Concentrations and bioaccessibility of polycyclic aromatic hydrocarbons in wastewater-irrigated soil using in vitro gastrointestinal test

BACKGROUND, AIM, AND SCOPE: Polycyclic aromatic hydrocarbons (PAHs) are widespread environmental contaminants and contribute to the pollution of soil environment. Soil ingestion is of increasing concern for assessing health risk from PAH-contaminated soils because soil ingestion is one of the potentially important pathways of exposure to environmental pollutants, particularly relevant for children playing at contaminated sites due to their hand-to-mouth activities. In vitro gastro-intestinal tests imitate the human digestive tract, based on the physiology of humans, generally more simple, less time-consuming, and especially more reproducible than animal tests. This study was conducted to investigate the level of PAH contamination and oral bioaccessibility in surface soils, using physiologically based in vitro gastro-intestinal tests regarding both gastric and small intestinal conditions. MATERIALS AND METHODS: Wastewater-irrigated soils were sampled from the metropolitan areas of Beijing and Tianjin, China, which were highly contaminated with PAHs. Reference soil samples were also collected for comparisons. At each site, four soils were sampled in the upper horizon at the depth of 0-20 cm randomly and were bulked together to form one composite sample. PAH concentrations and origin were investigated and a physiologically based in vitro test was conducted using all analytical grade reagents. Linear regression model was used to assess the relationship between total PAH concentrations in soils and soil organic carbon (SOC). RESULTS: A wide range of total PAH concentrations ranging from 1,304 to 3,369 mug kg(-1) in soils collected from different wastewater-irrigated sites in Tianjin, while ranging from 2,687 to 4,916 mug kg(-1) in soils collected from different wastewater-irrigated sites in Beijing, was detected. In general, total PAH concentrations in soils from Beijing sites were significantly higher than those from Tianjin sites, indicating a dominant contribution from both pyrogenic and petrogenic sources. Results indicated that the oral bioaccessibility of PAHs in small intestinal was significantly higher (from P < 0.05 to P < 0.001) than gastric condition. Similarly, the oral bioaccessibility of PAHs in contaminated sites was significantly higher (from P < or = 0.05 to P < 0.001) than in reference sites. Individual PAH ratios (three to six rings), a more accurate and reliable estimation about the emission sources, were used to distinguish the natural and anthropogenic PAH inputs in the soils. Results indicated that PAHs were both pyrogenic and petrogenic in nature. DISCUSSION: The identification of PAH sources and importance of in vitro test for PAH bioaccessibility were emphasized in this study. The oral bioaccessibility of individual PAHs in soils generally decreased with increasing ring numbers of PAHs in both the gastric and small intestinal conditions. However, the ratio of bioaccessibility of individual PAHs in gastric conditions to that in the small intestinal condition generally increased with increasing ring numbers, indicating the relatively pronounced effect of bile extract on improving the bioaccessibility of PAHs with relatively high ring numbers characterized by their high K ( ow ) values. Similarly, total PAH concentrations in soils were strongly correlated with SOC, indicating that SOC was the key factor determining the retention of PAHs in soils. CONCLUSIONS: Soils were contaminated with PAHs due to long-term wastewater irrigation. PAHs with two to six rings showed high concentrations with a significant increase over reference soils. Based on the molecular indices, it was suggested that PAHs in soils had both pyrogenic and petrogenic sources. It was also concluded that the oral bioaccessibility of total PAHs in the small intestinal condition was significantly higher than that in the gastric condition. Furthermore, the bioaccessibility of individual PAHs in soils generally decreased with the increasing ring numbers in both the gastric and small intestinal conditions. RECOMMENDATIONS AND PERSPECTIVES: It is suggested that more care should be given while establishing reliable soil criteria for PAHs, especially concerning the health of children who may ingest a considerable amount of PAH-contaminated soil via outdoor hand-to-mouth activities.     

Pollutants in Hong Kong soils: polycyclic aromatic hydrocarbons

An extensive soil survey was carried out to study the polycyclic aromatic hydrocarbon (PAH) contaminations in 138 soil samples collected throughout Hong Kong. Results demonstrated that there were low levels of PAH contaminations (median of summation operator 16US EPA PAHs=140 microg kg(-1)) for all land uses (urban park, greening area, country park, rural area, restored landfill, agricultural farmland, orchard farm, crematorium, industrial and near highway area). However, localized hotspots were identified with summation operator 16PAH concentrations as high as 19,500 microg kg(-1) in one urban park. These findings were also confirmed by multivariate analysis. Comparison of PAH profiles showed a widespread domination of its 4-ring member. The major contribution was vehicular emissions from petroleum, and however at the hotspots, the improper disposal of used motor oils. In general, the pollution levels for all the land uses were below the recommended values for residential and general purposes stated in soil quality guidelines such as Netherlands and Denmark except certain identified hotspots. The potential health hazards imposed by these hotspots were alarming, and their existence (3 out of 138 samples) suggested that sole monitoring of atmospheric PAHs may not adequately address the hidden risks to human in urban city.     

The lack of microbial degradation of polycyclic aromatic hydrocarbons from coal-rich soils

Analytical techniques used to assess the environmental risk of contamination from polycyclic aromatic hydrocarbons (PAHs) typically consider only abiotic sample parameters. Supercritical fluid extraction and sorption enthalpy experiments previously suggested slow desorption rates for PAH compounds in two coal-contaminated floodplain soils. In this study, the actual PAH availability for aerobic soil microorganisms was tested in two series of soil-slurry experiments. The experimental conditions supported microbial degradation of phenanthrene if it was weakly sorbed onto silica gel. Native coals and coal-derived particles in two soils effectively acted as very strong sorbents and prevented microbial PAH degradation. The long history of PAH exposure and degree of coal contamination apparently had no influence on the capability of the microbial soil community to overcome constraints of PAH availability. Within the context of the experimental conditions and the compounds chosen, our results confirm that coal-bound PAHs are not bioavailable and hence of low environmental concern.     

Assessment of honey contamination with polycyclic aromatic hydrocarbons

The aim of this study was to assess honey contamination by polycyclic aromatic hydrocarbons. Six species of honey were examined, as well as rape blossom and soil from villages P?czerzyno and Przybys?aw in West Pomerania, Poland. The instrumental analysis was performed using a HP 6890 gas chromatograph coupled to a HP 5973 mass spectrometer with selected ion monitoring (SIM). Quantification was done by gas chromatography-mass spectrometry (GC-MS) using perdeuterated internal standards. Both soil samples showed high levels of all 23 PAHs, whereas honey contained mostly non-carcinogenic PAHs of low molecular weight. The most contaminated honey from P?czerzyno contained 0.24 μg kg-1 benzo[a]pyrene. Moreover, despite low contamination of honey, a positive correlation was found between PAH content in honey, blossom and soil.     

Bacterial community structure in soils contaminated by polycyclic aromatic hydrocarbons

Bacterial community structure was examined in polycyclic aromatic hydrocarbon (PAH) contaminated soil taken from a timber treatment facility in southern Ireland. Profiles of soil bacterial communities were generated using a molecular fingerprinting technique, terminal restriction fragment length polymorphism (TRFLP), and results were interpreted using sophisticated multivariate statistical analysis. Findings suggested that there was a correlation between PAH structure and bacterial community composition. Initial characterisation of soil from the timber treatment facility indicated that PAH contamination was unevenly distributed across the site. Bacterial community composition was correlated with the type of PAH present, with microbial community structure associated with soil contaminated with two-ringed PAHs only being distinctly different to communities in soils contaminated with multi-component PAH mixtures. Typically the number of bacterial ribotypes detected in samples did not appear to be adversely affected by the level of contamination.     

Polycyclic aromatic hydrocarbons in the surface soils from outskirts of Beijing, China

Surface soils from the outskirts of Beijing were analyzed for 16 priority polycyclic aromatic hydrocarbons (PAHs) using gas chromatography and mass spectrometry (GC-MS). The distribution map of total PAHs content was obtained as a contour plot. The concentration range of 16 PAHs varied by over two orders of magnitude from 0.016 microg g-1 in rural to 3.884 microg g-1 in suburban soils with the relatively standard deviation of 70.5%, showing large differences in the extent of PAHs pollution at the various sampling sites. It was notable that the concentration of BaP was 0.005-0.270 microg g-1 with a mean of 0.055 microg g-1. In general, the distribution of PAHs centered on the high molecular weight PAHs known to be carcinogenic. The 4-6 ring PAHs represented about 66% in rural samples and 70% in suburban soils of the total PAHs found. There was relatively good relationship among most of the individual PAHs and the compounds of Pyr, BaA, Flu, BbF, BaP, Chr and Ph gave strong correlation (r>0.8) with the sum of PAHs. The selected marked compounds, a principal component analysis (PCA) and special PAHs compound ratios (Ph/An vs Flu/Pyr; summation operator COMB/ summation operator EPA-PAHs) suggest the pyrogenic origins, especially traffic exhausts, are the dominant sources of PAHs in Beijing outskirts soils.     

Distribution of polycyclic aromatic hydrocarbons in agricultural soils in South Korea

The content and type of polycyclic aromatic hydrocarbons (PAH) in soils from paddy fields and upland areas in South Korea were determined using gas chromatography linked to mass spectrometry (GC–MS). The distribution map of total PAH content was obtained as a contour plot using a geographical information system. The overall distribution of PAH was found to be closely related to the pollution sources, the size of city and the type of industry. The average content of total PAH in all samples was 236 μg kg⁻¹, and the range was from 23.3 to 2834 μg kg⁻¹. The highest concentrations were found in soils sampled near iron processing plants. The concentration of PAH decreased in the order fluoroanthene>benzo(b)fluoroanthene>pyrene. Special PAH compound ratios, such as phenanthrene/anthracene and fluoroanthene/pyrene, were calculated to evaluate the origin. The collected data suggested that the pyrogenic origins such as motor vehicle exhaust and heavy industry emission were the dominant source of PAH in Korean soils.     

均匀电场下多环芳烃在土壤中的迁移

当循环电解液流速为800 mL/h,电解液为无菌水时,电渗流流量、菲和芘在土壤中迁移量在电压梯度为1 V/cm作用下比电压梯度为0.5 V/cm时要多;电动注入表面活性剂Tween80和HPCD均可以提高菲和芘在土壤中的迁移,注入Tween80和HPCD浓度分别为500和1 000 mg/L时,相应地Phe提高5.8倍和11.7倍、芘提高2倍和3.4倍;而BaP在水中的溶解度太小,电场作用和电动注入表面活性剂对BaP在土壤中的迁移量影响很小。为建立电动修复有机污染物污染提供了技术基础。     

A multi-process phytoremediation system for removal of polycyclic aromatic hydrocarbons from contaminated soils

To improve phytoremediation processes, multiple techniques that comprise different aspects of contaminant removal from soils have been combined. Using creosote as a test contaminant, a multi-process phytoremediation system composed of physical (volatilization), photochemical (photooxidation) and microbial remediation, and phytoremediation (plant-assisted remediation) processes was developed. The techniques applied to realize these processes were land-farming (aeration and light exposure), introduction of contaminant degrading bacteria, plant growth promoting rhizobacteria (PGPR), and plant growth of contaminant-tolerant tall fescue (Festuca arundinacea). Over a 4-month period, the average efficiency of removal of 16 priority PAHs by the multi-process remediation system was twice that of land-farming, 50% more than bioremediation alone, and 45% more than phytoremediation by itself. Importantly, the multi-process system was capable of removing most of the highly hydrophobic, soil-bound PAHs from soil. The key elements for successful phytoremediation were the use of plant species that have the ability to proliferate in the presence of high levels of contaminants and strains of PGPR that increase plant tolerance to contaminants and accelerate plant growth in heavily contaminated soils. The synergistic use of these approaches resulted in rapid and massive biomass accumulation of plant tissue in contaminated soil, putatively providing more active metabolic processes, leading to more rapid and more complete removal of PAHs.     

Residue level of polycyclic aromatic hydrocarbons in Japanese paddy soils from 1959 to 2002

The residue level of 21 polycyclic aromatic hydrocarbons (PAHs) and the temporal changes in this level were investigated in paddy soils collected from particular experimental sites in Japan from 1959 to 2002. The average total PAH concentration in all the samples was 496 microg kg(-1), and it ranged from 52.9 to 2180 microg kg(-1). The residue level of the PAHs was the highest during the 1960s, rapidly decreased during the 1970s, and remained almost constant thereafter. Relatively high PAH concentrations were observed in soils from areas that experienced heavy snowfall and that had relatively low air temperature. The predominant PAHs were phenanthrene, fluoranthene, naphthalene, and pyrene, and their concentration overall and in relation to that of the total PAHs decreased each year since the 1960s. Similarities in the PAH profiles among the locations were determined using the concentration correlation matrix and cluster analysis, and ratios of the levels of specific PAH pairs were also calculated to determine their origin. The collected data suggested that the origins of soil PAHs changed chronologically from the burning of agricultural wastes such as stubble before the mid-1970s to the combustion of fossil fuel and its secondary products after the mid-1970s.     

Removal of polycyclic aromatic hydrocarbons from manufactured gas plant-contaminated soils using sunflower oil: laboratory column experiments

Laboratory column experiments were performed to remove PAHs (polycyclic aromatic hydrocarbons) from two contaminated soils using sunflower oil. Two liters of sunflower oil was added to the top of the columns (33 cm x 21 cm) packed with 1 kg of PAH-contaminated soil. The sunflower oil was applied sequentially in two different ways, i.e. five additions of 400 ml or two additions of 1l. The influence of PAH concentration and the volume of sunflower oil on PAH removal were examined. A soil respiration experiment was carried out and organic carbon contents of the soils were measured to determine degradability of remaining sunflower oil in the soils. Results showed that the sunflower oil was effective in removing PAHs from the two soils, more PAHs were removed by adding sunflower oil in two steps than in five steps, probably because of the slower flow rate in the former method. More than 90% of total PAHs was removed from a heavily contaminated soil (with a total 13 PAH concentration of 4721 mg kg(-1)) using 4 l of sunflower oil. A similar removal efficiency was obtained for another contaminated soil (with a total 13 PAH concentration of 724 mg kg(-1)), while only 2l was needed to give a similar efficiency. Approximately 4-5% of the sunflower oil remained in the soils. Soil respiration curves showed that remaining sunflower oil was degraded by allowing air exchange and supplying with nutrients. Organic carbon content of the soil was restored to original level after 180 d incubation. These results indicated that the sunflower oil had a great capacity to remove PAHs from contaminated soils, and sunflower oil solubilization can be an alternative technique for remediation of PAH contaminated soils.     

The effect of temperature on the rate of disappearance of polycyclic aromatic hydrocarbons from soils

The effect of temperature on the range and rate of disappearance of four polycyclic aromatic hydrocarbons (PAHs; fluorene, anthracene, pyrene and chrysene) added as a mixture of pure compounds to two different soils (light loam and loamy sand) was investigated over 180 days in a laboratory experiment. An increase in temperature from 10 to 25 degrees C enhanced the losses of all four PAHs from both soils. The effect of temperature on the rate of PAH disappearance depended on the physico-chemical properties of the compound and of the soil. The long half-lives at lower temperatures as obtained in the laboratory tests may suggest high persistence of higher molecular weight PAHs under some field conditions.     

改性膨润土对水体中多环芳烃的吸附

改性膨润土被广泛地应用于吸附水体中重金属离子和有机污染物,但关于改性膨润土吸附水体中多环芳烃混合物的动力学研究鲜见报道。利用十二烷基三甲溴化铵和十二烷基磺酸钠对膨润土进行改性,并将之应用于吸附水体中萘、蒽、菲和芘4种多环芳烃,考察了吸附剂投加量、时间和温度等条件对吸附效果的影响。实验结果表明,在25℃、吸附时间40 min、起始浓度为1.25 mg/mL、改性膨润土的投加量为4 g/L的条件下,该吸附剂对萘、蒽、菲和芘的吸附率分别为99.1%、99.6%、98.7%和98.9%。改性膨润土对水体中4种多环芳烃的吸附机理服从准二级动力学方程,该吸附剂吸附等温线服从Langmuir方程。     

Study of factors affecting on the extraction efficiency of polycyclic aromatic hydrocarbons from soils using open-vessel focused microwave-assisted extraction

As part of an evaluation of focused microwave-assisted extraction (FMAE) using an open-vessel system, the effects of matrix, moisture content, ageing, and solvent have been studied on the extraction efficiency of polycyclic aromatic hydrocarbons (PAHs) from spiked soils. PAHs were spiked onto three different uncontaminated air dried and originally wet soil matrices with 1- and 20-day ageing periods. Solvents used were hexane–acetone (1:1), cyclohexane–acetone (1:1) and dichloromethane. FMAE only required a small amount of solvent (20 ml) and short extraction time (10 min) in the open cell under 90 W of microwave power. The results revealed that the extraction efficiency strongly depends on the nature of soil matrix; moisture content may enhance the recoveries of PAHs for many cases; and, the influence of the type of solvent is not significant. A comparison between microwave extraction and 16-h Soxhlet extraction has been made on spiked soils. It evidenced that the microwave method under ambient pressure is a suitable alternative to Soxhlet method for the analysis of PAHs in soils. For the evaluation of the developed FMAE method, three reference materials were used. The PAHs recovered from three reference materials were in a good agreement with reference values.     

化学氧化法治理焦化厂PAHs污染土壤

针对焦化类工业场地多环芳烃(PAHs)污染土壤治理问题,选取北京某焦化厂PAHs污染土壤,对其进行化学氧化修复治理的室内模拟研究,实验采用高锰酸钾、Fenton试剂、双氧水和过硫酸钠4种氧化剂,测试了氧化剂的土壤氧化剂需求量(SOD),分析了4种氧化剂对15种PAHs的氧化效果以及反应过程中土壤总PAHs浓度和土壤有机质含量(SOM)随反应时间的变化。结果表明,北京某焦化厂PAHs污染土壤过硫酸钠SOD低于高锰酸钾SOD;Fenton试剂和双氧水对PAHs的总去除率分别为59.53%和62.72%,且对三环PAHs的去除率较好,高锰酸钾对PAHs的总去除率为59.24%,对蒽和苯并(a)芘的去除效果较好,活化过硫酸钠对PAHs的总去除率为68.87%;土壤有机质可通过对PAHs的吸附影响氧化剂的处理效果。     

Concentrations, sources and spatial distribution of polycyclic aromatic hydrocarbons in soils from Beijing, Tianjin and surrounding areas, North China

The concentrations, profiles, sources and spatial distribution of polycyclic aromatic hydrocarbons (PAHs) were determined in 40 surface soil samples collected from Beijing, Tianjin and surrounding areas, North China in 2007, and all sampling sites were far from industrial areas, roadsides and other pollution sources, and across a range of soil types in remote, rural villages and urban areas. The total concentrations of 16 PAHs ranged from 31.6 to 1475.0 ng/g, with an arithmetic average of 336.4 ng/g. The highest PAH concentrations were measured in urban soils, followed by rural village soils and soils from remote locations. The remote-rural village-urban PAH concentration gradient was related to population density, gross domestic product (GDP), long-range atmospheric transport and different types of land use. In addition, the PAH concentration was well correlated with the total organic carbon (TOC) concentration of the soil. The PAH profile suggested that coal combustion and biomass burning were primary PAH sources.     

Volatilization of polycyclic aromatic hydrocarbons from coal-tar-sealed pavement

The effects of the herbicide atrazine on the gill of the freshwater fish Prochilodus lineatus were evaluated after exposure of fish to 2, 10 and 25 μg L⁻¹ atrazine during 48 h (acute exposure) and 14 d (subchronic exposure). Ions and osmolality were measured in plasma and gill samples were taken to determine the Na⁺/K⁺-ATPase (NKA) and carbonic anhydrase (CA) activities and for morphological analysis. Plasma osmolality and Na⁺ and Cl⁻ ions changed depending on atrazine concentration, but atrazine exposure had no effect on the Na⁺/Cl⁻ ratio. NKA activity did not change after atrazine exposure, but CA activity decreased in fish exposed to 25 μg L⁻¹ for 14 d. Gill MRC density decreased after acute exposure but did not change in fish exposed to the subchronic treatment. The MRC density at the epithelial surface increased in fish exposed to 25 μg L⁻¹, and the MRC fractional area (MRCFA) increased in fish exposed to 10 μg L⁻¹. The changes in MRCs provide evidence of morphological adjustments to maintain ionic homeostasis in spite of the inhibition of CA activity at the highest atrazine concentration.     

Halogenated polycyclic aromatic hydrocarbons in the environment

Halogenated polycyclic aromatic hydrocarbons (HPAHs) have been reported to occur in air, sediment, fly ash, and biota samples. This review summarized current existing data on the environmental occurrence, behavior, physicochemical properties, emission sources, and toxic equivalents of HPAHs. Firstly, the physicochemical properties of HPAHs were summarized. Then, an overview of environmental occurrence of HPAHs in ambient matrices including biological samples was reviewed. Meanwhile, the emission sources and possible formation mechanisms of HPAHs were discussed. Apart from that, the aryl hydrocarbon receptor (AhR)-mediated activities were summarized, which indicated that the position and number of halogen atoms on the parent PAHs molecule were important determinant factors affecting the AhR-mediated activity of individual HPAHs congeners. Finally, some research recommendations on HPAHs were given.     

Removal of polycyclic aromatic hydrocarbons from aged-contaminated soil using cyclodextrins: experimental study

The removal of polycyclic aromatic hydrocarbons (PAHs) from soil using water as flushing agent is relatively ineffective due to their low aqueous solubility. However, addition of cyclodextrin (CD) in washing solutions has been shown to increase the removal efficiency several times. Herein are investigated the effectiveness of cyclodextrin to remove PAH occurring in industrially aged-contaminated soil. Beta-cyclodextrin (BCD), hydroxypropyl-beta-cyclodextrin (HPCD) and methyl-beta-cyclodextrin (MCD) solutions were used for soil flushing in column test to evaluate some influent parameters that can significantly increase the removal efficiency. The process parameters chosen were CD concentration, ratio of washing solution volume to soil weight, and temperature of washing solution. These parameters were found to have a significant and almost linear effect on PAH removal from the contaminated soil, except the temperature where no significant enhancement in PAH extraction was observed for temperature range from 5 to 35 degrees C. The PAHs extraction enhancement factor compared to water was about 200.