Passive samplers versus surfactant extraction for the evaluation of PAH availability in sediments with variable levels of contamination

The purpose of this study was to test the efficiency of passive solid samplers, polyoxymethylene (POM) strips and polydimethylsiloxane (PDMS) silicon tubing, to predict the bioavailability of native PAHs in contaminated sediments. Results were compared with worm bioaccumulation data and solid/liquid extraction using the surfactant Brij((R)) 700 (B700). The two passive samplers were found to act differently. The PDMS sampler overestimated the availability of PAHs in all studied sediments. The POM method provided results in accordance with those obtained with the B700 extraction. However, POM and B700 methods underestimated PAH availability in low contaminated sediments where biological factors (digestible organic matter) become important. Bioavailability of total PAHs was correctly predicted by POM and B700 in highly contaminated aluminum smelter sediments. A closer examination of individual PAH results indicated that both techniques overestimated the availability of large molecules with logK(ow)>6 suggesting a biological mechanism limiting uptake of larger PAHs which seems to be related to the molecular size of compounds.     

Partitioning of organochlorine pesticides from water to polyethylene passive samplers

The mass transfer rates and equilibrium partitioning behaviour of 14 diverse organochlorine pesticides (OCP) between water and polyethylene (PE) passive samplers, cut from custom made PE sheets and commercial polyethylene plastic bags, were quantified. Overall mass transfer coefficients, k_O, estimated PE membrane diffusion coefficients, D_PE, and PE-water partitioning coefficients, K_PE-water, are reported. In addition, the partitioning of three polycyclic aromatic hydrocarbons (PAHs) from water to PE is quantified and compared with literature values. K_PE-water values agreed mostly within a factor of two for both passive samplers and also with literature values for the reference PAHs. As PE is expected to exhibit similar sorption behaviour to long-chain alkanes, PE-water partitioning coefficients were compared to hexadecane-water partitioning coefficients estimated with the SPARC online calculator, COSMOtherm and a polyparameter linear free energy relationship based on the Abraham approach. The best correlation for all compounds tested was with COSMOtherm estimated hexadecane-water partitioning coefficients.     

Influence of temperature and origin of dissolved organic matter on the partitioning behavior of polycyclic aromatic hydrocarbons

Background, aim, and scope  

The behavior of polycyclic aromatic hydrocarbons (PAHs) is affected by dissolved organic matter (DOM) present in pore water of soils and sediments. Since partitioning to DOM reduces the bioavailable or freely dissolved PAH concentration in pore water, it is important to assess the effect of environmental variables on the magnitude of dissolved organic matter to water partition coefficients (K _DOC). The objective of this study was to apply passive samplers to measure freely dissolved PAHs allowing depletion from the aqueous phase. The method was applied to determine K _DOC at different temperatures for a selection of PAHs with natural DOM of very different origin.     

Multipoint moss passive samplers assessment of urban airborne polycyclic aromatic hydrocarbons: concentrations profile and distribution along Warsaw main streets

Polycyclic aromatic hydrocarbons (PAHs) distribution along 28 km of Warsaw main street have been surveyed in July 2000 using moss passive samplers as a simple and economic surrogate of direct air sampling. Altogether 74 samplers at 39 crossroads with traffic lights were placed on the lamp post approximately/=3.5 m above ground. PAHs levels determined in samplers are in range from 828 to 3573 ng/g moss dry weight. The spatial spread of pollution within this range is statistically close to normal distribution with mean value of 2332 ng/g. Variability within and between study areas are rationalized in terms of urban environmental factors. PAHs concentrations profiles across the town have appeared uniform. The dominant compounds are phenantrene, fluoranthene and pyrene. Their contribution is 49-68% of total PAHs burden.     

Polycyclic aromatic hydrocarbons in sediments,pore water and the amphipod Pontoporeia hoyi from Lake Michigan

Polycyclic aromatic hydrocarbon (PAH) concentrations were measured in Pontoporeia hoyi, the most abundant benthic organism in Lake Michigan, and in its associated sediment/pore water matrix. Individual PAH concentrations ranged from 10 ppb to 1 ppm in three sedimentary environments having different levels of organic carbon. Pore water concentrations appeared to be independent of sediment concentrations. P. hoyi bioconcentration factors ranged from approximately 10⁴ to 10⁵ for seven analyzed PAHs. A major fraction of the phenanthrene, fluoranthene and pyrene in P. hoyi appears to come from sediments and pore water, while chrysene and BaP are primarily obtained from water.     

Development of a black carbon-inclusive multi-media model: application for PAHs in Stockholm

A multi-media model was developed for predicting the fate of organic chemicals in the Greater Stockholm Area, Sweden, and applied to selected polycyclic aromatic hydrocarbons (PAHs). Although urban models have been previously developed, this model is novel in that it includes sorption to pyrogenically-derived particles, commonly termed "black carbon" (BC), within the model structure. To examine the influence of BC sorption on environmental fate of PAHs, two versions of the model were generated and run: one in which sorption to BC was included and one in which BC sorption was excluded. The inclusion of BC sorption did not cause any significant variations to air levels, but it did cause an average 20-30% increase in sediment concentrations related to increased sediment solids partitioning. The model also predicted reduced advective losses out of the model domain, as well as chemical potential to diffuse from sediments, whilst total chemical inventory increased. In all cases, the lighter PAHs were more affected by BC inclusion than their heavier counterparts. We advocate the addition of sorption to BC in future multi-media fate and exposure models, which as well as influencing fate will also alter (lower) chemical availability and, thus, wildlife exposure to hydrophobic chemicals. A quantification of the latter was derived with the help of the soot-inclusive model version, which estimated a lowering of dissolved water concentrations between five and >200 times for the different PAHs of this study.     

Contamination by polycyclic aromatic hydrocarbons in the Jiulong River Estuary and Western Xiamen Sea, China

The distribution of 16 polycyclic aromatic hydrocarbons (PAHs) was determined in water, sediment and pore water of the Jiulong River Estuary and Western Xiamen Sea, China. Total PAH concentrations varied from 6.96 to 26.9 microg/l in water, 59-1177 ng/ g dry weight in surficial sediments, and 158-949 microg/l in pore water. The PAHs were present in higher levels in pore water than in surface water, due possibly to higher concentrations of dissolved organic carbon or colloids with which the hydrophobic pollutants were strongly associated. Such a concentration gradient implies a potential flux of pollutants from sediment pore water to overlying water. The levels of PAHs in water and pore water were significantly higher than those found in 1998, suggesting recent inputs of these compounds into the area and re-working of sediment phase. The composition pattern of PAHs in the three phases was dominated by high molecular weight PAHs, in particular 5-ring PAHs. The salinity profile of dissolved PAHs suggested that they all behaved non-conservatively due to deviation from the theoretical dilution line. No correlation was found between PAH concentrations in sediment and those in pore water, and the correlation between the partition coefficients of PAHs and sediment organic carbon content was not significant, suggesting the complexity of the partition behaviour of PAHs. As a result of high PAH concentrations in water and pore water, it is likely that they may have caused mortality to certain exposed organisms.     

Simultaneous monitoring of profiles of polycyclic aromatic hydrocarbons in contaminated air with semipermeable membrane devices and spruce needles

Gaseous emissions of combusted electronic scrap, PVC, carpet and wood were monitored for polycyclic aromatic hydrocarbons (PAHs) by simultaneous use of semipermeable membrane devices (SPMDs) and shoots of spruce needles (Picea abies). It was found that phenanthrene, acenaphthylene and fluorene were the dominating PAHs in all samples. SPMDs and needles mainly sequestered PAH associated with the vapor phase. Particle-bound PAHs were only detected in small amounts, at which the needles tended to uptake more of these compounds in comparison to the SPMDs. Nevertheless, the logarithm of the concentrations of PAHs analyzed in both passive samplers after the same sampling period exhibited a significant linear correlation with correlation coefficients larger than 0.8073. SPMDs and spruce needles can complement each other in passive air sampling for compounds with a preference to the gas phase rather than aerosols.     

Evaluating the role of desorption in bioavailability of sediment-associated contaminants using oligochaetes, semipermeable membrane devices and Tenax extraction

The success of the rapidly desorbing fraction as an available fraction was challenged by using sediment ingesting and non-ingesting oligochaetes (Lumbriculus variegatus) together with passive samplers (semipermeable membrane devices, SPMDs) in accumulation and kinetic modelling exercises for carbon-14 labelled model compounds (pyrene, benzo[a]pyrene and 3,4,3',4'-tetrachlorobiphenyl). Passive samplers clearly produced lower uptake rate constants and steady state factors than either of the oligochaete treatments when residue concentrations were based on animal lipid or total SPMD weight. The rapidly desorbing chemical fractions in sediments did not show a significant relationship with the biota sediment accumulation factors or SPMD accumulation factors. A distinctly better relationship was observed between the accumulation factors and the desorption rate constants. The results support the assumption that desorption plays an important role in bioavailability, although animal behaviour and the diffusional limitations of hydrophobic contaminants in sediment together probably affect the actual available pool.     

Polycyclic aromatic hydrocarbons in ambient air in the Philippines derived from passive sampler with polyurethane foam disk

Passive samplers with polyurethane disks (PUF) were applied in the determination of the concentration of polycyclic aromatic hydrocarbons (PAHs) in ambient air in six residential areas in the Philippines during four simultaneous sampling periods. The uptake profiles of PAHs were determined at one site during one sampling period. Most of the PAHs that were detected in air at concentrations that were significantly higher than their analytical detection limits exhibited a linear uptake trend on the PUF disk. The linear uptake profiles of some high molecular weight (HMW) PAHs were not established and this is attributed to the low concentration of the compounds in air in the gaseous phase. The retention concentrations of phenanthrene-d-10 were determined after depuration in four sampling sites during two sampling periods. The sampling rate for phenanthrene-d-10 was calculated at the linear phase of the uptake using the k_A derived from depuration experiments and the relationship of k_A and sampling rate which was established in a previous passive sampling study. The average sampling rate obtained for phenanthrene d-10 (2.94±0.69 m³ d⁻¹) was applied for derivation of the concentrations of the PAHs in the field samples.The passive sampler with PUF disk and short integration time of 42–56 days is applicable for the derivation of the concentrations of PAHs in ambient air in the Philippines. The concentrations of the organic pollutants derived from the passive sampler showed variability for the six residential areas; reflecting the influence of possible sources of emission of the pollutants at the sites at the different sampling periods. The weather conditions, including the occurrence of a tropical cyclone, increased rainfall and high-relative humidity during the rainy season, had an influence on the concentrations of PAHs derived by the passive sampler.     

Mobile passive samplers: concept for a novel mode of exposure

Integrative passive sampling with devices such as semipermeable membrane devices generally relies on rigs for month-long static exposures in water. We evaluate here whether mobile exposures of passive samplers can provide reliable estimates of dissolved contaminant concentrations. Mobile exposures were obtained by towing samplers fastened to the end of a benthic trawl net. Significant and reproducible absorption of polycyclic aromatic hydrocarbons during 5 h-long deployments was made possible by high sampling rates resulting from high water turbulences during towing at 1.2-1.5 knots. Sampling rates (72-215 L d⁻¹) estimated from the dissipation of performance reference compounds were supported by in situ calibration with samplers exposed for a 30 days in the vicinity of the test site. Higher fluoranthene and pyrene absorption in samplers exposed to the trawling-induced sediment plume could be attributed to desorption from re-suspended sediments. This mode of exposure has the potential to be used in monitoring programmes.     

Influence of a large steel complex on the spatial distribution of volatile polycyclic aromatic hydrocarbons (PAHs) determined by passive air sampling using membrane-enclosed copolymer (MECOP)

Membrane-enclosed copolymer (MECOPs) samplers containing crystalline copolymers of ethylvinylbenzene-divinylbenzene in polyethylene membranes were used to assess the influence of a steel complex on the level and spatial distribution of polycyclic aromatic hydrocarbons (PAHs) in ambient air. MECOPs were deployed at six sites in Pohang, Korea for 37 days (August 9, 2005–September 14, 2005). Fluorene, phenanthrene, anthracene, and fluoranthene were dominant PAHs with the highest contribution of phenanthrene (59%) to the total amount of vapor-phase PAHs. The spatial distribution of total PAHs in the vapor phase ranging from 76 to 1077 ng MECOP⁻¹ and air dispersion modeling suggested that the steel complex was the major PAH source in Pohang. It was revealed that the major wind directions rather than the distance from the steel complex were a significant factor affecting the levels of PAHs at the sampling sites. Finally, we tried to convert MECOP concentrations (ng MECOP⁻¹) to air concentrations (ng m⁻³) with the modified sampling rates (m³ day⁻¹). This study demonstrates again that passive air samplers are useful tools for spatially resolved and time-integrated monitoring of semivolatile organic compounds (SOCs) in ambient air.     

Comparison of techniques for estimating PAH bioavailability: uptake in Eisenia fetida, passive samplers and leaching using various solvents and additives

The aim of this study was to evaluate different techniques for assessing the availability of polycyclic aromatic hydrocarbons (PAHs) in soil. This was done by comparing the amounts (total and relative) taken up by the earthworm Eisenia fetida with the amounts extracted by solid-phase microextraction (SPME), semi-permeable membrane devices (SPMDs), leaching with various solvent mixtures, leaching using additives, and sequential leaching. Bioconcentration factors of PAHs in the earthworms based on equilibrium partitioning theory resulted in poor correlations to observed values. This was most notable for PAHs with high concentrations in the studied soil. Evaluation by principal component analysis (PCA) showed distinct differences between the evaluated techniques and, generally, there were larger proportions of carcinogenic PAHs (4-6 fused rings) in the earthworms. These results suggest that it may be difficult to develop a chemical method that is capable of mimicking biological uptake, and thus estimating the bioavailability of PAHs.     

Activated carbon amendment to sequester PAHs in contaminated soil: a lysimeter field trial

Activated carbon (AC) amendment is an innovative method for the in situ remediation of contaminated soils. A field-scale AC amendment of either 2% powder or granular AC (PAC and GAC) to a PAH contaminated soil was carried out in Norway. The PAH concentration in drainage water from the field plot was measured with a direct solvent extraction and by deploying polyoxymethylene (POM) passive samplers. In addition, POM samplers were dug directly in the AC amended and unamended soil in order to monitor the reduction in free aqueous PAH concentrations in the soil pore water. The total PAH concentration in the drainage water, measured by direct solvent extraction of the water, was reduced by 14% for the PAC amendment and by 59% for GAC, 12 months after amendment. Measurements carried out with POM showed a reduction of 93% for PAC and 56% for GAC. The free aqueous PAH concentration in soil pore water was reduced 93% and 76%, 17 and 28 months after PAC amendment, compared to 84% and 69% for GAC. PAC, in contrast to GAC, was more effective for reducing freely dissolved concentrations than total dissolved ones. This could tentatively be explained by leaching of microscopic AC particles from PAC. Secondary chemical effects of the AC amendment were monitored by considering concentration changes in dissolved organic carbon (DOC) and nutrients. DOC was bound by AC, while the concentrations of nutrients (NO(3), NO(2), NH(4), PO(4), P-total, K, Ca and Mg) were variable and likely affected by external environmental factors.     

Source apportionment of polycyclic aromatic hydrocarbons in surface sediments of the Bohai Sea, China

A total of 112 surface sediment samples covering virtually the entire Bohai Sea were analyzed for polycyclic aromatic hydrocarbons (PAHs), in order to provide the extensive information of recent occurrence levels, distribution, possible sources, and potential biological risk of these compounds in this area. Surface sediment samples were collected from the Bohai Sea using a stainless steel grab sampler. Sixteen PAHs were determined by a Finnigan TRACE DSQ gas chromatography/mass spectrometry. Diagnostic ratios, cluster analysis, and principal component analysis (PCA) with multivariate linear regression (MLR) were performed to identify and quantitatively apportion the major sources of sedimentary PAHs in the Bohai Sea. Concentrations of total PAHs in the Bohai Sea ranged widely from 97.2 to 300.7 ng/g (mean, 175.7?±?37.3 ng/g). High concentrations of PAHs were found in the vicinity of Luan River Estuary-Qinhuangdao Harbor, Cao River Estuary-Bohai Sea Center, and north of the Yellow River Estuary. The three-ring PAHs were most abundant, accounting for about 37?±?5 % of total PAHs. The four-ring and five-ring PAHs were the next dominant ones comprising approximately 29?±?7and 23?±?3 % of total PAHs, respectively. Concentrations of acenaphthylene, acenaphthene, and dibenz[a,h]anthracene are higher than Canadian interim marine sediment quality guideline values at most of the sites in the study area. Contamination levels of PAHs in the Bohai Sea were low in comparison with other coastal sediments in China and developed countries. The distribution pattern of PAHs and source identification implied that PAH contamination in the Bohai Sea mainly originates from petrogenic and pyrogenic sources. Further PCA/MLR analysis suggested that the contributions of spilled oil products (petrogenic), coal combustion, and traffic-related pollution were 39, 38, and 23 %, respectively. Pyrogenic sources (coal combustion and traffic-related pollution) contributed 61 % of anthropogenic PAHs to sediments, which indicates that energy consumption could be a dominant factor in PAH pollution in this area. Acenaphthylene, acenaphthene, and dibenz[a,h]anthracene are the three main species of PAHs with more ecotoxicological concern in the Bohai Sea.     

The levels of PAHs and aryl hydrocarbon receptor effects in sediments of Taihu Lake,China

A total of 16 priority polycyclic aromatic hydrocarbons (PAHs) in sediment samples from Taihu Lake were analyzed by instruments, and sediment extracts were assayed for aryl hydrocarbon receptor (AhR)-mediated ethoxyresorufin-o-deethylase (EROD) induction using a rat hepatoma cell line (H4IIE). The cause–effect relationship between the observed EROD activity and chemical concentrations of PAHs was examined. Our results showed that sediment extracts could induce significant AhR effects, and the bioassay-derived 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents of raw extracts (TEQ_bios) ranged from 2.7 to 39.8 pg g^?1 dw. Chemical analysis showed that 16 PAHs were all detected in all samples, and their total concentrations (Σ₁₆PAHs) ranged from 179.8 to 1,669.4 ng g^?1 dw. The abundance of sedimentary PAHs in the three regions (Meiliang Bay, Gonghu Bay, and Xukou Bay) showed a decreasing trend from the inflow region to the outflow region. Chemical analysis-derived TEQs (TEQ_cals) contributed by PAHs ranged from 1.6 to 20.7 pg g^?1 dw. The mean contribution rates (CRs) of PAHs to TEQ_bios were 48.9 %. In Meiliang Bay, EROD effects of 60 % samples were caused by PAHs whose CRs were more than 60 %, while in most sampling sites of Gonghu Bay and Xukou Bay, the CRs of PAHs to TEQ_bios were basically below 40 %. In addition, preliminary ecological risk assessment found that PAHs in sediments have very low ecological impact based on the chemical data of PAHs, while the sediments might pose an unacceptable risk to aquatic organisms and their predators based on the data of TEQ_bio. These findings showed that EROD effects of sediment extracts from Taihu Lake were also caused by other compounds, such as dioxins, polychlorinated biphenyls, etc., together.     

Polycyclic aromatic hydrocarbons in the sediments of the South China Sea

Sixteen sediment samples, collected from the South China Sea, were analyzed for 11 parent polycyclic aromatic hydrocarbons (PAHs) using gas chromatography and gas chromatography-mass spectrometry. Total concentrations of the 11 PAHs studied in the sediments ranged from 24.7 to 275.4 ng/g with a mean of 145.9 ng/g dry sediment. PAH concentrations displayed a consistent distribution trend with the sediment organic carbon content. The linear regression analysis showed that the total concentration of PAHs in the sediment was significantly correlated to the sediment organic carbon content with a correlation coefficient of 0.735 (n=16). Special PAH compound ratios, such as phenanthrene/anthracene and fluoranthene/pyrene, were calculated to evaluate the relative importance of different origins. The collected data showed that pyrolytic input from anthropogenic combustion processes was predominant at almost all the stations investigated. Only one station, located in the proximity of oil wells, appeared to be contaminated predominantly by petrogenic input. Three anthropogenic PAHs, i.e. pyrene, benzo[a]pyrene and benzo[e]pyrene, exhibited similar distribution patterns in the studied area, implying that these compounds possess identical sources. However, perylene did not entirely follow the distribution trend of the three PAHs, suggesting that the sediment perylene probably derived from other sources such as in situ biogenic origins. Dibenzothiophene, a sulfur heterocyclic aromatic compound, was also measured in this study.     

Gas- and particle-phase distribution of polycyclic aromatic hydrocarbons in two-stroke, 50-cm3 moped emissions

Gas- and particle-phase polycyclic aromatic hydrocarbons (PAHs) concentrations evaluated in the exhaust of 10 two-stroke, 50-cm³ mopeds belonging to three different levels of emission legislation (EURO-0, EURO-1 and EURO-2) were used to assess the prevalent mechanism driving the gas/particle partitioning of PAHs in moped exhaust. Sampling was performed on a dynamometer bench both during the “cold-start” and the “hot” phases of the ECE-47 driving cycle. Gas and particulate phase PAHs were collected on polyurethane foam (PUF) plugs and 47-mm Pallflex T60A20 filters, respectively, under isokinetic conditions by using sampling probes inserted into the dilution tunnel of a Constant Volume Sampling – Critical Flow Venturi (CVS–CFV) system.The results show that semi-volatile PAHs were predominantly partitioned to the particle phase. The soluble organic fraction (SOF) of the collected particulates ranged between 72 and 98%. Measured total suspended particulate matter normalized partition coefficients (K_p) were predicted within a factor of 3–5 by assuming absorption into the organic fraction according to a model developed by Harner and Bidleman [Harner, T., Bidleman, T.F., 1998. Octanol–air partition coefficient for describing particle/gas partitioning of aromatic compounds in urban air. Environmental Science & Technology 32, 1494–1502.]. This suggests that the gas/particle partitioning in moped exhaust is mainly driven by the high fraction of organic matter of the emitted particles and that absorption could be the main partitioning mechanism of PAHs.     

Contrasting effects of black carbon amendments on PAH bioaccumulation by Chironomus plumosus larvae in two distinct sediments: role of water absorption and particle ingestion

Two sediment matrices with different characteristics were amended with chars from different sources for bioaccumulation assay with filter-feeding Chironomus plumosus larvae. Chars greatly decreased porewater concentrations of PAHs (C_iw) measured using polyethylene devices in sediments. In organic rich sediment matrix-based systems where suspended char particles were absent, PAH concentrations in larvae (C_iB) were significantly correlated with C_iw, and there was no difference in water-based bioaccumulation factors (BAFs) between different treatments, suggesting that water absorption was the main contaminant uptake route for larvae. In organic poor sediment matrix-based systems where suspended char particles were present, poor Pearson correlation between C_iB and C_iw was found, but there was a significant linear increase of BAF values with char contents, which indicated that ingestion of suspended char particles could also be important for PAH bioaccumulation. Therefore, we need to rethink of the effectiveness and risks for the application of black carbon to sediment/soil remediation.     

Passive sampling of ambient, gaseous air pollutants: an assessment from an ecological perspective

During some past two decades there has been a growing interest among air pollution-vegetation effects-scientists to use passive sampling systems for quantifying ambient, gaseous air pollutant concentrations, particularly in remote and wilderness areas. On the positive side, excluding the laboratory analysis costs, passive samplers are inexpensive, easy to use and do not require electricity to operate. Therefore, they are very attractive for use in regional-scale air quality assessments. Passive samplers allow the quantification of cumulative air pollutant exposures, as total or average pollutant concentrations over a sampling duration. Such systems function either by chemical absorption or by physical adsorption of the gaseous pollutant of interest onto the sampling medium. Selection of a passive sampler must be based on its known or tested characteristics of specificity and linearity of response to the chemical constituent being collected. In addition, the effects of wind velocity, radiation, temperature and relative humidity must be addressed in the context of absorbent/adsorbent performance and sampling rate. Because of all these considerations, passive samplers may provide under- or overestimations of the cumulative exposures, compared to the corresponding data from co-located continuous monitors or active samplers, although such statistical variance can be minimized by taking necessary precautions. On the negative side, cumulative exposures cannot identify short-term (相似文献