Enantiomeric separation of metolachlor and its metabolites using LC-MS and CZE

The stereoisomers of metolachlor and its two polar metabolites [ethane sulfonic acid (ESA) and oxanilic acid (OXA)] were separated using liquid chromatography-mass spectrometry (LC-MS) and capillary zone electrophoresis (CZE), respectively. The separation of metolachlor enantiomers was achieved using a LC-MS equipped with a chiral stationary phase based on cellulose tris(3,5-dimethylphenyl carbamate) and an atmospheric pressure chemical ionization source operated under positive ion mode. The enantiomers of ESA and OXA were separated using CZE with gamma-cyclodextrin (gamma-CD) as chiral selector. Various CZE conditions were investigated to achieve the best resolution of the ESA and OXA enantiomers. The optimum background CZE electrolyte was found to consist of borate buffer (pH=9) containing 20% methanol (v/v) and 2.5% gamma-CD (w/v). Maximum resolution of ESA and OXA enantiomers was achieved using a capillary temperature of 15 degrees C and applied voltage of 30 kV. The applicability of the LC-MS and CZE methods was demonstrated successfully on the enantiomeric analysis of metolachlor and its metabolites in samples from a soil and water degradation study that was set up to probe the stereoselectivity of metolachlor biodegradation. These techniques allow the enantiomeric ratios of the target analytes to be followed over time during the degradation process and thus will prove useful in determining the role of chirality in pesticide degradation and metabolite formation.     

An assessment of the risks associated with polychlorinated biphenyls found in the stomach contents of stranded Indo-Pacific Humpback Dolphins (Sousa chinensis) and Finless Porpoises (Neophocaena phocaenoides) from Hong Kong waters

The risks to Indo-Pacific Humpback Dolphins and Finless Porpoises associated with polychlorinated biphenyls (PCBs) were assessed. Stomach contents from twelve stranded Humpback Dolphins and sixteen stranded Finless Porpoises were collected. Concentrations of total and isomer-specific PCBs in the stomach contents were determined using dual-column gas chromatography equipped with electron capture detectors (GC-ECD). Risks due to the PCBs were assessed in three scenarios, based on total PCBs (summation of 41 PCB congeners), total toxicity equivalency (TEQs) and PCB 118, using the toxicity reference values (TRVs) as the threshold effects benchmarks. The calculated risk quotients (RQs) showed that risks due to PCBs were generally low or negligible. Specifically, RQs from total TEQs and total PCBs for Finless Porpoises are below one, suggesting that PCBs should be a low risk for the Finless Porpoise in Hong Kong waters. However, the Humpback Dolphin has RQs larger than 1 for total TEQs and total PCBs when the 95th percentile data were used in the evaluation. This indicates that further investigation may be needed to examine more closely the potential impact of toxic contaminants in the habitat of the Humpback Dolphin.     

Brominated flame retardant concentrations and trends in abiotic media

BFR burdens in abiotic media have been less studied than in biota, despite their essential value as an aide to identifying sources, temporal and geographic trends and exposure routes. Many polymer products consist of several percent by weight of BFRs. Global trade in these can result in rapid and wholesale BFR movement. Loss from in-use products of nonreactive BFRs may be important, particularly in respect to indoor exposure. In the case of BDE-209, discharges from publicly owned treatment works may be substantial. BFR burdens in air, water and sewage sludge respond rapidly to changes in environmental BFR inputs. PBDEs have been the most widely studied. In many locales PBDE burdens in these media now surpass those of PCBs. Air and water near sources and urban areas are typically enriched relative to rural locales. The more volatile PBDEs dominate in the vapor phase, while BDE-209 typically predominates on particulates. Evidence exists for long-range transport of the more volatile PBDEs. A greater diversity of BFRs (mostly PBDEs, HBCD and TBBP-A) has been detected in sewage sludges. Land application of these sludges on agricultural fields is one conduit for soil contamination. In general, environmental concentrations of BDE-209 appear to be increasing, while penta-BDE burdens in Europe may have peaked. Sediments function as longer-term integrators of environmental burdens. Concentrations of common BFRs therein may be substantial near point sources. Evidence for debromination in the environment has been limited to date. However, some laboratory and field observations suggest it is possible to a limited extent.     

Pesticides and metabolites in cassava, eucalyptus, plum and cashew leaves and roots in relation to a point source in Kibaha, Tanzania

Leaves of Eucalyptus sp., Prunus domestica (plum), and Anacardium occidentale (cashew), as well as roots and leaves of Manihot esculenta (cassava) were used to study the local distribution of pesticides and metabolites from a point source, an old storage site at Vikuge farm in Tanzania. The GPC-cleaned extracts were analyzed by GC-ECD and GC/MS. Eleven organochlorine pesticide residues namely pentachloroanisole, p,p'-DDT, o,p'-DDT, p,p'-DDE, o,p'-DDE, p,p'-DDD, o,p'-DDD, alpha-HCH, beta-HCH, delta-HCH and epsilon-HCH were detected in the samples. The concentrations of total DDT were 818 ng/g fw in Eucalyptus sp., 16 ng/g fw in A. occidentale and 4 ng/g fw in P. domestica. In M. esculenta, total DDT ranged from 191 to 586 ng/g fw in roots and 7 to 425 ng/g fw in leaves. The concentrations of total HCH were up to 15 ng/g fw in Eucalyptus sp., while the concentrations of pentachloroanisole were up to 2 ng/g fw in leaves of M. esculenta. There are very strong positive correlations in the concentrations of the detected compounds, suggesting that they have a common source. The low DDE/DDT ratios (0.02-0.07) in all samples indicate input of non-degraded DDT from the source. The high alpha-HCH/gamma-HCH ratios in some samples (>3.1-10) indicate input of technical HCH. The concentrations of total DDT in cassava roots were either very close to, or greater than, the FAO/WHO limit, indicating risks and concern to public health.     

Passive sampler derived air concentrations of PBDEs along an urban-rural transect: spatial and temporal trends

Passive air samplers consisting of polyurethane foam (PUF) disks housed in chambers were deployed at several sites along a approximately 75 km urban-rural gradient in Toronto and analyzed for polybrominated diphenyl ethers (PBDEs). Samplers were allowed to integrate gas-phase PBDEs over three consecutive seasons starting in the summer of 2000. PBDEs were fairly uniform along the transect with air concentrations in Toronto (10-30 pgm(-3)) about a factor of two greater than at rural sites. Lowest concentrations were observed during the winter and probably associated with reduced inputs from indoor sources of PBDEs and to a preference for PBDEs to partition to the particle-phase at colder temperatures. The composition of PBDEs in the air samples did not differ across the transect or for the different seasons.     

Contaminant mass discharge estimation in groundwater based on multi-level point measurements: a numerical evaluation of expected errors

Different methods for the field-scale estimation of contaminant mass discharge in groundwater at control planes based on multi-level well data are numerically analysed for the expected estimation error. We consider "direct" methods based on time-integrated measuring of mass flux, as well as "indirect" methods, where estimates are derived from concentration measurements. The appropriateness of the methods is evaluated by means of modelled data provided by simulation of mass transport in a three-dimensional model domain. Uncertain heterogeneous aquifer conditions are addressed by means of Monte-Carlo simulations with aquifer conductivity as a random space function. We investigate extensively the role of the interplay between the spatial resolution of the sampling grid and aquifer heterogeneity with respect to the accuracy of the mass discharge estimation. It is shown that estimation errors can be reduced only if spatial sampling intervals are in due proportion to spatial correlation length scales. The ranking of the methods with regard to estimation error is shown to be heavily dependent on both the given sampling resolution and prevailing aquifer heterogeneity. Regarding the "indirect" estimation methods, we demonstrate the great importance of a consistent averaging of the parameters used for the discharge estimation.     

Changes in air saturation and air-water interfacial area during surfactant-enhanced air sparging in saturated sand

Reduction in the surface tension of groundwater, prior to air sparging for removal of volatile organic contaminant from aquifer, can greatly enhance the air content and the extent of influence when air sparging is implemented. However, detailed information on the functional relationship between water saturation, air-water contact area induced by air sparging and the surface tension of water has not been available. In this study, the influence of adding water-soluble anionic surfactant (sodium dodecyl benzene sulfonate) into groundwater before air sparging on the air-water interfacial area and water saturation was investigated using a laboratory-scale sand packed column. It was found that water saturation decreases with decreasing surface tension of water until it reaches a point where this trend is reversed so that water saturation increases with further decrease in the surface tension. The lowest water saturation of 0.58 was achieved at a surface tension of 45.4 dyn/cm, which is considered as the optimum surface tension for maximum de-saturation for the initially water-saturated sand used in this study. The air-water contact area generated in the sand column due to air sparging was measured using a gaseous interfacial tracer, n-decane, and was found to monotonically increase with decreasing water saturation. The results of this study provide useful design information for surfactant-enhanced air sparging removal of volatile contaminants from aquifers.     

Geochemical and Pb isotopic evidence for sources and dispersal of metal contamination in stream sediments from the mining and smelting district of Príbram, Czech Republic

Stream sediments from the mining and smelting district of Príbram, Czech Republic, were studied to determine the degree, sources and dispersal of metal contamination using a combination of bulk metal and mineralogical determinations, sequential extractions and Pb isotopic analyses. The highest metal concentrations were found 3-4 km downstream from the main polymetallic mining site (9800 mg Pb kg(-1), 26 039 mg Zn kg(-1), 316.4 mg Cd kg(-1), 256.9 mg Cu kg(-1)). The calculated enrichment factors (EFs) confirmed the extreme degree of contamination by Pb, Zn and Cd (EF>40). Lead, Zn and Cd are bound mainly to Fe oxides and hydroxides. In the most contaminated samples Pb is also present as Pb carbonates and litharge (PbO). Lead isotopic analysis indicates that the predominant source of stream sediment contamination is historic Pb-Ag mining and primary Pb smelting (206Pb/207Pb=1.16), while the role of secondary smelting (car battery processing) is negligible.     

Levels of trace elements in green turtle eggs collected from Hong Kong: Evidence of risks due to selenium and nickel

Concentrations of 22 trace elements were determined in green turtle (Chelonia mydas) eggs collected from Hong Kong. Concentrations of selenium, lead and nickel in these eggs were generally higher than those reported in other studies. The predicted no effect concentrations (PNEC; ng/g wet weight) of Pb (1000), Se (340 and 6000 for the worst-case and best-case scenarios, respectively) and Ni (17) in the green turtle eggs were estimated. Hazard quotients (HQs) estimate that Se (HQs: 0.2-24.5) and Ni (HQs: 4.0-26.4) may pose some risks to the turtles. Our study also found that concentrations of Ag, Se, Zn, Hg and Pb in the shell of the turtle eggs were significantly correlated with levels in the whole egg contents (yolk+albumen). Once the precise relationships of specific elements are established, egg-shell concentrations may be used as a non-lethal, non-invasive, surrogate for predicting whole egg burden of certain contaminants in marine turtles.     

Fixation of metals in soil constituents and potential remobilization by hyperaccumulating and non-hyperaccumulating plants: results from an isotopic dilution study

In this study isotopic dilution methods were used to investigate the hypothesis that access to metals associated with specific chemical components in the soil that are not available to non-accumulator species could be involved in hyperaccumulation. The hyperaccumulator Thlaspi caerulescens and a non-accumulator species, Brassica napus, were grown in Cd and Zn enriched soil components calcite, goethite, charcoal and cryptomelane. The metal enriched components were aged to allow transformation of a proportion of added metals to non-labile forms. Results from the isotopic dilution L value method showed that despite taking up more metals, T. caerulescens accessed the same pool of metals as B. napus. Hence differential access to different solid-phase pools of metals appears to be an unlikely mechanism underlying metal hyperaccumulation. For all components except charcoal, L values for Cd and Zn were greater than the corresponding E values suggesting that E values may tend to underestimate the bioavailable fraction of metals in soils.