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1.
Freely dissolved aqueous concentrations in the soil pore water represent an important aspect of bioavailability and risk assessment of contaminated soils. In this study, a negligible depletive partitioning based sampling technique was validated and applied to measure free concentrations of polycyclic aromatic hydrocarbons (PAHs) in spiked, aged and field-contaminated soils. Detailed kinetic studies were performed to select appropriate equilibration times. Freely dissolved aqueous concentrations in the pore water were compared to total concentrations, and sorption coefficients were calculated. Results show that equilibrium partition models can predict sorption coefficients of freshly spiked and lab-aged soils rather accurately. However, freely dissolved pore water concentrations of field-contaminated soils are orders of magnitude lower than model predictions. Consequently, environmental risks can be highly overestimated with these models. The simple and sensitive partitioning-based sampling technique used in this study, could, therefore, be applicable to improve site-specific risk assessment of field-contaminated soils.  相似文献   

2.
Freely dissolved pore water concentrations are difficult to assess in complex matrixes such as soils or sediments. In this study, a negligible-depletion partitioning-based sampling technique was applied to measure freely dissolved pore water concentrations. A poly(dimethylsiloxane) (PDMS)-coated glass fiber was exposed to a slurry of a soil spiked with several PAHs at concentrations ranging from 2 to 2000 mg/kg. PAH-concentrations in the PDMS coating increased linearly with the total soil concentration until a certain maximum was reached. Freely dissolved pore water concentrations were calculated using PDMS-water partition coefficients, and the calculated maximum pore water concentrations corresponded with the aqueous solubility of the tested compounds. Furthermore, the sampling technique is very sensitive because it can detect freely dissolved pore water concentrations in the ng/L range for the tested PAHs. Freely dissolved pore water concentrations are an important parameter for the exposure of organisms in soil. Saturation of the pore water with increasing soil concentrations should therefore be considered in soil toxicity testing. Sorption coefficients that were calculated from freely dissolved concentrations were slightly higher than estimates based on octanol-water partition coefficients. These differences are discussed in relation to the effects of dissolved organic matter in soil pore water on the determination of sorption coefficients.  相似文献   

3.
Lipid-free polyethylene membrane tubing (LFT) has been further developed in response to a growing need for an inexpensive and simple time-integrative sampling device for dissolved hydrophobic contaminants in water. The LFT sampler is based on the diffusion of dissolved hydrophobic target compounds through the aqueous boundary layer and into the polyethylene membrane, mimicking uptake by organisms. We demonstrate through laboratory and field validation studies that LFT provided the same benefits as many other passive sampling devices, withoutthe potential of analytical interference from lipid impurities. A total of 370 LFTs and semipermeable membrane devices were deployed for 21 days in paired studies at highly urbanized, undeveloped, and two Superfund sites, representing several river conditions. A simple internal surrogate spiking method served as an in situ calibration indicator of the effects of environmental conditions on the uptake rates. A modified extraction method for the LFT increased recoveries while decreasing solvent use and labor compared to other organic extraction procedures. LFT sampling rates were estimated using ratios, in situ calibration and modeling for over 45 target analytes, including PAHs, PCBs, and pesticides.  相似文献   

4.
Adding activated carbon (AC) to contaminated sediment has been suggested as an effective method for sediment remediation. AC binds chemicals such as polycyclic aromatic hydrocarbons (PAHs), thus reducing the toxicity of the sediment. Negative effects of AC on benthic organisms have also been reported. Here, we present a conceptual model to quantify the trade-off, in terms of biomass changes, between the advantageous PAH toxicity reduction and the negative effects of AC on populations of benthic species. The model describes population growth, incorporates concentration-effect relationships for PAHs in the pore water and for AC, and uses an equilibrium sorption model to estimate PAH pore water concentrations as a function of AC dosage. We calibrated the model using bioassay data and analyzed it by calculating isoclines of zero population growth for two species. For the sediment evaluated here, the results show that AC may safely protect the benthic habitat against considerable sediment PAH concentrations as long as the AC dosage remains below 4%.  相似文献   

5.
In this paper we report an extension of our previous work on the triolein-embedded cellulose acetate membrane (TECAM) as a passive sampling device (PSD) and describe the results from simultaneous exposure of TECAMs and triolein-containing semipermeable membrane devices (SPMDs) to PAHs in lake water for 16 days. The data obtained provided a comparison of the uptake rates of specific PAHs by the two PSDs. Using 16-day accumulation tests, similar PAH distribution patterns in TECAMs and in SPMDs (R2 = 0.89, p < 0.0001) were observed. However, it was noted that TECAMs could take up greater amounts of PAHs than SPMDs (735 ng/g of TECAM vs 630 ng/g of SPMD). Uptake rate constants of TECAMs and SPMDs for 16 priority pollutant (PP) PAHs, corrected for dissolved organic carbon, ranged from 0.28 to 2.94 L d(-1) and from 0.16 to 0.91 L d(-1), respectively. The elimination rate constants of TECAMs were 1.4-6.7 times greater than those observed for SPMDs, thereby indicating that PAHs required shorter times to achieve equilibrium in TECAMs than in SPMDs. Thus, the results of the present study suggest that TECAMs have significant potential as a good monitor to assess the pollution of hydrophobic pollutants in aquatic environments.  相似文献   

6.
Polycyclic aromatic hydrocarbons (PAHs), which are generated by heat treatment and smoke curing of meat, pose a risk to human health. At present, the determination of these unwanted contaminants requires costly, time-consuming chemical analysis of smoked meat. An alternative is effect-directed high-throughput bioassays, which could also be used as a pre-screening method. The authors recently adapted the in vitro chemical-activated luciferase gene expression (CALUX) assay as a rapid, sensitive, and inexpensive screening technique for compounds such as dioxins, polychlorinated biphenyls, and PAHs. The aim of the present study was to apply a practical approach under realistic conditions. Custom-made meat samples produced under defined conditions with different PAH levels were analysed using this bioassay and gas chromatography-mass spectrometry (GC/MS) to determine the influence of different smoking conditions (temperature and duration) on PAH levels. It was found that cold smoking for up to 6 h did not result in strong PAH contamination, whereas hot (65°C) and longer smoking times caused a considerable increase in both the bioassay response and the levels of 31 individually determined PAHs. The response in the effect-based bioassay was in good agreement with the values of chemical analysis. The bioassay made it possible to determine accurately the degree of contamination. The results show that this assay is suitable for high-throughput screening for unknown levels of toxicologically relevant PAHs in meat samples and is sensitive enough to differentiate between different PAH levels generated under various smoking conditions. Effect-based screening techniques, therefore, provide a new instrument for official food monitoring.  相似文献   

7.
Semipermeable membrane devices (SPMDs) were exposed at ten sampling points, each representing a different stage in the treatment process, in a municipal sewage treatment plant. Differences in SPMD uptake kinetics of polycyclic aromatic hydrocarbons (PAHs) due to variations in conditions at the sampling sites were evaluated by using five performance reference compounds (PRCs) with log K(ow) values of 4.20 to 6.34. PRC release rate constants (k(e,PRC) values) were calculated for PRCs for which 50-98% of the initial amounts were lost during the sampling period. The k(e,PRC) values were high, ranging from 0.08 to 0.11 day(-1) for the studied PRCs, at sampling site W1 (raw sewage), the only sampling site where significant amounts of the PRCs with log K(ow) values > 5 were released from the SPMDs. At the other sampling sites, only PRCs with log K(ow) values between 4.20 and 4.50 were released in significant amounts. The release rates at these sites were lowest (0.04 day(-1)) at sampling site W9 (the secondary clarifier) and highest (0.18 day(-1)) at W8 (the active sludge aeration basin). Differences between sampling rates (R(s)) obtained using published laboratory-calibrated data and PRC-corrected R(s) values were visualized by principal component analysis (PCA). The water concentrations of 24 studied PAHs fell substantially during the course of the sewage treatment process. However, low molecular weight PAHs were more effectively removed than high molecular weight PAHs. Significant deviations between actual and estimated water concentrations may arise unless PRC-corrected R(s) values are applied.  相似文献   

8.
The Hebei Spirit oil spill occurred in December 2007 approximately 10 km off the coast of Taean, South Korea, on the Yellow Sea. However, the exposure and potential effects remain largely unknown. A total of 50 surface and subsurface sediment samples were collected from 22 sampling locations at the spill site in order to determine the concentration, distribution, composition of residual crudes, and to evaluate the potential ecological risk after two years of oil exposure. Samples were extracted and analyzed for 16 polycyclic aromatic hydrocarbons (PAHs), 20 alkyl-PAHs, 15 aliphatic hydrocarbons, and total petroleum hydrocarbons using GC-MSD. AhR-mediated activity associated with organic sediment extracts was screened using the H4IIE-luc cell bioassay. The response of the benthic invertebrate community was assessed by mapping the macrobenthic fauna. Elevated concentrations of residual crudes from the oil spill were primarily found in muddy bottoms, particularly in subsurface layers. In general, the bioassay results were consistent with the chemistry data in a dose-dependent manner, although the mass-balance was incomplete. More weathered samples containing greater fractions of alkylated PAHs exhibited greater AhR activity, due to the occurrence of recalcitrant AhR agonists present in residual oils. The macrobenthic population distribution exhibits signs of species-specific tolerances and/or recolonization of certain species such as Batillaria during weathering periods. Although the Hebei Spirit oil spill was a severe oil exposure, it appears the site is recovering two years later.  相似文献   

9.
Settled house dust (SHD) may be a significant source of children's indoor exposure to hazardous substances including polycyclic aromatic hydrocarbons (PAHs). In this study, organic extracts of sieved vacuum cleaner dust from 51 homes were examined for the presence of 13 PAHs via GC/MS. PAHs were found in all samples with levels of total PAHs ranging between 1.5 and 325 microg g(-1). The PAH concentrations in the SHD were correlated with information contained in corresponding household questionnaires. Analyses showed levels of PAHs to be negatively associated with noncombustion activities such as vacuum cleaning frequency. A risk assessment was conducted to evaluate the excess lifetime cancer risks posed to preschool aged children who ingested PAHs in SHD. The assessment revealed that exposure to PAHs at levels found in 90% of the homes (< 40 microg g(-1)) would result in excess cancer risks that are considered acceptable (i.e., 1-100 x 10(-6)). However, exposure to higher levels of PAHs found in five homes yielded risks that could be higher than 1 x 10(-4).  相似文献   

10.
Semipermeable membrane devices (SPMDs) are passive samplers used to measure the vapor phase of organic pollutants in air. This study tested whether extremely high wind-speeds during a 21-day sampling increased the sampling rates of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs), and whether the release of performance reference compounds (PRCs) was related to the uptakes at different wind-speeds. Five samplers were deployed in an indoor, unheated, and dark wind tunnel with different wind-speeds at each site (6-50 m s(-1)). In addition, one sampler was deployed outside the wind tunnel and one outside the building. To test whether a sampler, designed to reduce the wind-speeds, decreased the uptake and release rates, each sampler in the wind tunnel included two SPMDs positioned inside a protective device and one unprotected SPMD outside the device. The highest amounts of PAHs and PCBs were found in the SPMDs exposed to the assumed highest wind-speeds. Thus, the SPMD sampling rates increased with increasing wind-speeds, indicating that the uptake was largely controlled by the boundary layer at the membrane-air interface. The coefficient of variance (introduced by the 21-day sampling and the chemical analysis) for the air concentrations of three PAHs and three PCBs, calculated using the PRC data, was 28-46%. Thus, the PRCs had a high ability to predict site effects of wind and assess the actual sampling situation. Comparison between protected and unprotected SPMDs showed that the sampler design reduced the wind-speed inside the devices and thereby the uptake and release rates.  相似文献   

11.
The determination of predicted no-effect concentrations (PNECs) and sediment quality guidelines (SQGs) of toxic chemicals in marine sediment is extremely important in ecological risk assessment. However, current methods of deriving sediment PNECs or threshold effect levels (TELs) are primarily based on laboratory ecotoxicity bioassays that may not be ecologically and environmentally relevant. This study explores the possibility of utilizing field data of benthic communities and contaminant loadings concurrently measured in sediment samples collected from the Norwegian continental shelf to derive SQGs. This unique dataset contains abundance data for ca. 2200 benthic species measured at over 4200 sampling stations, along with co-occurring concentration data for >25 chemical species. Using barium, cadmium, and total polycyclic aromatic hydrocarbons (PAHs) as examples, this paper describes a novel approach that makes use of the above data set for constructing field-based species sensitivity distributions (f-SSDs). Field-based SQGs are then derived based on the f-SSDs and HCx values [hazardous concentration for x% of species or the (100-x)% protection level] by the nonparametric bootstrap method. Our results for Cd and total PAHs indicate that there are some discrepancies between the SQGs currently in use in various countries and our field-data-derived SQGs. The field-data-derived criteria appear to be more environmentally relevant and realistic. Here, we suggest that the f-SSDs can be directly used as benchmarks for probabilistic risk assessment, while the field-data-derived SQGs can be used as site-specific guidelines or integrated into current SQGs.  相似文献   

12.
A study was conducted to measure atmospheric concentrations of PAHs and PCBs and estimate their fluxes between air and water in the northern San Francisco Estuary. Ambient air samples were collected once every 12 days at a single sampling site in Concord, CA, from June to November 2000, using a modified high-volume air-sampling device equipped with glass fiber filters and polyurethane foam. Concentrations of total PAHs and PCBs ranged from 5.7 to 56 and 0.17 to 0.32 ng/m3, respectively. PAHs and PCBs in the ambient air were predominantly in the vapor phase (83-99%). Gaseous fluxes of PAHs in the estuary showed high seasonal variation, ranging from 110 ng x m(-2) x day(-1) efflux in August to 1,050 ng x m(-2) x day(-1) influx in November. Gaseous PCBs showed consistent net volatilization 12.2-24 ng x m(-1) x day(-1)) for this period. Particle settling contributed estimated net deposition fluxes of 45-960 ng x m(-2) day(-1) for PAHs and 0.39-2.1 ng x m(m(-2) x day(-1) for PCBs. Combining these fluxes, PAHs were either deposited to or lost from the estuary via the atmosphere, depending on the month. In contrast, there consistently was net emission of PCBs from the estuary to the atmosphere.  相似文献   

13.
Semipermeable membrane devices (SPMDs) were deployed at six sites in the Bangkok region, Thailand, to investigate spatial variations in atmospheric concentrations of polycyclic aromatic hydrocarbons (PAHs). Sampling sites affected by various levels of traffic intensity were studied. In addition, PAH levels were determined in a common human food plant (water spinach) harvested from canals and ponds in the sampling areas. Significant differences in atmospheric PAH concentrations between sites were found, with 10 times higher PAH levels in the urban areas compared to the rural areas. Increasing concentrations of 1-methylphenanthrene relative to phenanthrene were found in the urban air close to the city center, indicating that traffic probably contributed to the higher PAH concentrations detected. Due to SPMD's passive sampling technique, their long-term operation and high ability to detect spatial differences, they proved to be suitable for semiquantitative field studies of PAHs. The PAH compounds sampled with SPMDs were mainly associated with gaseous PAHs, while both gas phase and particle-bound PAHs were detected in the plant samples. The relative abundance ratios of some PAHs in the plants were not well correlated with the ratios detected in the SPMDs, indicating that gas-phase exposure made low contribution to the PAH concentrations in the plants. However, similarities in the profiles of 3-ring PAHs between the SPMD and plant samples indicate that gas-phase exchange occurs between the atmosphere and the plants.  相似文献   

14.
Literature values of atmospheric polycyclic aromatic hydrocarbon (PAH) concentrations from sampling sites around the world were found, and using a high-resolution human population grid, the population within a 25-km radius of each sampling site was calculated. A regression of concentration vs population revealed much about PAH concentration differences among regions as well as site locations within a continent. The best fit for the regression was for sampling locations in North America. A small amount of scatter was present for the regression of all developed countries indicating slight differences in emission regulations or energy usage. The regression from this plot was used as a benchmark for the expected relationship between PAHs and human population. Sites located within 25 km of a coasttended to have concentrations lower than expected, due to dilution with clean ocean air, while sites near industrial outputs or other point sources had higher than expected concentrations. Sites from developing countries typically had PAH concentrations that were far higher than those of the rest of the world.  相似文献   

15.
The effectiveness of thin-layer sand capping for contaminated sediment management (capping with a layer of thickness comparable to the depth of benthic interactions) is explored through experiments with laboratory-scale microcosms populated with the deposit-feeding oligochaete, Ilyodilus templetoni. Passive sampling of pore water concentrations in the microcosms using polydimethylsiloxane (PDMS)-coated fibers enabled quantification of high-resolution vertical concentration profiles that were used to infer contaminant migration rates and mechanisms. Observed concentration profiles were consistent with models that combine traditional contaminant transport processes (sorption-retarded diffusion) with bioturbation. Predictions of bioaccumulation based on contaminant pore water concentrations within the surface layer of the cap correlated well with observed bioaccumulation (correlation coefficient of 0.92). The results of this study show that thin-layer sand caps of contaminated sediments can be effective at reducing the bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) provided the thickness of the cap layer exceeds the depth of organism interaction with the sediments and the pore water concentrations within the biologically active zone remain low (e.g., when molecular diffusion controls transport from the underlying sediment layer).  相似文献   

16.
The importance of monitoring the transport of organic contaminants in soil and groundwater, and the pros and cons of existing sampling methods, are outlined. A new, alternative sampling method is proposed, using a passive sampler that functions as a water-permeable, semi-infinite sink for passing solutes of interest. Tracers integrated in the device store information on the volume of water passing through the sampler during the installation period. The conceptual basis of the sampling method is described. This device enables flux-proportional monitoring of the concentrations of mobile contaminants in the soil and groundwater. 14C-labeled phenanthrene (PHEN) and glyphosate (GLY) are used as case study compounds in laboratory experiments. The sorption capacities and uptake kinetics of 13 adsorbents are screened and compared, as well as the dissolution kinetics of three tracer salts: calcium citrate, calcium fluoride (CaF2), and calcium hydrogen phosphate (CaHPO4). The application of the passive sampler is then demonstrated in long-term laboratory experiments, using large soil columns under steady-state hydraulic conditions. The accumulated flux of PHEN was sampled with an accuracy of 3.6%-17.8%, using graphitized carbon, hexagonal mesoporous silica, and cross-linked polymers as adsorbents. The accumulated flux of GLY was sampled with an accuracy of 12.4%, using gamma-alumina as an adsorbent. The advantages and limitations of this new environmental monitoring method are discussed.  相似文献   

17.
Polycyclic aromatic hydrocarbons (PAHs) are generated during smoke curing and other heating treatments of food and represent a large class of chemical pollutants including a number of carcinogens. At present, PAHs are frequently detected by costly and time-consuming chemical analysis. Effect-directed in vitro cell-based bioassays of contaminants can offer a rapid, sensitive, and relatively inexpensive alternative for screening of contaminants in comparison to instrumental analysis. They enable estimation of total biological activity of all compounds acting through the same mode of binding. The aryl hydrocarbon receptor as a binding site plays an important role in PAH-induced carcinogenesis. The in vitro chemical-activated luciferase expression assay (using conditions to detect PAH) was investigated for its applicability for effect-directed analysis of PAH levels in smoked meat. There was an intra-assay variability of 0 to 15% and a mean coefficient of variation of 25% (3 to 50%) for the cleanup and bioassay analysis of the smoked pork samples. There was a correlation between the total responses of the bioassay and the individual amounts of the PAHs with a high molecular weight. The comparison of 2,3,7,8-tetrachlorodibenzo-p-dioxin and benzo[k]fluoranthene used as standard in the in vitro chemical-activated luciferase expression assay resulted in benzo[k]fluoranthene being able to be used as an alternative, nontoxic standard in the bioassay. This bioassay is an applicable effect-directed functional prescreening method for the analysis of PAHs in smoked meat and appears to have potential in being used for food control in the future.  相似文献   

18.
In this study, three types of solid-phase microextraction (SPME) passive samplers, including a fiber-retracted device, a polydimethylsiloxane (PDMS)-rod and a PDMS-membrane, were evaluated to determine the time weighted average (TWA) concentrations of polycyclic aromatic hydrocarbons (PAHs) in Hamilton Harbor (the western tip of Lake Ontario, ON, Canada). Field trials demonstrated that these types of SPME samplers are suitable for the long-term monitoring of organic pollutants in water. These samplers possess all of the advantages of SPME: they are solvent-free, sampling, extraction and concentration are combined into one step, and they can be directly injected into a gas chromatograph (GC) for analysis without further treatment. These samplers also address the additional needs of a passive sampling technique: they are economical, easy to deploy, and the TWA concentrations of target analytes can be obtained with one sampler. Moreover, the mass uptake of these samplers is independent of the face velocity, or the effect can be calibrated, which is desirable for long-term field sampling, especially when the convection conditions of the sampling environment are difficult to measure and calibrate. Among the three types of SPME samplers that were tested, the PDMS-membrane possesses the highest surface-to-volume ratio, which results in the highest sensitivity and mass uptake and the lowest detection level.  相似文献   

19.
On the basis of a monthly sampling effort from March 2005 to February 2006, the total concentrations of the sums of 27 and 15 polycyclic aromatic hydrocarbons (defined as sigma27PAHs and sigma15PAHs, respectively) in riverine runoff of the Pearl River Delta (PRD), China, and associated fluxes were determined. No clear temporal and spatial trends of PAH concentrations were found at all eight riverine runoff outlets where the samples were collected. The annual fluxes of sigma27PAHs and sigma15PAHs from the PRD to the coastal ocean were 60.2 and 33.9 metric tons, respectively. Assuming that riverine flux was positively related to the regional emission of PAHs, the annual riverine fluxes from five major rivers in China to the global oceans were estimated, which are quite significant relative to other major rivers of the world. On the basis of mass balance considerations, approximately 87% of sigma15PAHs inputting to the Pearl River Estuary and northern South China Sea was derived from riverine runoff from the PRD. In addition, approcimately 22.3 metric tons of sigma15PAHs annually outflow to open seas, which is equivalent to a concentration of 0.34 pg/L in the global oceans if the PAHs are evenly distributed in the upper 200 m of the water column. A comparison with the global background level of PAHs indicated that approximately 0.4% of PAHs in the open oceans may have been contributed by 1-year discharge from the PRD.  相似文献   

20.
Sediment pore water concentrations of polychlorinated biphenyls (PCBs) in a contaminated mudflat in San Francisco Bay, CA were determined by field-deployed polyethylene devices (PEDs). Sequential sampling of PEDs deployed in the field showed large differences in uptake rates and time to equilibrium compared to PEDs mixed with field-collected sediment in the laboratory. We demonstrate a modeling approach that involves the use of impregnated performance reference compounds (PRCs) and interpretation of the data either by PCB molar volume adjustment or environmental adjustment factors to measure pore water concentrations of 118 PCB congeners. Both adjustment methods predicted comparable sampling rates, and PCB pore water concentrations estimated by use of the molar volume adjustment method were similar to values analytically measured in pore waters from the laboratory and field. The utility of PEDs for sampling pore water in the field was evaluated at a tidal mudflat amended with activated carbon to sequester PCBs. Pore water concentrations decreased up to 60% within 18 months after activated carbon amendment, as compared to a mechanical-mixed control plot Results of this study illustrate PEDs provide an inexpensive, in situ method to measure total PCB contamination in sediment pore water using a small set of PRCs.  相似文献   

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