Identification of the dimethylbenzyl mercapturic acid in urine of rats treated with 1,2,3-trimethylbenzene.

The structure was investigated of the mercapturic acid excreted in urine of rats after the i.p. administration of 1,2,3-trimethylbenzene. Of the two regioisomeric mercapturic acids, i.e. N-acetyl-S-(2,3-dimethylbenzyl)-L-cysteine and N-acetyl-S-(2,6-dimethyl-benzyl)-L-cysteine, only the former was isolated by preparative HPLC and identified, by comparison with an authentic specimen. The excretion rate of the mercapturate was estimated to be approximately 5% of dose, not a substantial metabolic route.     

Current status and future needs for biological and environmental reference materials certified for methylmercury compounds.

A good quality control/quality assurance programme should be implemented in all environmental or health related studies on mercury and its organic compounds, particularly, for monomethylmercury (MeHg) which is the most toxic mercury compound. This can be achieved initially by analysing suitable certified reference materials (CRMs), which are available from various producers such as the National Institute of Standards and Technology (NIST) from USA, National Institute of Environmental Studies (NIES), National Research Council of Canada (NRCC), Standards, Measurements and Testing programme (SM&T) of the European Commission, and the International Atomic Energy Agency (IAEA). It is well understood that these materials are not covering present needs, as most of them are of the marine origin, while many laboratories are conducting research and monitoring in terrestrial ecosystems and fresh water environment. In addition, CRMs for human exposure assessment, such as blood, urine, and hair at several levels of concentrations are still lacking. Therefore, many other actions should be undertaken to achieve, improve and/or maintain quality of data, including participation in interlaboratory studies, proficiency testing and production of laboratory reference materials. A review of these actions has shown that MeHg compounds determination in samples such as soil, sediment and water is rather difficult and the results are also method dependent. In addition, it has been shown that some of the most frequently employed analytical methods may be a subject to spurious MeHg formation in the presence of high concentrations of inorganic mercury and organic matter. These findings have put a number of previous data on MeHg in question and consequently prompt actions were undertaken by a number of well experienced laboratories and producers of CRMs. So far, it is shown that the results obtained by various laboratories using different analytical techniques agree well with certified values in all RMs certified for MeHg. This suggests that comparability of data can be achieved, which however is not a guarantee of the true values.     

Biodegradation of coplanar polychlorinated biphenyls by anaerobic microorganisms from estuarine sediments.

In this study, we investigated the biodegradability of biphenyl and 5 congeners (one non-planar and four coplanar) of polychlorinated biphenyl (PCB). Biphenyl, the non-planar congener 2,3',4',5-tetrachlorobiphenyl (25-34 CB), and the four coplanar congeners 3,3',4,4'-tetrachlorobiphenyl (34-34 CB), 3,4,4',5-tetrachlorobiphenyl (345-4 CB), 3,3',4,4',5-pentachlorobiphenyl (345-34 CB), and 3,3',4,4',5,5'-hexachlorobiphenyl (345-345 CB) were amended at a concentration of 10 mg/L into anoxic sediment slurries collected from the estuaries of the Tansui River and the Erjen River. During 2 years' incubation under sulfidogenic conditions, biphenyl was persistent, while all other chlorinated congeners, except for 345-345 CB, were dechlorinated with or without a lag period in sediment slurries collected from both rivers. Dechlorination of coplanar and non-planar congeners began with para chlorine removal. All para chlorines from the mono-, di-, and trichlorobiphenyl groups could be removed by sediment slurries from both rivers. Microbial communities in sediment from the Erjen River additionally fostered meta-dechlorination activity, but only after removal of all the para chlorines. Addition of Tween 20 (0.05%, v/v) into sediment slurries from the Tansui River did not enhance dechlorination rates or extents, but the addition of toluene- or 3-chlorobenzoate-adapted sediments enhanced dechlorination of 34-34 CB and 345-4 CB.     

Metabolism and body-burden of PCBs in lactating dairy cows.

This paper uses data from a detailed 4 month PCB mass balance study on lactating cows fed a naturally contaminated background diet to quantify the metabolism and body-burdens of a range of PCB congeners. Dietary intake fluxes and milk and faecal output fluxes reported previously are combined with subcutaneous fat and blood PCB concentrations and with data from tissue/organ samples from a slaughtered animal to estimate the degree of metabolism within the cow. A total body burden is derived, showing that fat deposits account for approximately 98% of total PCB present in the lactating cow. The daily intake through feed (ng day-1) accounted for between 0.9 and 1.5% of the total body burden for persistent congeners (e.g. PCB 153) and up to 43% for those congeners which are readily metabolised (e.g. PCB 52). Detailed balances for a range of tri- to octa-chlorinated PCBs are presented and clearly demonstrate that many congeners are metabolised effectively by lactating dairy cows (e.g. PCB 149) whilst others are efficiently transferred to human dairy food products. An approach to predicting the degree of metabolism for individual PCB congeners is presented which gives good agreement with observations.     

Occurrence and behavior of wastewater indicators in the Santa Ana River and the underlying aquifers.

The occurrence and behavior of wastewater indicator compounds in the Santa Ana River (SAR) water and the underlying aquifer recharged by the SAR has been studied. The SAR contains a high proportion of tertiary treated wastewater effluents, up to 100% during summer and fall. The following water quality parameters were quantified: four specific wastewater indicator compounds, ethylene diaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), a naphthalene dicarboxylate (NDC) isomer, alkylphenol polyethoxy carboxylates (APECs), and selected haloacetic acids (HAAs), nitrate, dissolved oxygen (DO), DOC, total carbohydrate, and phenolic substances. Statistical analysis indicated that normal distribution was adequate to describe the probability distribution of the constituents in most cases. In the river, the concentrations of wastewater indicator compounds decreased as the fraction of storm runoff increased. EDTA and NDC were detected in a monitoring well near the river and in two production wells 1.8 and 2.7 km down gradient with little apparent attenuation. By contrast, NTA, APECs, bromochloro- and dibromoacetic acids appeared to be attenuated significantly during infiltration of river water and groundwater transport.     

Distribution in Portugal of some pollutants in the lichen Parmelia sulcata

During the months of July and August 1993 a lichen (Parmelia sulcata Taylor) collection campaign was held in Portugal where samples were obtained from olive tree bark at 228 sites, following a grid of 10 x 10 km along the Atlantic coast and 50 x 50 km in the interior of the country. The samples were analysed by instrumental neutron activation analysis and proton induced X-ray emission techniques. Concentration data patterns for the pollutants As, Cr, Hg, Ni, Pb, S, Sb, Se, and V were obtained for the whole country surface by making use of an extinction rule of 1/r(3), preventing any cut-off distance from being artificially introduced. Some pollution sources were identified: (1) oil-powered plants on the Lisbon-Setúbal axis (V, Ni), (2) coal-power plants in Porto and Sines (S, Se), (3) traffic in the northern area and the Lisbon-Setúbal axis (Pb), (4) a chemical industry south of Porto (Hg, As), and (5) soil influence (Cr, Sb). Arsenic and chromium results largely exceed, in a few areas, the concentrations acceptable to plants, and in a few spots also Hg, Ni, and Pb data.     

Tracing sources of atmospheric sulphur using epiphytic lichens

The overall objective of this work was to measure the spatial variation of sulphur isotopic composition of lichens across the island of Newfoundland in order to assess the degree to which the atmosphere is being affected by long-range transport of anthropogenic sulphur from eastern North America, and/or local pollution sources. A contour map (based on over 80 composite samples of the lichen Alectoria sarmentosa) illustrates the spatial distribution of sulphur isotopic composition of the Newfoundland atmosphere. It shows a gradient of delta(34)S of sulphur in lichen, decreasing from the coast to the interior of the island. It also shows local anomalies corresponding to the city of St. John's, the Come-By-Chance Oil Refinery, mining areas and fossil-fuel powered pulp and paper mills in central and western Newfoundland. The study strongly suggests that the isotopic composition of sulphur in the Newfoundland atmosphere is influenced more by the ocean (sea salt sulphate) and local anthropogenic activities in the province, than by long-range transport of continental North American sulphate.     

Vanadium contamination and the relation between vanadium and other elements in wild birds

There is little information on vanadium (V) contamination in wildlife. In the present study, the mean V contents in liver and kidney from 41 wild Japanese water birds were less than 3.69 and 8.11 microg/g dry wt, respectively. The V contents in the liver and kidney of the spotbill duck were more than two times higher than those of other species in Japan. Spotbill ducks obtained in a residential district had a strong correlation between the V contents in the kidneys and those in the livers (R=0.924), and also between V and Ti, Cd, and Li contents in the liver (R>0.8). These results suggest that V accumulation in wild birds reflects the degree of environmental contamination.     

Interactive effects of ozone and elevated carbon dioxide on the growth and physiology of black cherry, green ash, and yellow-poplar seedlings

Potted seedlings of black cherry (Prunus serotina Ehrh.) (BC), green ash (Fraxinus pennsylvanica Marsh.) (GA), and yellow-poplar (Liriodendron tulipifera L.) (YP) were exposed to one of the four treatments: (1) charcoal-filtered air (CF) at ambient CO(2) (control); (2) twice ambient O(3) (2 x O(3)); (3) twice ambient CO(2) (650 microl l(-1)) plus CF air (2 x CO(2)); or (4) twice ambient CO(2) (650 microl l(-1)) plus twice ambient O(3) (2 x CO(2) + 2 x O(3)). The treatments were duplicated in eight continuously stirred tank reactors for 10 weeks. Gas exchange was measured during the last 3 weeks of treatment and all seedlings were destructively harvested after 10 weeks. Significant interactive effects of O(3) and CO(2) on the gas exchange of all three species were limited. The effects of elevated CO(2) and O(3), singly and combined, on light-saturated net photosynthesis (A(max)) and stomatal conductance (g(s)) were inconsistent across species. In all three species, elevated O(3) had no effect on g(s). Elevated CO(2) significantly increased A(max) in GA and YP foliage, and decreased g(s) in YP foliage. Maximum carbon exchange rates and quantum efficiencies derived from light-response curves increased, while compensation irradiance and dark respiration decreased in all three species when exposed to 2 x CO(2). Elevated O(3) affected few of these parameters but any change that was observed was opposite to that from exposure to 2 x CO(2)-air. Interactive effects of CO(2) and O(3) on light-response parameters were limited. Carboxylation efficiencies, derived from CO(2)-response curves (A/C(i) curves) decreased only in YP foliage exposed to 2 x CO(2)-air. In general, growth was significantly stimulated by 2 x CO(2) in all three species; though there were few significant growth responses following exposure to 2 x O(3) or the combination of 2 x CO(2) plus 2 x O(3). Results indicate that responses to interacting stressors such as O(3) and CO(2) are species specific.     

The variability and intrinsic remediation of a BTEX plume in anaerobic sulphate-rich groundwater

Data from long-term groundwater sampling, limited coring, and associated studies are synthesised to assess the variability and intrinsic remediation/natural attenuation of a dissolved hydrocarbon plume in sulphate-rich anaerobic groundwater. Fine vertical scale (0.25- and 0.5-m depth intervals) and horizontal plume-scale (>400 m) characteristics of the plume were mapped over a 5-year period from 1991 to 1996. The plume of dissolved BTEX (benzene, toluene, ethylbenzene, xylene) and other organic compounds originated from leakage of gasoline from a subsurface fuel storage tank. The plume was up to 420 m long, less than 50 m wide and 3 m thick. In the first few years of monitoring, BTEX concentrations near the point of leakage were in approximate equilibrium with non-aqueous phase liquid (NAPL) gasoline. NAPL composition of core material and long-term trends in ratios of BTEX concentrations in groundwater indicated significant depletion (water washing, volatilisation and possibly biodegradation) of benzene from residual NAPL after 1992. Large fluctuations in BTEX concentrations in individual boreholes were shown to be largely attributable to seasonal groundwater flow variations. A combination of temporal and spatial groundwater quality data was required to adequately assess the stationarity of plumes, so as to allow inference of intrinsic remediation. Contoured concentration data for the period 1991 to 1996 indicated that plumes of toluene and o-xylene were, at best, only partially steady state (pseudo-steady state) due to seasonal groundwater flow changes. From this analysis, it was inferred that significant remediation by natural biodegradation was occurring for BTEX component plumes such as toluene and o-xylene, but provided no conclusive evidence of benzene biodegradation. Issues associated with field quantification of intrinsic remediation from groundwater sampling are highlighted. Preferential intrinsic biodegradation of selected organic compounds within the BTEX plume was shown to be occurring, in parallel with sulphate reduction and bicarbonate production. Ratios of average hydrocarbon concentrations to benzene for the period 1991 to 1992 were used to estimate degradation rates (half-lives) at various distances along the plume. The estimates varied with distance, the narrowest range being, for toluene, 110 to 260 days. These estimates were comparable to rates determined previously from an in situ tracer test and from plume-scale modelling.