Polycyclic aromatic hydrocarbon sampling in wastewaters using semipermeable membrane devices: accuracy of time-weighted average concentration estimations of truly dissolved compounds

Semipermeable membrane devices (SPMDs) previously spiked with performance reference compounds were exposed in wastewater. After 6 days of exposure, 13 polycyclic aromatic hydrocarbons (PAHs) were quantified in SPMDs. Exchange rate constants and time-weighted average (TWA) concentrations of SPMD-available PAHs in water were calculated. The bias of using SPMDs to estimate an actual TWA concentration if the concentration in water fluctuates, as can be expected in wastewater, was studied with numerical simulations. The bias increased with the exchange rate constant. However, most exchange rate constants evaluated in SPMDs exposed in wastewater were small enough for SPMDs to estimate a TWA concentration of PAHs even when the water concentration varied. TWA-SPMD-available concentrations were always below total dissolved (operationally defined as 0.7 microm) concentrations, indicating that part of the dissolved PAHs was not available for sampling. In situ partitioning coefficients K(DOC) were computed and found to be slightly higher than data from the literature. This confirms that only truly dissolved PAHs should be sampled by SPMDs in wastewater.     

Use of semipermeable membrane devices (SPMDs)

Triolein-containing semipermeable membrane devices (SPMDs) were employed as passive samplers to provide data on the bioavailable fraction of organic, waterborne, organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polynuclear aromatic hydrocarbons (PAHs) in streams flowing through a highly polluted industrial area of Bitterfeld in Saxony-Anhalt, Germany. The contamination of the region with organic pollutants originates in wastewater effluents from the chemical industry, from over one-hundred years of lignite exploitation, and from chemical waste dumps. The main objective was to characterise time-integrated levels of dissolved contaminants, to use them for identification of spatial trends of contamination, and their relationship to potential pollution sources. SPMDs were deployed for 43 days in the summer of 1998 at four sampling sites. The total concentration of pollutants at sampling sites was found to range from a low of 0.8 microgram/SPMD to 25 micrograms/SPMD for PAHs, and from 0.4 microgram/SPMD to 22 micrograms/SPMD for OCPs, respectively. None of the selected PCB congeners was present at quantifiable levels at any sampling site. A point source of water pollution with OCPs and PAHs was identified in the river system considering the total contaminant concentrations and the distribution of individual compounds accumulated by SPMDs at different sampling sites. SPMD-data was also used to estimate average ambient water concentrations of the contaminants at each field site and compared with concentrations measured in bulk water extracts. The truly dissolved or bioavailable portion of contaminants at different sampling sites ranged from 4% to 86% for the PAHs, and from 8% to 18% for the OCPs included in the estimation. The fraction of individual compounds found in the freely dissolved form can be attributed to the range of their hydrophobicity. In comparison with liquid/liquid extraction of water samples, the SPMD method is more suitable for an assessment of the background concentrations of hydrophobic organic contaminants because of substantially lower method quantification limits. Moreover, contaminant residues sequestered by the SPMDs represent an estimation of the dissolved or readily bioavailable concentration of hydrophobic contaminants in water, which is not provided by most analytical approaches.     

Acute toxicity and genotoxicity of aquatic hydrophobic pollutants sampled with semipermeable membrane devices

Triolein-filled semipermeable membrane devices (SPMDs) were deployed for 4 weeks in polluted water sources in Lithuania. The mixtures of pollutants sampled by the SPMDs were fractionated by size-exclusion chromatography (SEC). The fraction containing average molecular weight compounds such as polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides was screened by gas chromatography and mass spectrometry. The whole (non-fractionated) samples and their SEC fractions were tested in bioassays including Microtox, Mutatox, Daphnia pulex immobilization assay and the sister chromatid exchange (SCE) in human lymphocytes in vitro test. The Microtox test was most sensitive with the estimated EC(50) values in the range of milligrams or even micrograms per milliliter based on the amount of the SPMD triolein. Part of the observed toxicity was caused by elemental sulfur co-sampled by the SPMDs from sediments. The sum of toxicity equivalents of the SEC fractions was smaller than the relative toxicity of the whole samples indicating the presence of synergistic interactions in the complex mixtures of chemical pollutants. The toxic or genotoxic response induced by the chemical mixtures and their fractions was smaller in the D. pulex, Mutatox and SCE tests. In Mutatox, a positive response was only detected without the S9 metabolic activation which indicates the presence of mainly direct-acting mutagens in the samples. Interpretation of the Mutatox data was difficult due to the complexity of dose-response and time-response relationships. The study has demonstrated the potential as well as some limitations of SPMDs in the monitoring of biological effects of bioavailable organic pollutants in the aquatic environment.     

Application of semipermeable membrane device (SPMD) to assess air genotoxicity in an occupational environment

Semipermeable membrane device (SPMD) is a passive sampler that sequesters lipophilic contaminants, mimicking the bioconcentration in the fatty tissue of organisms. This study was designed to assess the use of SPMD and biological tests (Comet assay and Ames test) for air monitoring. For this purpose an occupational environment with expected polycyclic aromatic hydrocarbons (PAHs) contamination (coke plant) was selected for a case study. The SPMDs were deployed in five occupational contaminated sites and in a control site. The SPMD dialysates were chemically analysed and examined for in vitro DNA-damaging activity in human cells (Jurkat) by Comet assay and for mutagenicity with the Ames test (TA98 strain, w/o S9). Total suspended particulates were also collected and analysed (GC–MS). No biological effect of SPMD extract was revealed in the control site. On the other hand, air samples collected with SPMDs within the coke plant showed variable degrees of genotoxic and mutagenic activity. The highest effects were associated with the highest PAH level recovered in the SPMDs extracts and in particulate samples.Results obtained support the sensitivity of biological tests associated to SPMD sampling for evaluating the health risk of potentially contaminated work environments highlighting the usefulness of SPMDs for environmental air quality monitoring.     

In situ monitoring of urban air in Southern Italy with the Tradescantia micronucleus bioassay and semipermeable membrane devices (SPMDs)

This study was designed to assess toxic and genotoxic compounds in the urban air of Caserta, South Italy using cuttings from the plant Tradescantia #4430. In situ monitoring of gaseous pollutans was made at 17 sampling points in two seasons of the year. Genotoxicity was evaluated by recording the micronuclei in meiotic pollen mother cells (Trad-MCN assay). In addition, the passive sampler semipermeable membrane devices (SPMDs) were deployed at the sampling points with a significant increase in micronuclei frequency. SPMDs concentrated priority organic pollutants were identified by high performance liquid chromatography and gas chromatography, while toxicity and mutagenesis were assessed on the bacterium Vibrio fischeri using the Microtox and Mutatox systems respectively. Significant toxic and mutagenic effects were observed at different points on the town grid and SPMDs effectively concentrated trace contaminants. The relationship between what was present in the air sampled by SPMDs and the micronuclei frequency was also explored.     

Photodegradation of polyaromatic hydrocarbons in passive air samplers: field testing different deployment chambers

Semi-permeable membrane devices (SPMDs) were loaded with deuterated anthracene and pyrene as performance reference compounds (PRCs) and deployed at a test site in four different chambers (open and closed box chamber, bowl chamber and cage chamber) for 29 days. The losses of PRCs and the uptake of polyaromatic hydrocarbons (PAHs) from the ambient air were quantified. UV-B levels measured in each deployment chamber indicated that SPMDs would be exposed to the most UV-B in the cage chamber and open box chamber. Significantly less PAHs were quantified in SPMDs deployed in the cage chamber and open box chamber compared to samplers from the other two chambers, suggesting that photodegradation of PAHs had occurred. The loss of PRCs confirmed these results but also showed that photodegradation was occurring in the closed box chamber. The bowl chamber appears to provide the best protection from the influence of direct photodegradation.     

Use of semi-permeable membrane devices to monitor pollutants in water and assess their effects: a laboratory test and field verification

Uptake of eight pesticides of different classes (organochlorines, synthetic pyrethroids, dinitroanilines, amides) by semi-permeable membrane devices (SPMDs) was studied in a laboratory continuous-flow system. After 20 days of exposure, membrane concentration factors were in the range of 50 000-120 000 for all the analytes except for the amide herbicides propachlor and alachlor, which were not detected in any of the SPMDs. The kinetic data and mathematical models were used to calculate analyte uptake rate constants, SPMD lipid/water partition coefficients, average sampling rates and concentrations of the pesticides in water. To assess the effects of concentrated pesticides, standard bioassays (Salmonella/histidine reversion assay and bioluminescence inhibition in Vibrio fischeri test) were incorporated in the SPMD technique. To test the method in an environmental situation, SPMDs were deployed in polluted sites in Lithuania. Polynuclear aromatic hydrocarbons were the major pollutants detected in the SPMDs deployed in the field. All the SPMD dialysates were highly toxic in the bioluminescence inhibition test but no mutagenic activity was observed in the Salmonella/histidine reversion assay.     

Distribution of polycyclic aromatic hydrocarbons in surface water and sediment near a drinking water reservoir in Northeastern China

The levels of polycyclic aromatic hydrocarbons (PAHs) in the water and the sediment samples collected near the Mopanshan Reservoir—the most important drinking water resource of Harbin City in Northeast China—were examined. A total of 16 PAHs were concurrently identified and quantified in the three water bodies tested (Lalin River, Mangniu River, and Mopanshan Reservoir) and in the Mopanshan drinking water treatment plant during the high- and low water periods. The total PAH concentrations in the water and sediment samples ranged from 122.7 to 639.8 ng/L and from 89.1 to 749.0 ng/g dry weight, respectively. Similar spatial and temporal trends were also found for both samples. The lowest Σ₁₆PAH concentration of the Mopanshan Reservoir was obtained during the high water period; by contrast, the Lalin River had the highest concentration during the low water period. The PAH profiles resembling the three water bodies, with high percentages of low-molecular weight PAHs and dominated by two- to three-ring PAHs (78.4 to 89.0 %). Two of the molecular indices used reflected the possible PAH sources, indicating the main input from coal combustion, especially during the low water period. The conventional drinking water treatment operations resulted in a 20.7 to 67.0 % decrease in the different-ringed PAHs in the Mopanshan-treated drinking water. These findings indicate that human activities negatively affect the drinking water resource. Without the obvious removal of the PAHs in the waterworks, drinking water poses certain potential health risks to people.     

Nonylphenolic compounds in drinking and surface waters downstream of treated textile and pulp and paper effluents: a survey and preliminary assessment of their potential effects on public health and aquatic life

Eleven drinking water treatment plants, located downstream of textile plants or pulp and paper mills, have been sampled monthly during a year for the analysis of 17 nonylphenol ethoxylates (NP1-17EO) and two nonylphenoxycarboxylic acids (NP1-2EC). At all but one plant, results in the drinking water, for the sum of these 19 substances, range between below detection levels and 6.7 microg/l. Annual means are between 0.02 and 2.8 microg/l. At the other plant, the yearly average concentration is 10.4 microg/l and the monthly maximum is 43.3 microg/l. In the surface (pre-treatment) water, the annual mean concentrations of the 11 plants range between 0.14 and 17.8 microg/l and the recorded instantaneous maximum is 55.3 microg/l. According to Canadian health authorities, drinking water is a negligible route of human exposure to nonylphenolic compounds, even at the highest concentrations found in this study. After transformation of the data into nonylphenol equivalents, about 20% of the surface water samples exceed the Canadian 1 microg/l nonylphenol water quality guideline for the protection of aquatic life. Some results also exceed Québec's 6 microg/l nonylphenol guideline. The efficiency of the plants in removing nonylphenolic compounds from drinking water is highly variable, ranging from 11% to 99%.     

Monitoring PAHs in the Brisbane River and Moreton Bay, Australia, using semipermeable membrane devices and EROD activity in yellowfin bream, Acanthopagrus australis

Two water quality monitoring strategies designed to sample hydrophobic organic contaminants have been applied and evaluated across an expected concentration gradient in PAHs in the Moreton region. Semipermeable membrane devices (SPMDs) that sequester contaminants via passive diffusion across a membrane were used to evaluate the concentration of PAHs at four and five sites in spring and summer 2001/2002, respectively. In addition, induction of hepatic cytochrome P4501, EROD activity, in yellowfin bream, Acanthopagrus australis, captured in the vicinity of SPMD sampling sites following deployment in summer was used as a biomarker of exposure to PAHs and related chemicals. SPMDs identified a clear and reproducible gradient in PAH contamination with levels increasing from east to west in Moreton Bay and upstream in the Brisbane River. The highest PAH concentrations expressed as B(a)P-toxicity equivalents (TEQs) were found in urban areas, which were also furthest upstream and experienced the least flushing. Cytochrome P4501 induction in A. australis was similar at all sites. The absence of clear trends in EROD activity may be attributable to factors not measured in this study or variable residency time of A. australis in contaminated areas. It is also possible that fish in the Moreton region are displaying enzymatic adaptation, which has been reported previously for fish subjected to chronic exposure to organic contaminants. These potential interferences complicate interpretation of EROD activity from feral biota. It is, therefore, suggested that future monitoring combine the two methods by applying passive sampler extracts to in vitro EROD assays.     

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.     

Impact of chemical oxidation on soil quality

Oxidation treatment helps to reduce the polycyclic aromatic hydrocarbon (PAH) load in contaminated soils but it may also have an effect on the soil quality. The impact of permanganate and Fenton oxidation on soil quality is investigated. Soil quality is restricted here to the potential for plant growth. Soil samples were collected from an agricultural field (S1) and a former coking plant (S4). Agricultural soil was spiked with phenanthrene (PHE) and pyrene (PYR) at two concentrations (S2: 700 mg PHE kg⁻¹, S3: 700 mg PHE kg⁻¹ and 2100 mg PYR kg⁻¹). Soils were treated with both oxidation processes, and analyzed for PAHs and a set of agronomic parameters. A plant germination and growth test was run with rye-grass on treated soils. Results showed that both treatments produced the expected reduction of PAH concentration (from 64% to 97%). Besides, a significant loss of organic C and N, and strong changes in available nutrients were observed. Permanganate treatment increased the specific surface area and the cation exchange capacity in relation to manganese dioxide precipitation, and produced a rise in pH. Fenton oxidation decreased soil pH and increased the water retention capacity. Plant growth was negatively affected by permanganate, related to lower soil permeability and aeration. Both treatments had an effect on soil properties but Fenton oxidation appeared to be more compatible with revegetation.     

Reproductive toxicity assessment of surface water of the Tai section of the Yangtze River, China by in vitro bioassays coupled with chemical analysis

Reproductive toxicity of organic extracts of the surface water from the Tai section of the Yangtze River was assessed by in vitro cytotoxity assays and selected persistent organic pollutants including PCBs, OCPs and PAHs were quantified by instrumental analysis. Eleven of the US EPA priority PAHs were detected. Individual PAHs were found to range from 0.7 to 20 ng/L. Concentrations of BaP did not exceed the national drinking water source quality standard of China. However, a 286-fold concentrated organic extract induced significant reproductive toxicity in adult male rats. The morphology of cells, MTT assay and LDH release assay were all affected by exposure to the organic extracts of water. The results of the reproductive toxicity indicated that PAHs posed the greatest risk of the chemicals studied. The compounds present in the water could be bioconcentrated and result in adverse effects.     

The identification of readily bioavailable pollutants in lake shkodra/skadar using semipermeable membrane devices (SPMDs), bioassays and chemical analysis

GOAL, SCOPE AND BACKGROUND: Lake Shkodra/Skadar is the largest lake in the Balkans region and located on the border between Albania to the south and Montenegro to the north. Because of the wide range of endemic, rare or endangered plant and animal species it supports, Lake Shkodra/Skadar and its extensive associated wetlands are internationally recognised as a site of significance and importance (Ramsar site). In recent years, social and economic changes in both Albania and Montenegro have lead to unprecedented levels of urban and industrial effluent entering the lake. Of particular concern is the increasing input of toxic hydrophobic organic pollutants (HOPs) into the lake and the degree to which these compounds are available for uptake by aquatic biota. Semipermeable membrane devices (SPMDs) have been shown to sample the readily bioavailable fraction (dissolved phase) of waterborne HOPs and in doing so provide relevant data for exposure assessment. The aim of the current study was to use SPMD-based sampling in conjunction with appropriate bioassays and chemical analysis to identify readily bioavailable HOPs in the lake. METHODS: SPMDs were constructed and deployed at three sites in the Albanian sector and three sites in the Montenegrin sector of Lake Skadar/Shkodra for 21 days. Following the dialytic recovery of target analytes and size exclusion chromatographic clean-up, aliquots of SPMD samples were subjected to GC-MS scan analysis for major components, GC-MS SIM analysis for 16 priority pollutant polycyclic aromatic hydrocarbons (PP-PAHs) and assayed for EROD-inducing, estrogenic and mutagenic potential using rainbow trout liver cells (RTL-W1), the yeast estrogen screen (YES) and the Ames Test, respectively. RESULTS AND DISCUSSION: A total of 39 compounds were tentatively identified in SPMD samples from the six sampling sites. Alkylated PAHs were the most abundant and ubiquitous compounds present along with various sterols and sterol derivatives. Numerous other compounds remain unidentified. 15 of the 16 targeted PP-PAHs were present in samples from one or more of the sampling sites indicating these compounds are both readily bioavailable and widely distributed in Lake Shkodra/Skadar. Total PP-PAH concentrations ranged between 3991 ng/SPMD and 10695 ng/SPMD. Bioassays carried out on SPMD samples revealed significant EROD-inducing and estrogenic potential at five of the six sampling sites indicating toxicologically relevant compounds are readily available for uptake by resident aquatic biota. EROD-inducing potential was positively correlated with targeted PP-PAH concentration (r2 = 0.74). However, comparison of bioassay- and analytically-derived toxicity equivalents revealed targeted PP-PAHs were responsible for less than 0.06% of the total EROD-inducing potential. CONCLUSIONS AND OUTLOOK: The combination of SPMD-based sampling with appropriate bioassays and chemical analysis provided an effective tool for the identification of environmentally relevant waterborne pollutants in Lake Shkodra/Skadar. Our results show that toxicologically relevant HOPs including EROD-inducing and potentially estrogenic compounds are widely distributed in the lake and readily available for uptake by aquatic biota. Our results also suggest that alkylated PAHs rather than parent compounds may be of greater toxicological relevance in the lake. As anthropogenic influences continue to increase, SPMD-based sampling is expected to play a central role in future research concerned with the identification, monitoring and assessment of the risk posed by HOPs to Lake Shkodra/Skadar's aquatic biota.     

自然水体中主要有毒有机物的研究进展

介绍了主要有毒有机物多环芳烃(PAHs)、多氯联苯(PCBs)、有机氯农药(OCPs)在环境中的危害及其来源,着重评述了近年来中国自然水体中和沉积物中该类污染物的研究进展,指出新的检测技术的开发、有毒有机物的生殖毒性和生态环境风险影响方法学的研究及污染区域污染控制、消减及修复是今后该领域的工作重点.     

A comparison of polycyclic aromatic hydrocarbon and petroleum hydrocarbon uptake by mussels (Perna viridis) and semi-permeable membrane devices (SPMDs) in Hong Kong coastal waters

The ability of mussels (Perna viridis) and semi-permeable membrane devices (SPMDs) to accumulate polycyclic aromatic hydrocarbons (PAHs) and petroleum hydrocarbons (PHCs) from five sites in Hong Kong's coastal waters was compared. Mussels consistently had higher levels of contaminants, but their utility was limited at one highly polluted site due to mortality. Mussels and SPMDs ranked sites differently in terms of individual contaminant levels. Although SPMDs overcome many of the disadvantages of using living organisms to measure contaminants in marine waters, they cannot be used as "mimics" due to different PAH and PHC accumulation patterns.     

PAHs and nitrated PAHs in air of five European countries determined using SPMDs as passive samplers

The gas phase polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs in the atmosphere of five European countries (Austria, the Czech Republic, Poland, Slovakia and Sweden) were measured simultaneously during two 21-day passive sampling campaigns using semipermeable membrane devices (SPMDs). SPMD samplers, consisting of a pair of SPMDs covered by a metal umbrella, were deployed at 40 locations ranging from remote and rural to urban and industrial, at a similar time during each of the two sampling campaigns (autumn 1999, except in Poland, winter 1999, and summer 2000). The total amounts of PAHs and nitro-PAHs found in the SPMDs ranged between 5.0–1.2×10³ and 1.1×10⁻³–4.0 ng SPMD⁻¹ day⁻¹, respectively. The measured environmental sampling conditions were similar between sites and, thus, the variations in the SPMD data reflected the spatial differences in gas phase concentrations of nitro-PAHs and PAHs within and between countries. The gas phase concentrations of nitro-PAHs and PAHs found in East Europe (Slovakia, the Czech Republic and Poland 1999) were 10 times higher than those measured in Sweden, Austria and Poland in 2000. In each country, the levels of PAHs and nitro-PAHs differed by one–three orders of magnitudes amongst sampling sites. The highest within-country spatial differences were found in Poland where levels of PAHs and nitro-PAHs were about one and two orders of magnitudes, respectively, higher in winter 1999 than in summer 2000, probably due to increasing emissions of coal combustion for residential heating. Differences in PAH-patterns between sites were visualized by the multivariate projection method, principal component analysis (PCA). However, no specific source patterns were found, probably since imissions rather than emissions were measured, so the PAHs detected at many sites originated from multiple sources.     

Assessment of bioavailable PAH, PCB and OCP concentrations in water, using semipermeable membrane devices (SPMDs), sediments and caged carp

Bioavailable water concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed at several freshwater sites in and around the city of Amsterdam. Carp (Cyprinus carpio) were caged for 4 weeks at 10 sites, together with semipermeable membrane devices (SPMDs). In addition, sediment samples were taken at each site. SPMDs and sediments were analysed for PAHs, PCBs and OCPs. Carp muscle tissues were analysed for PCBs and OCP, while PAH metabolites were assessed in fish bile. Contaminant concentrations in the water phase were estimated using three different methods: 1. Using fish tissue concentrations and literature bioconcentration factors (BCFs), 2. Using SPMD levels and a kinetic SPMD uptake model, and 3. Using sediment levels and literature sorption coefficients (K_ocs). Since PAH accumulation in fish is not considered an accurate indicator of PAH exposure, calculated aqueous PAH concentrations from SPMD data were compared with semiquantitatively determined biliary PAH metabolite levels. Contaminant concentrations in the water phase estimated with fish data (Cw_fish) and SPMD data (Cw_spmd) were more in line for compounds with lower K_ow than for compounds with higher K_ow values. This indicates that the assumption of fish–water sorption equilibrium was not valid. At most sites, sediment-based water levels (Cw_sed) were comparable with the Cw_spmd, although large differences were observed at certain sites. A significant correlation was observed between biliary PAH metabolite levels in fish and aqueous PAH concentrations estimated with SPMD data, suggesting that both methods may be accurate indicators of PAH exposure in aquatic ecosystems.     

Pollution survey of polycyclic aromatic hydrocarbons in surface water of Hangzhou, China

The concentrations of 10 polycyclic aromatic hydrocarbons (PAHs) were simultaneously measured for five times (July and November 1999–2002) in four water bodies of Hangzhou, China. To investigate possible sources of PAH contamination, sediments, soils, runoff water and atmospheric particles of the region were also analyzed for their PAH contents. The maximum levels of PAHs in the water bodies (34.4–67.7 μg/l) were found in July, while significantly lower PAH concentrations (4.7–15.3 μg/l) were measured in November. The contamination is substantial and it may have resulted in acute toxic effects on aquatic organisms. The measured PAH concentrations in sediments and soils (224–4222 ng/g), runoff water (8.3 μg/l) and air particles (2.3 μg/m³) are discussed in relation to concentrations and patterns found in the surface water bodies. Comparison of PAH levels in sediments and soils led to the conclusion that the erosion of soil material does not contribute significantly to the contamination of sediments. The atmospheric PAH deposition to water bodies in the city area of Hangzhou was estimated to be 530 tons/a, while the contribution of surface runoff water was estimated to be 30.7 tons/a. The ratios of selected PAH were then used to illuminate the possible origin of PAHs in the examined samples (petrogenic, pyrogenic).     

Levels of persistent organic pollutants in the Neretva River (Bosnia and Herzegovina) determined by deployment of semipermeable membrane devices (SPMD)

The main objective of this study was to determine levels of certain persistent organic pollutants (POPs) in Neretva River, Bosnia and Herzegovina (BiH), which is currently facing implementation of the Stockholm Convention on persistent organic pollutants (POPs) and environmental protection strategies. This is the very first report on the deployment of semipermeable membrane devices (SPMDs) in BiH. SPMDs were used for continuous 3-weeks sampling of POPs at three locations, covering 220 km long stream of the Neretva River. Water concentrations of polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs) and polybrominated diphenylethers (PBDEs) were calculated using performance reference compounds (PRCs). The total OCP concentrations ranged from 40 to 140 pg L^?1 and most of compounds were detected only in lower course of the river. Total PAH ranged from 160 to 4000 pg L^?1 and show a clear spatial variation. Dominant PAHs were phenanthrene, fluoranthene, fluorene and acenaphthene. Total PCB ranged from undetectable to 120 pg L^?1. From the group of 15 PBDE congeners investigated, only PBDE-47 and PBDE-99 were detected. Since the concentrations of broad spectrum of POPs found in the Neretva River are quite low, future actions should be focused on preservation rather than on sanitation measures. Regular monitoring should anyhow be established.