Singapore's coastal environment. The distribution of higher molecular weight i.e. (4–5 ring) individual PAHs corresponded to mixture profiles typical of those originating from high temperature combustion processes subjected to photolytic degradation during long-range atmospheric transportation. A comparison of total PAH concentration data for sediments collected from Singapore relative to those reported for other countries indicates a moderate level of PAH contamination in Singapore's coastal marine sediments.