A comparison of mussels (Perna viridis) and semi-permeable membrane devices (SPMDs) for monitoring chlorinated trace organic contaminants in Hong Kong coastal waters

A comparison of mussels (Perna viridis) and semi-permeable membrane devices (SPMDs) was carried out at five sites, representing a gradient of contaminant concentrations, in Hong Kong coastal waters. Mussels, originally collected from a “clean” location, were deployed along with SPMDs at each site for 30 days. Analyses for chlorinated pesticides and polychlorinated biphenyls (PCBs) indicated that SPMDs have potential as monitoring tools, and to some extent can overcome the problems associated with mussels, such as natural variability, differing age, sex, and physical condition. However, in most cases, SPMDs failed to rank the sites in the same order as mussels in terms of contaminant concentrations. Nonetheless, in localities where mussels cannot survive – as shown at Kwun Tong in the present experiment – SPMDs may be valuable in providing an indication of potentially bio-available lipophilic pollutants.     

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.     

A rapidly equilibrating, thin film, passive water sampler for organic contaminants; characterization and field testing

Improving methods for assessing the spatial and temporal resolution of organic compound concentrations in marine environments is important to the sustainable management of our coastal systems. Here we evaluate the use of ethylene vinyl acetate (EVA) as a candidate polymer for thin-film passive sampling in waters of marine environments. Log K_EVA−W partition coefficients correlate well (r² = 0.87) with Log K_OW values for selected pesticides and polychlorinated biphenyls (PCBs) where Log K_EVA−W = 1.04 Log K_OW + 0.22. EVA is a suitable polymer for passive sampling due to both its high affinity for organic compounds and its ease of coating at sub-micron film thicknesses on various substrates. Twelve-day field deployments were effective in detecting target compounds with good precision making EVA a potential multi-media fugacity meter.     

Characterization of polychlorinated biphenyls and brominated flame retardants in sludge,sediment and fish from municipal dumpsite at Surabaya,Indonesia

We investigated the PCBs, PBDEs and HBCDs contamination in sludge, sediments and fish from various locations including raw leachate pond, leachate treatment plans (LTPs), control wells and reference site at open landfill of municipal dumpsite, Surabaya City, Indonesia. 62 PCBs and 14 PBDEs congeners, and 3 HBCDs isomers were identified and quantified using GC–MS and LC–MS/MS, respectively. Concentration ranges and median (value in parentheses) of PCBs, PBDEs and HBCDs were from not detected (ND) to 60 (3.9) ng g⁻¹ dw, 0.0075 to 45 (4.5) ng g⁻¹ dw and ND to 2.8 (0.052) ng g⁻¹ dw in sludge and sediments, respectively. While in two polled of fish samples were 30–55 ng g⁻¹ lw, 6.6–11 ng g⁻¹ lw and 1.6–3.3 ng g⁻¹ lw, respectively. Among the sampling sites, the highest level of PCBs and PBDEs were detected in sludge from raw leachate pond. However, PCBs and PBDEs levels were showing decreased in LTP-1 that could be due to the bacterial degradation but not in LTP-2, HBCDs were more stable in both LTPs. Levels of PCBs and BFRs in sludge at the present study were lower than those reported in sewage sludge reported from some other countries. PCBs profiles were mainly composed in that order by CB-138, -153, -180, -101, -118 and -28, while by BDE-47, -99, -100, -153, -154 and -28 for PBDEs in sludge, sediments and fish. Profiles of HBCDs were predominantly composed by γ- and α-isomers in sludge and fish, respectively. Debromination, dechlorination, commercial formulations used and congener-specific accumulation of those contaminants are the factors influenced the profiles.     

A monitoring study of workers handling pesticides in warehouses and godowns

Abstract

Monitoring observations made on 60 operators involved in pesticide application work in godowns and warehouses and 60 matched control workers are reported. Occupational exposure history and medical history are noted. Biochemical investigations, plasma and RBC cholinesterase estimations are included along with medical examination of the workers. Workers were found to be mostly exposed to Celphos, DDVP, Malathion, Pyrethrum, etc, and the use of protective devices were very limited. Cases of significant reduction in plasma and RBC cholinesterase activity were found. Frequency of symptoms like dizziness, headache, lachrymation, burning sensation in eyes, nausea and anorexia, etc, were much more in the exposed workers. No cases of clinical poisoning attributable to occupational exposure to pesticides were reported by the workers.     

Field evaluation of two diffusive samplers and two adsorbent media to determine 1,3-butadiene and benzene levels in air

Two types of diffusive samplers, both of which are compatible with thermal desorption, but differ in their geometry—SKC-Ultra (badge-type) and Radiello (radial symmetry-type)—were evaluated indoors and outdoors under varying temperature, humidity and wind speed conditions, using the graphitized adsorbents Carbopack X or Carbograph 5 to measure 1,3-butadiene and benzene in ambient air. The results obtained by diffusive sampling were compared with results obtained using a conventional active sampling method over both long (1 week) and shorter periods (6–24 h). Analysis and detection were performed using an automatic thermal desorber (ATD) connected to a gas chromatograph-flame ionization detector (GC/FID). Results from each sampler and adsorbent combination were examined using ordinary or multiple linear regression analysis. The overall uncertainty (OU) was also determined. In general, the results obtained with both samplers showed good agreement with those obtained by active sampling. Carbopack X appeared to be a more efficient adsorbent than Carbograph 5 for 1,3-butadiene, but the two adsorbents were equivalent for benzene. No effects of either humidity or air velocity were observed. Minor temperature effects were observed for both samplers for 1,3-butadiene. In summary, the results confirmed the accuracy of sampling rates previously determined for the two samplers and adsorbents. We consider the two samplers to be suitable for stationary and personal monitoring for the general population of 1,3-butadiene and benzene in various environments, indoors and outdoors. They are almost independent of meteorological conditions and may be suitable for monitoring industrial atmospheres.     

Transport of polycyclic aromatic hydrocarbons in highly vulnerable karst systems

Fluxes of polycyclic aromatic hydrocarbons (PAHs) were investigated along the route of transport in a south German karst system. Atmospheric deposition, seepage water in caves and spring water at the outlet of the catchment were monitored continuously over 1.5 years allowing the establishment of an input/output mass balance at the catchment scale. The results reveal that, even in the highly vulnerable karst catchment, PAHs are effectively retained in the soils. Only during high discharge events, such as snowmelt in spring, increasing PAH concentrations at the outlet of the catchment indicates a mobilization of the pollutants. These events are typically correlated with increasing particle concentrations. Based on our results, we conclude that particle-facilitated transport is the dominating cause of PAH mobilization. In summary, PAHs accumulate over time in soils and only occasionally high discharge events cause a short concentration pulse to be flushed through the karst system.     

Assessing seasonal and spatial trends of persistent organic pollutants (POPs) in Indian agricultural regions using PUF disk passive air samplers

The first survey of persistent organic pollutant (POP) concentrations in air across several Indian agricultural regions was conducted in 2006-2007. Passive samplers comprising polyurethane foam (PUF) disks were deployed on a quarterly basis at seven stations in agricultural regions, one urban site and one background site. The project was conducted as a sub-project of the Global Atmospheric Passive Sampling (GAPS) Network. In addition to revealing new information on air concentrations of several organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs), the study has demonstrated the feasibility of conducting regional-scale monitoring for POPs in India using PUF disk samplers. The following analytes were detected with relatively high concentrations in air (mean for 2006 and 2007, pg/m³): α- and γ-hexachlorocyclohexane (HCH) (292 and 812, respectively); endosulfan I and II (2770 and 902, respectively); p,p′-DDE and p,p′-DDT (247 and 931, respectively); and for the sum of 48 PCBs, 12,100 (including a site with extremely high air concentrations in 2007) and 972 (when excluding data for this site).     

Snapping turtles (Chelydra serpentina) as bioindicators in Canadian areas of concern in the Great Lakes Basin. II. Changes in hatching success and hatchling deformities in relation to persistent organic pollutants

Hatching success and deformities in snapping turtle hatchlings (Chelydra serpentina) were evaluated using eggs collected from 14 sites in the Canadian lower Great Lakes, including Areas of Concern (AOC), between 2001 and 2004. Eggs were analyzed for PCBs, PBDEs, and pesticides. Between 2002 and 2004, hatchling deformity rates were highest in two AOCs (18.3-28.3%) compared to the reference sites (5.3-11.3%). Hatching success was poorest in three AOCs (71.3-73.1%) compared to the reference sites (86.0-92.7%). Hatching success and deformity rates were generally poorer in 2001 compared to 2002-2004, irrespective of the study location and could be due to egg handling stress in 2001. Hatching success and deformities were generally worst from the Wheatley Harbour, St. Lawrence River (Cornwall), Detroit River, and Hamilton Harbour AOCs. Associations between contaminant burdens with embryonic development were sufficiently poor that the biological relevance is questionable. Stressors not measured may have contributed to development abnormalities.     

Pesticides in the groundwater of a spring draining a sandy aquifer: temporal variability of concentrations and fluxes

A 250 ha agricultural catchment has been characterized with respect to its hydrogeology and groundwater contamination by pesticides from October 1999 to August 2004. Five years after the ending of atrazine (At) application, used since the sixties, At and deethylatrazine (DEA) are still systematically quantified at the outlet of the watershed with concentrations from 0.07 to 0.43 microg l(-1) for At, and between 0.14 and 1.16 microg l(-1) for DEA. Isoproturon and chlortoluron are detected in only one (0.3 microg l(-1)) and two (0.7 and 2.0 microg l(-1)) of the 124 semi-monthly samples, respectively. DEA concentrations can be very different between two samples with a 15-day time step. The annual mean exported fluxes of cumulated At and DEA are stable, which indicates a long time transfer in the unsaturated or saturated zone with a progressive leaching of the stock of At and DEA probably accumulated in the soil and the vadose zone. These fluxes, between 0.90% and 2.82% of the annual mean dose of At applied before 1999, similar to those calculated in several studies at the bottom of the root zone, could be explained by low adsorption and degradation properties of At and DEA in the unsaturated and saturated zone.     

Runoff of pesticides from rice fields in the Ile de Camargue (Rhône river delta, France): field study and modeling

A field study on the runoff of pesticides was conducted during the cultivation period in 2004 on a hydraulically isolated rice farm of 120 ha surface with one central water outlet. Four pesticides were studied: Alphamethrin, MCPA, Oxadiazon, and Pretilachlor. Alphamethrin concentrations in runoff never exceeded 0.001 microg L(-1). The three other pesticides were found in concentrations between 5.2 and 28.2 microg L(-1) in the runoff water shortly after the application and decreased thereafter. The data for MCPA compared reasonably well with predictions by an analytical runoff model, accounting for volatilization, degradation, leaching to groundwater, and sorption to soil. The runoff model estimated that runoff accounted for as much as 18-42% of mass loss for MCPA. Less runoff is observed and predicted for Oxadiazon and Pretilachlor. It was concluded that runoff from rice paddies carries important loads of dissolved pesticides to the wetlands in the Ile de Camargue, and that the model can be used to predict this runoff.     

PBDE flame retardants and PCBs in migrating Steller sea lions (Eumetopias jubatus) in the Strait of Georgia, British Columbia, Canada

Polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) were measured in blubber biopsy samples from 22 live-captured Steller sea lions (Eumetopias jubatus) that had just entered the Strait of Georgia, British Columbia, Canada, for their overwintering feeding season. ∑PBDE ranged from 50 μg kg⁻¹ (lipid weight) in adult females to 3780 μg kg⁻¹ in subadult individuals. ∑PCBs ranged from 272 μg kg⁻¹ in adult females to 14 280 μg kg⁻¹ in subadult individuals. While most PBDE and PCB congeners were transferred through milk to pups, PCBs with log K_OW > 7.0 (PCBs 206, 207, 208 and 209) appeared constrained, resulting in a lighter mixture in pups compared to adult females. The ratio of individual PCB congeners by metabolic group (Groups I, II, III, IV and V) to PCB-153 regressed against length of males suggested poor biotransformation of these compounds (slopes did not differ from zero, p > 0.05). PBDE congeners 49, 99, 153 and 183 appeared bioaccumulative (slopes of ratio BDE/PCB 153 versus length were higher than zero, p < 0.05), but the dominance of the single congener, BDE-47 (64% of total PBDEs), likely due in part to debromination pathways, reduced our ability to explore congener-specific dynamics of PBDEs in these pinnipeds. With 80% of our Steller sea lions exceeding a recent toxicity reference value for PCBs, the fasting-associated mobilization of these contaminants raises concerns about a heightened vulnerability to adverse effects during annual migrations.     

Uptake of PAHs into polyoxymethylene and application to oil-soot (lampblack)-impacted soil samples

Polyoxymethylene (POM) is a polymeric material used increasingly in passive sampling of hydrophobic organic contaminants such as PAHs and PCBs in soils and sediments. In this study, we examined the sorption behavior of 12 PAH compounds to POM and observed linear isotherms spanning two orders of magnitude of aqueous concentrations. Uptake kinetic studies performed in batch systems for up to 54 d with two different volume ratios of POM-to-aqueous phase were evaluated with coupled diffusion and mass transfer models to simulate the movement of PAHs during the uptake process and to assess the physicochemical properties and experimental conditions that control uptake rates. Diffusion coefficients of PAHs in POM were estimated to be well correlated with diffusants' molecular weights as D(POM) proportional, variant(MW)(-3), descending from 2.3 x 10(-10) cm(2) s(-1) for naphthalene to 7.0 x 10(-11) cm(2) s(-1) for pyrene. The uptake rates for PAHs with log K(ow)<5.8 were controlled by the POM phase and the hydrophobicity of PAH compounds. For more hydrophobic PAH compounds, the aqueous boundary layer played an increasingly important role in determining the overall mass transfer rate. The POM partitioning technique was demonstrated to agree well with two other procedures for measuring PAH soil-water distribution coefficients in oil-soot (lampblack) containing soil samples.     

Little effect of excessive biofouling on the uptake of organic contaminants by semipermeable membrane devices

The effects of water flow rate and antifouling agents on the extent of biofouling and on the uptake of non-polar organic contaminants by semipermeable membrane devices (SPMDs) were studied during four field experiments in the Western Wadden Sea. Biofouling densities on the sampler surface ranged from 0.3 to 16 g dry weight dm⁻². Water sampling rates were estimated from the dissipation rates of performance reference compounds (PRCs). The antifouling agents Irgarol and capsaicin (33 mg per ml triolein) had no noticeable effect on the extent of fouling, and caused only a 5–10% increase in the absorbed amounts. Enhanced flow rates had only a minimal effect on the amount of biofouling, but caused the water sampling rates to increase by a factor of 1.2–2. Increases in PRC-derived sampling rates were reflected by increases in the absorbed amounts for compounds that were in the linear uptake stage of the sampling process. The results imply (1) that extreme biofouling does not always result in reduced sampling rates, (2) that extreme biofouling does not preclude the existence of flow effects on the sampling rates, and (3) that differences in uptake rates are quantitatively reflected by the dissipation rates of PRCs.     

Ozone distribution and phytotoxic potential in mixed conifer forests of the San Bernardino Mountains, southern California

In the San Bernardino Mountains of southern California, ozone (O(3)) concentrations have been elevated since the 1950s with peaks reaching 600ppb and summer seasonal averages >100ppb in the 1970s. During that period increased mortality of ponderosa and Jeffrey pines occurred. Between the late 1970s and late1990s, O(3) concentrations decreased with peaks approximately 180ppb and approximately 60ppb seasonal averages. However, since the late 1990s concentrations have not changed. Monitoring during summers of 2002-2006 showed that O(3) concentrations (2-week averages) for individual years were much higher in western sites (58-69ppb) than eastern sites (44-50ppb). Potential O(3) phytotoxicity measured as various exposure indices was very high, reaching SUM00 - 173.5ppmh, SUM60 - 112.7ppmh, W126 - 98.3ppmh, and AOT40 - 75ppmh, representing the highest values reported for mountain areas in North America and Europe.     

Passive air monitoring of PCBs and PCNs across East Asia: a comprehensive congener evaluation for source characterization

A comprehensive congener specific evaluation of polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) in the atmosphere was conducted across East Asia in spring 2008, applying polyurethane foam (PUF) disk passive air sampler (PAS) as monitoring device. Mean concentrations derived for Japan, China and Korea were 184 ± 24, 1100 ± 118, and 156 ± 20 pg m⁻³ for ∑₂₀₂ PCBs, and 9.5 ± 1.5, 61 ± 6, and 16 ± 2.4 pg m⁻³ for ∑₆₃ PCNs, respectively. Relative to reported data from 2004, the present results suggest that air PCBs concentrations have not changed much in Japan and Korea, while it has increased by one order of magnitude in China. From principal component analysis, combustion emerged highly culpable in contemporary emissions of both PCBs and PCNs across the East Asian sub-region. Another factor derived as important to air PCBs was re-emissions/volatilization. Signals from PCBs formulations were also picked, but their general importance was virtually consigned to the re-emissions/volatilization tendencies. On the contrary, counterpart PCNs formulations did not appear to contribute much to air PCNs.     

In-vivo passive sampling to measure elimination kinetics in bioaccumulation tests

The application of in-tissue passive sampling to quantify chemical kinetics in fish bioconcentration experiments was investigated. A passive sampler consisting of an acupuncture needle covered with a PDMS tube was developed together with a method for its deployment in rainbow trout. The time to steady state for chemical uptake into the passive sampler was >1 d, so it was employed as a kinetically limited sampler with a deployment time of 2 h. The passive sampler was employed in parallel with the established whole tissue extraction method to study the elimination kinetics of 10 diverse chemicals in rainbow trout. 4-n-nonylphenol and 2,4,6-tri-tert-butylphenol were close to or below the limit of quantification in the sampler. For chlorpyrifos, musk xylene, hexachlorobenzene, 2,5-dichlorobiphenyl and p,p′-DDT, the elimination rate constants determined with the passive sampler method and the established method agreed within 18%. Poorer agreement (35%) was observed for 2,3,4-trichloroanisole and p-diisopropylbenzene because fewer data were obtained with the passive sampling method due to its lower sensitivity. The work shows that in-tissue passive sampling can be employed to measure contaminant elimination kinetics in fish. This opens up the possibility of studying contaminant kinetics in individual fish, thereby reducing the fish requirements and analytical costs for the determination of bioconcentration factors.     

Wastewater treatment plants and landfills emit volatile methyl siloxanes (VMSs) to the atmosphere: investigations using a new passive air sampler

Volatile methyl siloxanes (VMSs) are a class of chemicals with an increasing range of applications and widespread distribution in the environment. Passive air samplers (PAS) comprising sorbent-impregnated polyurethane-foam (SIP) disks were first calibrated and then deployed around two wastewater treatment plants (WWTPs) and at two landfill sites to investigate inputs of VMSs to air. SIP-derived air concentrations for ΣVMSs (ng/m³) at background sites on the perimeter of the WWTP were 479 ± 82.3 and comparable to results for the upwind samples at the landfills (333 ± 194). Order of magnitude higher concentrations of ΣVMSs (ng/m³) were found for on-site samples at the WWTPs (3980 ± 2620) and landfills (4670 ± 3360). Yearly emissions (kg/yr) to air were estimated and ranged from 60-2100 and 80-250, respectively, for the cyclic VMSs. These findings demonstrate and quantify for the first time, waste sector emissions of VMSs to the atmosphere.     

Application of Automated Mass Spectrometry Deconvolution and Identification Software for Pesticide Analysis in Surface Waters

A new approach to surface water analysis has been investigated in order to enhance the detection of different organic contaminants in Nathan Creek, British Columbia. Water samples from Nathan Creek were prepared by liquid/liquid extraction using dichloromethane (DCM) as an extraction solvent and analyzed by gas chromatography mass spectrometry method in scan mode (GC-MS scan). To increase sensitivity for pesticides detection, acquired scan data were further analyzed by Automated Mass Spectrometry Deconvolution and Identification Software (AMDIS) incorporated into the Agilent Deconvolution Reporting Software (DRS), which also includes mass spectral libraries for 567 pesticides. Extracts were reanalyzed by gas chromatography mass spectrometry single ion monitoring (GC-MS-SIM) to confirm and quantitate detected pesticides. Pesticides: atrazine, dimethoate, diazinone, metalaxyl, myclobutanil, napropamide, oxadiazon, propazine and simazine were detected at three sampling sites on the mainstream of the Nathan Creek. Results of the study are further discussed in terms of detectivity and identification level for each pesticide found. The proposed approach of monitoring pesticides in surface waters enables their detection and identification at trace levels.