Uptake of some selected aquatic pollutants in semipermeable membrane devices (SPMDs) and the polar organic chemical integrative sampler (POCIS)

The uptake characteristics of semipermeable membrane devices (SPMDs) and polar organic chemical integrative samplers (POCISs) were examined for mono, di and tributyltin, triphenyltin, pyrene, benzo[a]pyrene, 4-tert-butylphenol, 4-n-nonylphenol, PCBs 77 and 153, PBDE 47, lindane, triclosan and DDT. Exposure in a flow through system continued for 28 days with samplers removed every 7 days in order to study the relevant uptake kinetics. Uptake remained linear for POCISs with sampling rates (Rs) of up to 0.2 L d(-1). For SPMDs uptake varied from linear to approaching equilibrium with Rs values of up to 14 L d(-1). 7 out of 9 results for SPMDs could be explained by an empirical model (nonylphenol and lindane were exceptions). None of the four organo-tin compounds studied were detected in POCISs and only tributyltin was accumulated significantly by SPMDs. The establishment of these sampling rates allows the calculation of time weighted water concentrations for several important contaminants. Using presented methods, sampling rates and exposure conditions, theoretical detection limits for selected compounds by SPMDs were between 11-68 pg L(-1), which is well below the environment quality standard proposed for those compounds that are included in the European Water Framework Directive.     

Organotin compounds in a Norwegian fjord. A comparison of concentration levels in semipermeable membrane devices (SPMDs), blue mussels (Mytilus edulis) and water samples

Monitoring concentrations of organic pollutants in water is essential to predict effects and to initiate preventive steps. Results from the analysis of water samples provide snapshots of a situation, whereas monitoring using semipermeable membrane devices (SPMDs) provides a time-integrated picture of the concentration of pollutants in water. In this investigation, SPMDs, caged mussels and water samples were used to monitor the levels of organotin compounds in the inner Oslofjord, Norway, over a period of 12 weeks. The work-up procedure for the analysis of organotins was optimised, focusing on the clean-up procedure using gel permeation chromatography (GPC). By using several GPC columns, as much as 1 g of triolein could be employed. This reduces the background emission noise on the baseline, leading to an improvement in the detection limits. The main uptake of tributyltin (TBT) in mussels and SPMDs levelled off after 14 days. A longer uptake period was indicated for SPMDs at stations with a high water concentration of TBT (5-10 ng Sn L(-1)) compared with those with a low water concentration of TBT (approximately 1 ng Sn L(-1)). A concentration gradient was observed for water, SPMDs and mussels from the innermost station close to Oslo harbour to the station further out in the fjord, indicating that the three analysed matrices give approximately the same pollution gradient. The bioconcentration factor (BCF) for TBT in mussels was in the range 12-14 000 (wet weight) and, for SPMDs, 10-12 000 (fat). A good correlation with the TBT water concentrations was achieved within a period of 14-30 days of exposure for mussels and after 2-3 months for SPMDs. A good correlation was also found between the TBT concentration in SPMDs and mussels at the end of the experiment. SPMDs can therefore be used to predict concentrations of TBT in both water and mussels.     

The use of semipermeable membrane devices as passive samplers to determine persistent organic compounds in indoor air

In the study reported here semipermeable membrane devices (SPMDs) were used to sample 28 PAHs and 19 PCBs in the gas phase in 15 single-family houses located in an area where domestic wood burning is widespread. Eight of the households used wood burning appliances whereas the others used other systems for residential heating. Most of the studied compounds were found in the houses: the PAHs at levels that were similar to or slightly higher than published SPMD-sampled levels for background or urban sites in Sweden, and the PCBs at levels that were somewhat lower than those recently found in both indoor and outdoor urban locations. A principal component analysis revealed that wood-burning heating systems may contribute to PAHs in indoor air. The sources may be emissions indoors or penetration from outdoors. The convenience of SPMD technology facilitates its use for semi-quantitative screening and monitoring of various persistent organic compounds indoors in dwellings and working environments.     

Performance of semipermeable membrane devices for sampling of organic contaminants in groundwater

Lipid-filled semipermeable membrane devices (SPMDs) are receiving increasing attention as passive, in situ samplers for the assessment of environmental pollutant exposure. Although SPMDs have been successfully used in a variety of field studies in surface waters, only a few studies have addressed their characteristics as groundwater samplers. In this study, the performance of the SPMDs for monitoring organic contaminants in groundwater was evaluated in a pilot field application in an area severely contaminated by chemical waste, especially by chlorinated hydrocarbons. The spatial distribution of hydrophobic groundwater contaminants was assessed using a combination of passive sampling with SPMDs and non-target semiquantitative GC-MS analysis. More than 100 contaminants were identified and semiquantitatively determined in SPMD samples. Along the 6 field sites under investigation, a large concentration gradient was observed, which confirms a very limited mobility of hydrophobic substances in dissolved form in the aquifer. The in situ extraction potential of the SPMD is limited by groundwater flow, when the exchange volume of well water during an exposure is lower than the SPMD clearance volume for the analytes. This study demonstrates that SPMDs present a useful tool for sampling and analyzing of groundwater polluted with complex mixtures of hydrophobic chemicals and provides guidance for further development of passive sampling technology for groundwater.     

Field uptake rates of hydrophobic organic contaminants by semipermeable membrane devices: environmental monitoring considerations

The uptake rates of selected hydrophobic organic contaminants (HOCs) by semipermeable membrane devices (SPMDs)--a polyethylene layflat containing the lipid triolein--were investigated under natural conditions. SPMDs were exposed in three sampling sites (industrial, urban, and agricultural areas) in the Tajo River (Toledo, Spain) for 5, 11 and 20 d. The organochlorine compounds 4,4'-DDT, 4,4'-DDE, alpha-HCH, gamma-HCH, pentachlorobenzene, hexachlorobenzene, and polychlorinated biphenyls (PCBs), and the 16 priority pollutant polycyclic aromatic hydrocarbons (PAHs) were detected in the SPMDs deployed in the three sampling sites. A linear uptake rate was found for DDTs and for 4-Cl- and 5-Cl-substituted PCB congeners in all sampling sites. Concentrations of HCHs (80.3 ng g(-1) SPMD for alpha-HCH and 109 ng g(-1) SPMD for gamma-HCH after 20 d of exposure) increased according to a linear uptake rate in the SPMDs deployed in the sampling site located in the agricultural area. Likewise, a marked increase of total PAH concentration (up to 300 ng g(-1) SPMD after 20 d of exposure) was solely found in the sampling site situated near a thermoelectric power station. Examination of individual PAHs revealed that PAHs with log K(OW) between 4.2 and 5.7 displayed a linear uptake rate over the 20 d of exposure. Water concentrations (ng L(-1)) of HCB (0.80-2.48), lindane (1.30-11.5), 4,4'-DDT (0.61-2.02), 4,4'-DDE (6.89-11.6) and total PAHs (12.0-26.7) estimated by a linear uptake kinetic model were found to be high in comparison with other polluted aquatic systems, and similar to concentrations in other Spanish rivers. Our results suggest that SPMD kinetic uptake studies in the natural environment are recommended for identifying point-pollution sources, and that shorter times of SPMD exposure (approximately 1 week) are desirable to minimize one of the main problems of field SPMD deployment, i.e., the biofouling, which negatively affects the estimation of the dissolved HOC concentrations.     

Monitoring of labile metals in turbid coastal seawater using diffusive gradients in thin-films

Diffusive gradients in thin-films (DGT) have been investigated for in situ monitoring of labile metals in north Australian coastal seawater. Field and experimental data showed that DGT devices provided adequate detection limits, accuracy and precision for monitoring of near-pristine levels of labile Mn, Co, Cu, Cd and Pb when deployed for periods of 3 days. However, Zn could not be adequately determined due to high blank levels. The ratio of DGT-labile to 0.45 microm-filtered metal levels in natural seawater ranged from 0.44-0.63 for Cu but was close to unity for Co and Cd. Elevated levels of suspended particulate matter up to 57.3 mg l(-1) did not have an adverse effect on the performance of DGT.     

Comparison of the use of mussels and semipermeable membrane devices for monitoring and assessment of accumulation of mutagenic pollutants in marine environment in combination with a novel microbiological mutagenicity assay

A novel microbiological mutagenicity assay, based on bioluminescence of a marine bacterium Vibrio harveyi mutant strain, potentially suitable for monitoring and assessment of mutagenic pollution of marine environment, has been described recently. Here, we tested the use of this assay, in combination with either mussels (Mytilus sp.) or semipermeable membrane devices (SPMDs), in assessment of accumulation of mutagens in marine water (samples of Baltic Sea water were tested). Either similar results were obtained in both systems or higher signals in the SPMD-based system were detected, depending on the tested water samples. We conclude that the use of both mussels and SPMDs in combination with the V. harveyi bioluminescence mutagenicity assay is a method suitable for monitoring and assessment of accumulation of mutagenic pollutants in marine environment, but in some cases the SPMD-based system may provide a more sensitive test.     

半渗透膜采样技术监测城市污水处理流程中的难降解有毒有机污染物

应用新型半透膜采样技术（ＳＰＭＤ）,监测某城市污水处理流程中８个点污水中两类难降解有毒有机污染物多氯联苯（ＰＣＢ）和多环芳烃（ＰＡＨ）,同时同地采集水样,气相色谱质谱联机,选择性离子扫描方式对各ＰＣＢ异构体和ＰＡＨ定性定量。与水样液液萃取相比,ＳＰＭＤ采样技术显著提高了分析的准确度。根据测定的采样器中污染物浓度,推算采样期间该点污水中的平均浓度,与瞬间水样分析结果符合程度较好。半透膜采样方法可用于污水处理工艺流程中多氯联苯和多环芳烃污染物的定性和半定量监测     

Analysis of volatile organic compounds (VOCs) in sediments using in situ SPME sampling

A new method of determining the composition of sediment/soil gases and their volatile organic compound (VOC) content is described. VOCs were collected in situ from intertidal sediments in the Menai Strait and surrounding areas. The sampling was performed using a portable sampler comprising a funnel coupled to a SPME fibre. Gases were extracted from the sediments using a small vacuum pump pulling 100 mL min(-1) at atmospheric pressure. Sixty one different compounds were detected in the samples, and their fluxes and concentrations were determined. The compounds were classified into groups: halogenated, sulfur containing compounds, aldehydes, BTEXs (benzene, toluene, ethyl benzene and xylene) and aliphatic hydrocarbons. Results of principal component analysis (PCA) showed that the chemical composition of extracted gas was influenced primarily by sediment type. Muddy anoxic sediments were dominated by halogenated and sulfur containing compounds and sandy sediments had more aldehydes and BTEXs.     

Monitoring urban heavy metal pollution using the House Sparrow (Passer domesticus)

The House Sparrow (Passer domesticus) is one of the most successful birds in the urban environment, and has a global distribution. The present study aims to provide baseline data about metals in sparrows from urban environments in the West Bank and to investigate the possibility of using the House Sparrow to monitor metal pollution in urban environments. Concentrations of Cu, Cd, Pb and Zn were measured in different tissues and organs of male and female juvenile (1-4 weeks old) and adult House Sparrows from the West Bank. Tissues and organs had the following order of metal richness: liver > stomach > bone > lung, feathers > muscles > egg contents, brain > heart > egg shell. Significant correlation coefficients were observed for the concentrations of Cu, Pb, and Zn in the egg shell and for the egg contents. Male and female Sparrows showed no significant differences in their metal concentrations. Adult Sparrows collected from rural areas were found to have significantly less Cu, Pb, and Zn (but not Cd) concentrations than those from urban environments. In order to investigate metal accumulation with age, metal concentrations were plotted against age stage (egg, 1-, 2-, 3-, and 4-week-old juveniles and adults). Significant relationships were observed between age stage and Cu, Pb, and Zn concentrations. The results provide some evidence for the potential of the House Sparrow as a biomonitor for urban heavy metal pollution. However, further issues regarding metal physiological regulation and the correlations between metals in the environment and those in tissues of the House Sparrows have to be addressed before recommending this bird as a biomonitor for urban metal pollution.     

顶空固相微萃取-毛细管气相色谱表面发射火焰光度法测定淡水中有机锡化合物

采用固相微萃取(SPME)技术对河水样品中的丁基锡化合物进行富集后直接用气相色谱分离测定.实验中应用了涂层性质和厚度各不相同的商品纤维,也应用了自制的吸附纤维,将所得结果进行比较,发现100μm聚二甲基硅氧烷涂层萃取各丁基锡化合物的灵敏度及重现性均是最好的.将依此为基础建立的SPME-GC-FPD方法用于河水中有机锡化合物的测定,方法非常灵敏和快速.     

Monitoring of pharmaceutically active compounds on the Guadalquivir River basin (Spain): occurrence and risk assessment

Guadalquivir River (South of Spain) is among the major freshwater sources of the European Atlantic basin. Until now scientific efforts have been focused on contamination by heavy metals and some priority pollutants in Guadalquivir River. However, the presence of "emerging contaminants", such as pharmaceutically active compounds, has not yet been studied. In this work the occurrence and risk assessment of sixteen pharmaceutically active compounds, belonging to different therapeutic groups, in Guadalquivir River during its course through Seville city are reported. Wastewater effluents from four wastewater treatment plants discharging into Guadalquivir River and river water samples were analyzed. All studied pharmaceutically active compounds, except sulfamethoxazole, trimethoprim, estrone and clofibric acid, were detected in effluent wastewaters at concentration levels up to 28.9 μg L(-1). Among the pharmaceutically active compounds found in effluent wastewater, seven were present in Guadalquivir River samples at concentration levels up to 0.75 μg L(-1), which indicated an important dilution from effluent discharge. Environmental risk assessment reveals that potential ecotoxicological risk cannot be expected on Guadalquivir River at measured concentration levels. Only, the lipid regulator gemfibrozil showed a medium risk for the environment. The risk for acute toxic effects in the environment with the current use of active pharmaceutical ingredients is unlikely. However, the results do not rule out the potential for chronic environmental effects.     

Speciation of inorganic arsenic in coastal seawater from Ionian and Tyrrhenian Seas (Sicily, Italy) using derivative anodic stripping chronopotentiometry

The purpose of this paper was to use derivative anodic stripping chronopotentiometry (dASCP) as a sensitive and accurate technique, to determine the concentrations of dissolved As (III) and As (V) in coastal seawater samples from the Straits of Messina, the Ionian and the Tyrrhenian seas, and to investigate the relationship between the anthropogenic activities on the coastal areas and the concentration of dissolved inorganic arsenic in seawaters. The obtained data indicated that As (V) was the most abundant species, with concentration ranging from 26.7 to 307 nM, whereas As (III) levels were lower than 48 nM in all the samples. In particular, As (III) and As (V) levels significantly decreased from high to low anthropogenic activities zones (p < 0.00001, ANOVA), with the reference samples, from a wildlife reserve, showing the lowest values. Furthermore it was observed that human activities influenced inorganic arsenic speciation, since the zones that received high human input presented the highest As(V)/As (III) ratio.     

Monitoring for Lead Pollution using Feathers of Feral Pigeons (Columba livia) from Korea

We investigated lead exposure conditions using unwashed feathers of feral pigeons as a monitor for lead pollution from rural, central urban, and four industrial complex areas in Korea with different ambient lead concentrations. Overall, the lead levels in the feathers increased when the atmospheric lead levels increased, so that the lead levels in the feathers from urban and industrial areas were two to four times greater than those in the rural area. However, there are no significant differences in the liver lead concentrations between rural and the other areas, suggesting that the lead originated from ingestion are not differences in locations. A positive correlation was found between the concentration of lead in livers and feathers from rural, indicating that the feather lead concentrations in this area seem to mainly reflect the internal tissue lead through the metabolic process. However, there are no significant correlations in the other areas, and we observed a relatively higher lead accumulation ratio of feathers to livers. It, therefore, indicates that external contamination onto the feather surface may be an important source for lead levels in feathers rather than transfer from internal tissue lead.     

Study of heavy metal pollution in seawater of Kepez harbor of Canakkale (Turkey)

In this work, the heavy metals cadmium and lead in Kepez harbor were studied with regard to the determination of the environmental pollution levels. Seawater samples of the Dardanelles (Canakkale Strait) were collected from the nearest station to Kepez harbor in July 2007. Then, the concentrations of these metals were determined after simple pretreatment of samples by the proposed inductively coupled plasma?Catomic emission spectrometry (ICP-AES) method. The analysis of a given sample is completed in about 15 min by the ICP-AES method, and the concentrations of Cd and Pb were found to be 73.80 mg L^???1 (relative standard deviation [RSD], 1.07%) and 9.39 mg L^???1 (RSD, 0.70%), respectively. The accuracy of the applied ICP technique was checked by recovery studies, and good recoveries were obtained. The pollution levels of Cd and Pb recorded in this study were compared with those in other studies to analyze the water sample in Kepez harbor.     

Monitoring and validating spatio-temporal dynamics of biogeochemical properties in Mersin Bay (Turkey) using Landsat ETM+

The objective of this study was to devise and validate simple models for estimating spatio-temporal dynamics of seven optically (in)active biogeochemical properties in Mersin Bay using Landsat 7 Enhanced Thematic Mapper Plus (ETM+) data and GIS. Spatio-temporal dynamics of Secchi depth (S (depth)), dissolved oxygen (DO), nitrite nitrogen (NO(2)-N), nitrate nitrogen (NO?-N), silicate (SiO?), 5-day biological oxygen demand (BOD5), and chlorophyll-a (Chl-a) were estimated using best-fit multiple linear regression (MLR) models as a function of Landsat 7 ETM+ and ground data in 2007 and 2008, latitude, longitude, and day of year. Validation of the MLR models against Landsat and ground data in 2005 led to r values ranging from 0.39 for NO?-N (P?=?0.008) to 0.79 for S (depth) (P?相似文献   

Preparation and evaluation of candidate certified reference materials (CRMs) for nutrients in seawater

Certified reference materials (CRMs) are an essential part of the quality assurance (QA) necessary for the reliable analytical measurement of nutrients in seawater. The CRMs currently available for these analyses are not matrix matched to marine samples. QUASIMEME routinely produces test materials for the nutrients in seawater and nutrients in estuarine water and low-salinity open water Laboratory Performance Studies (LPS) that are both homogeneous and stable. QUASIMEME, in conjunction with Eurofins Scientific, Denmark have produced two reference materials (RMs). The homogeneity testing and preliminary stability studies were carried out by QUASIMEME, and the results are presented in this article. Participants of the QUASIMEME LPS who demonstrated satisfactory long-term performance for the analysis of nutrients in seawater and nutrients in estuarine water and low-salinity open water were invited to take part in the certification exercise. Twenty laboratories returned data, a summary of which is also presented. The certification and long-term stability testing and additional data analysis were carried out by Eurofins Scientific, Denmark, and are outwith the scope of this article and not reported here. Eurofins Scientific, Denmark have marketed these RMs as part of their range of VKI Reference Materials (further information is available from eurofins@eurofins.dk).     

Monitoring pollution in Tunisian coasts using a scale of classification based on biochemical markers in worms Nereis (Hediste) diversicolor

This paper aims to assess the marine environment quality along the Tunisian coasts using a statistical approach based on biomarkers response in the polychaete worms Nereis (Hediste) diversicolor. Worms were collected from six sites: Bizerta Lagoon, Gargour, Nakta, Mahres, Skhira and from Teboulba considered as a reference site. The biomarkers selected in this work were (1) the activities of cytochrome P450-dependent NADPH cytochrome c reductase (NADPH red) as phase I enzyme, (2) glutathione S-transferase as phase II enzyme and (3) the acetylcholinesterase activity as neurotoxicity marker. Oxidative stress was evaluated using catalase activity and malondialdehyde accumulation. For each biomarker, a discriminatory factor was calculated and a response index was allocated. For each site, a multi-marker pollution index was calculated as the sum of the response index of each of the five more discriminating biomarkers. The results show differences between sites compared with the reference samples. The multi-marker approach confirms that worms from Bizerta and Mahress have been submitted to highly polluted environment. Mahress shows the highest multi-marker pollution index, indicating a highly contamination status.     

Monitoring and modeling of disinfection by-products (DBPs)

In the United States, the newly promulgateddisinfectant/disinfection by-product (D/DBP) regulationsforce water treatment utilities to be more concerned withfinished and distributed water qualities. In this study,monitoring of DBP formation was conducted from three Frenchwater treatment plants trying to assess DBP variationsthrough time and space. Compared to the in-plant totaltrihalomethanes (TTHM) levels, TTHM levels in thedistribution system increased from less than 150% to morethan 300%. Significant variations for TTHM and bromate(BrO₃ ^-) levels throughout the seasons were alsoobserved; generally higher levels in the summer and lowerlevels in the winter. Combining chemical DBP models(empirical power functional models) and hydraulicsimulations, DBPs including TTHM and BrO₃ ^- weresuccessfully simulated from the full-scale monitoring data,indicating that empirical DBP model can be a potential toolto access DBP formation in actual plants. This study alsoprovides the protocols to assess DBP simulations in thewater treatment systems.     

运用热脱附/GC/MS分析研究室内空气中TVOC浓度及种类分布

利用热脱附/GC/MS联用技术定性、定量(半定量)分析了多组有代表性的室内空气样品。结果表明,室内空气挥发性有机气体的主要成分是苯系物、烃类、醛酮类、酯类等;装修后3个月内的家居室内空气中的苯25%超标,甲苯58%超标,二甲苯79%超标,TVOC 100%超标;一年后,仅TVOC还有11%的超标。办公室情况类似。