Simultaneous monitoring of PCDD/Fs and PCBs in contaminated air with semipermeable membrane devices and fresh spruce needles

The contaminated air with burning plastic floor and electronic scrap was monitored with semipermeable membrane devices (SPMDs) and fresh unpolluted spruce needles at the same time for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs). It was found that there were more polychlorinated dibenzofurans (PCDFs) than polychlorinated dibenzo-p-dioxins (PCDDs) collected from contaminated air. The total amounts of PCBs were much higher than that of PCDD/Fs, but the contribution of them to the WHO-TEQ was less than that of PCDD/Fs. Triolein-containing SPMDs can absorb much more PCDD/Fs and PCBs than spruce needles when they were exposed in contaminated air simultaneously. The logarithm of the concentrations of PCDD/Fs and PCBs in SPMDs and in spruce needles at the same sampling time exhibited a significant linear correlation, the correlation coefficients were larger than 0.86 for PCDD/Fs and 0.92 for PCBs. SPMDs and spruce needles are effective passive air sampler for PCDD/Fs and PCBs. SPMDs and spruce needles can complement each other in passive air sampling.     

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.     

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.     

Development of a comprehensive analytical method for the determination of chlorinated paraffins in spruce needles applied in passive air sampling

Conifer needles are used for the monitoring of atmospheric persistent organic pollutants. The objective of the present study was to develop a method for the detection of airborne chlorinated paraffins (CPs) using spruce needles as a passive sampler. The method is based on liquid extraction of the cuticular wax layer followed by chromatographic fractionation and detection of CPs using two different GCMS techniques. Total CP concentrations (sum of short (SCCP), medium (MCCP) and long chain CPs (LCCP)) were determined by EI-MS/MS. SCCP and MCCP levels as well as congener group patterns (n-alkane chain length, chlorine content) could be evaluated using ECNI-LRMS. For the first time, data on environmental airborne CPs on spruce needles taken within the Monitoring Network in the Alpine Region for Persistent and other Organic Pollutants (MONARPOP) are presented providing evidence that spruce needles are a suitable passive sampling system for the monitoring of atmospheric CPs.     

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.     

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.     

Comparison of active and passive sampling for the determination of persistent organic pollutants (POPs) in sewage treatment plants

Semipermeable membrane devices (SPMDs) and conventional active sampling methods were used for the sampling of wastewater from the wastewater treatment plant of Thessaloniki, northern Greece. The occurrence of 22 POPs was shown by both sampling methods. The most abundant compounds were heptachlor-exo-epoxide and PCBs-52; -101 and -180. Concentrations of POPs detected by active sampling and those estimated by the SPMDs matched very well in some cases, but significant mismatches were also observed. Regression analysis of the results detected by both methods showed moderate correlations. The highest uptake rate of hydrophobic compounds by SPMDs was observed for analytes with log K(OW) between 5.5 and 6.0. Our data suggest that active and passive sampling are complimentary, and that at least for the outflow of a WWTP, SPMDs could be used for the routine monitoring of compounds that are listed at the Water Framework Directive of the European Commissions.     

Can pine needles indicate trends in the air pollution levels at remote sites?

Data from ten years of integrated monitoring were used here to evaluate whether pine needles are a feasible tool for an assessment of long-term trends of the atmospheric contamination. Pine needles collected once a year were compared to high volume air samples collected for 24 h, every 7 days, and passive air samples integrated over 28-day periods. Results showed the same concentration patterns of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) captured in needles and high volume samples. Passive air samplers were less efficient in sampling the particle-bound compounds. Theoretical air volume equivalent to each needle sample (V_EQ) was calculated as a ratio of the needle concentration over the mean air concentration. Results indicated different equivalent volumes for PAHs and organochlorines, possibly due to the faster degradation rates of PAHs in needles. The most important finding is that in the long term a needle monitoring gives very similar information on temporal trends of the atmospheric pollution as does a high volume air monitoring.     

Photolysis of polycyclic aromatic hydrocarbons adsorbed on spruce [Picea abies (L) Karst] needles under sunlight irradiation

Photolysis of polycyclic aromatic hydrocarbons (PAHs) sorbed on surfaces of spruce [Picea abies (L.) Karst.] needles under sunlight irradiation was investigated. PAHs were produced by combustion of polyvinyl chloride (PVC), wood, high-density polyethylene (HDPE), and styrene in a stove. The factors of sunlight irradiation on the surfaces of spruce needles were taken into consideration when investigating the kinetic parameters. The photolysis of the 18 PAHs under study follows first-order kinetics. The photolysis half-lives range from 15 h for dibenzo(a,h)anthracene to 75 h for phenanthrene. Photolysis of some PAHs on surfaces of spruce needles may play an important role on the fate of PAHs in the environment.     

Semipermeable membrane devices accumulate conserved ratios of sterane and hopane petroleum biomarkers

Semipermeable membrane devices (SPMDs) are commonly used as a time-integrated measure of aqueous concentrations of persistent hydrophobic chemicals, including PAH, pesticides, dioxins, and PCBs. Another class of persistent hydrophobic chemicals is petroleum biomarker compounds (hopanes and steranes) that are used for hydrocarbon source identification and allocation. In this study three different passive sampling device designs were exposed to a complex hydrocarbon mixture (Alaska North Slope crude) in a laboratory experiment to determine uptake rates of biomarkers into SPMDs. In addition to the standard triolein filled SPMDs, iso-octane filled SPMDs (ISPMDs) and unfilled low-density polyethylene strips (PESDs) were tested. Uptake rates and effective sampling rates were determined for 53 compounds. There was little variation in sampling rates among the individual biomarkers; average values (ld(-1)) for hopanes were 0.43+/-0.07 (PESD), 0.33+/-0.06 (SPMD), and 0.44+/-0.03 (ISPMD) and average sterane sampling rates were 0.57+/-0.04 (PESD), 0.42+/-0.03 (SPMD), and 0.53+/-0.03 (ISPMD). The primary reason for biomarker analysis is for source discrimination of petroleum. Nineteen different diagnostic ratios were measured, and were found to be remarkably well conserved between the oil, water, and all three devices. This indicates that SPMDs, PESDs, and ISPMDs should each be effective for source discrimination studies of petroleum contamination.     

Pine needle and semi-permeable membrane device derived organochlorine compounds (OCPs) concentrations in air in Mersin Province to Taurus,Turkey

Abstract

Organochlorine pesticides (OCPs) were analyzed in three different ages (half-, 1.5-, 2.5-year-old) for needles and semi permeable membrane devices (SPMDs) at three deployment periods from sea level to 1881 meter above sea level. Individual HCHs concentrations ranged between 1.4 and 129?pg/g fw depending on the age and sampling season while 2.5-year-old needles showed higher HCHs levels compared to half and 1.5- year-old. Correlation between elevation and HCH concentration in SPMDs was found but not in needle samples. Concentrations of HCHs in SPMDs indicated clearly cold condensation effect on accumulation in winter period and increased with altitude. Concentrations of DDTs in half and 1.5-year-old needles were lower than 2.5-year-old needles. The highest total concentration of DDTs was detected in 1-year-period SPMD. Higher concentrations were found in 2.5-year-old needles for other OCPs. Seasonal and altitude-dependent changes were not observed for other OCPs in SMPDs. Total accumulation of OCPs in SPMDs were found higher than in needles. On the contrary, an increased accumulation rate was observed for HCHs in SPMD. In general, Total concentrations of DDTs and HCHs were similar to total of other OCPs in all altitudes when dominating endosulfan wasnot taken into account in the computation of total concentration of other OCPs.     

Disappearance of polycyclic aromatic hydrocarbons sorbed on surfaces of pine [Pinua thunbergii] needles under irradiation of sunlight: Volatilization and photolysis

The solar photodegradation of 16 polycyclic aromatic hydrocarbons (PAHs), sorbed on surfaces of pine [Pinua thunbergii] needles was investigated. The PAHs were produced by combustion of polystyrene and exposed onto the surfaces of pine needles. The disappearance of PAHs sorbed on the pine needle surfaces is mainly caused by volatilization and photolysis, with photolysis playing a major role. The volatilization rates correlate with PAH molecular weight significantly. The photolysis of the 16 PAHs follows first-order kinetics and their photolysis half-lives (t_1/2,P) range from 12.9 h for naphthalene to 65.4 h for fluorene. The PAHs have similar half-lives whether they are sorbed on spruce or pine needles. Compared with water, the cuticular waxes of pine needles can stabilize photolysis of PAHs and facilitate accumulation of PAHs. t_1/2,P for selected PAHs correlate with semi-empirically calculated energy of the highest occupied orbital (E_HOMO). Photochemical behaviors of PAHs are dependent not only on their molecular structures but also the physical–chemical properties of the substrate on which they are adsorbed.     

Application of semipermeable membrane device for assessing toxicity in drinking water

Semipermeable membrane devices (SPMDs) mimic passive diffusive transport of bioavailable hydrophobic organic compounds through biological membranes and their partitioning between lipids and environmental levels. Our study was developed on a surface water treatment plant based in Turin, Northern Italy. The investigated plant treats Po River surface water and it supplies about 20% of the drinking water required by Turin city (about one million inhabitants). Surface water (input) and drinking water (output) were monitored with SPMDs from October 2001 to January 2004, over a period of 30 days. The contaminant residues, monthly extracted from SPMDs by dialysis in organic solvent, were tested with the Microtox^TM acute toxic test and with the Ames mutagenicity test. Same extracts were also analyzed with gaschromatography—mass spectrometry technique in order to characterise the organic pollutants sampled, especially Polycyclic Aromatic Hydrocarbons (PAHs).

Although the PAHs mean concentration is about one hundred times lower in the output samples, the mean toxic units are similar in drinking and surface water.

Our data indicate that the SPMD is a suitable tool to assess the possible toxicity in drinking water.     

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.     

Conifer needles as passive biomonitors of the spatial and temporal distribution of DDT from a point source

Needles of two conifer species, Picea abies and Pinus nigra, were used as passive samplers for monitoring air contamination by sampling at increasing distances from a suspected point source of DDT. Needle concentrations declined with increasing distance downwind of the point source allowing to identify spatial and temporal trends of accumulation. This suggested that conifer needles are effective biomonitors of contamination levels in areas characterized by the presence of semi-volatile substances. Differences in uptake were apparent between the species. Needle morphology and structure were studied with scanning electron microscope (SEM) as were dimensional parameters (surface area, volume). The results suggest that the concentrations depend on a mechanism involving the inner structure of the needles, specifically the number and accessibility of resin channels rather than their surface area. Pine needles have more channels with greater accessibility than spruce. The results suggest that spruce is more suitable for short term measurement while pine for determining long term cumulative exposure.     

Uptake rates of alkylphenols, PAHs and carbazoles in semipermeable membrane devices (SPMDs) and polar organic chemical integrative samplers (POCIS)

Passive sampling devices provide a useful contribution to the monitoring of contaminants in the aquatic environment. However, calibration data needed for the calculation of water concentrations from sampler accumulations are restricted to a limited number of compound classes. Thus uptake of a range of alkylated phenols (AP), polycyclic aromatic hydrocarbons (PAH) and carbazoles was determined for semipermeable membrane devices (SPMDs) and polar organic chemical integrative samplers (POCIS) using a flow through exposure system. Sampling rates ranged from 0.02 to 0.26 l d(-1) for POCIS and 0.02 to 13.83 l d(-1) for SPMDs. Observed SPMD uptake was also compared to that predicted by an empirical model including the use of performance reference compounds (PRCs). Predicted sampling rates did not differ by more than a factor of 1.3 from experimental values for PAH, providing further evidence that the PRC approach can be successfully used to determine in situ sampling rates for these compounds. Experimental sampling rates for AP in SPMDs were, however, much lower than predicted. This discrepancy was too large to be explained by small uncertainties in the calibration system or in the calculations. Based on these data we conclude that while hydrophobic AP are accumulated by SPMDs their partitioning cannot be predicted from their logK(ow) using current methods. Due to this lower than expected uptake, sampling rates were only higher in SPMDs than POCIS in the range of logK(ow)>5.0. Simultaneous deployment of both sampler types allows the study of compounds with a broad range of physicochemical properties.     

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.     

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.     

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.     

Feasibility of a simple laboratory approach for determining temperature influence on SPMD–air partition coefficients of selected compounds

Semipermeable membrane devices (SPMDs) are a widely used passive sampling methodology for both waterborne and airborne hydrophobic organic contaminants. The exchange kinetics and partition coefficients of an analyte in a SPMD are mediated by its physicochemical properties and certain environmental conditions. Controlled laboratory experiments are used for determining the SPMD–air (K_sa's) partition coefficients and the exchange kinetics of organic vapors. This study focused on determining a simple approach for measuring equilibrium K_sa's for naphthalene (Naph), o-chlorophenol (o-CPh) and p-dichlorobenzene (p-DCB) over a wide range of temperatures. SPMDs were exposed to test chemical vapors in small, gas-tight chambers at four different temperatures (−16, −4, 22 and 40 °C). The exposure times ranged from 6 h to 28 d depending on test temperature. K_sa's or non-equilibrium concentrations in SPMDs were determined for all compounds, temperatures and exposure periods with the exception of Naph, which could not be quantified in SPMDs until 4 weeks at the −16 °C temperature. To perform this study the assumption of constant and saturated atmospheric concentrations in test chambers was made. It could influence the results, which suggest that flow through experimental system and performance reference compounds should be used for SPMD calibration.