Atmospheric deposition of silver and thallium since 12 370 14C years BP recorded by a Swiss peat bog profile, and comparison with lead and cadmium

A peat core from an ombrotrophic bog in Switzerland provides the first complete, long-term record (14 500 years) of atmospheric Ag and Tl deposition. The lack of enrichment of Ag and Tl in the basal peat layer shows that mineral dissolution in the underlying sediments has not contributed measurably to the Ag and Tl inventories in the peat column, and that Ag and Tl were supplied exclusively by atmospheric deposition. The temporal and spatial distribution of modern peaks in Ag and Tl concentrations are similar to those of Pb which is known to be immobile in peat profiles. Silver and Tl, therefore, are effectively immobile in the peat bog also, allowing an atmospheric deposition chronology to be reconstructed. Silver concentrations vary by up to 114x and Tl up to 241x. While Holocene climate change and land use history can explain the variation in metal concentrations and enrichment factors (EF) in ancient peats (i.e. pre-dating the Roman Period), anthropogenic sources have to be invoked to explain the very high EF values (up to 123 in the case of Ag and 12 in the case of Tl) in peat samples since the middle of the 19th Century. The "natural background" EF of Tl in ancient peats is remarkably close to unity, indicating a lack of significant enrichment of this element in atmospheric aerosols due to chemical weathering of crustal rocks. Silver, on the other hand, shows a pronounced enrichment from 8030 to 5230 (14)C years BP (12x compared to crustal rocks); this may be due to weathering phenomena or biological processes, both of which are driven by climate. Even compared to the natural enrichment of Ag during the mid-Holocene, however, the enrichments of Ag and Tl in modern peats from the Industrial Period are at least an order of magnitude greater. The Pb/Ag and Tl/Ag ratios show that Pb and Tl are preferentially released, compared to Ag, during smelting of argentiferous Pb ores mined during the Roman and Medieval Periods.     

A simple,cost-effective multispecies toxicity test using organisms with a cosmopolitan distribution

Difficulties in making accurate, ecosystem-level predictions of environmental effects of chemicals, mixtures, and effluents based solely on the results of tests on single species have necessitated the development of more environmentally realistic, predictive testing methods. This paper describes a multispecies, community-level toxicity test based on the colonization of artificial substrates by microbial species. Tests examined the colonization of initially barren polyurethane foam artificial substrates by Protozoa from a species source colonized in a natural system. Differences in colonization were examined in microecosystems amended with low levels of cadmium, a very toxic heavy metal, and TFM, an organic biocide used against larval sea lamprey. Tests examined differences in colonization over 28 days. For cadmium, effect levels were estimated to be near 1 g 1^–1, in the low range of effect levels determined from chronic single species tests. For TFM, effect levels were estimated to be between 1 and 10 ppm, overlapping the concentrations used in environmental applications. The colonization response, which depends on naked microbial cells reproducing and migrating through toxicant amended water to new substrates, is very sensitive. Tests based on colonization can be adapted to use species from a target receiving system or can use species from a designated natural source. Field validation of these tests can employ nearly identical methods to those used in laboratory studies to assess the accuracy of predictions based on test system data.     

The analysis of monitoring data with the aid of time-series analysis

Methods derived from time-series analysis are proposed for processing monitoring data. The necessity for the use of these methods is demonstrated. In a case study time-series analysis was applied to assess the impact of the closure of the Grevelingen estuary (S. W. Netherlands) in 1971 on a local wintering population of Oystercatchers (Haematopus ostralegus) in the adjacent Oosterschelde estuary.Communication No. 328 of the Delta Institute for Hydrobiological Research.     

Sulfate and conductivity as field indicators for detecting coal-mining pollution

A water quality assessment was conducted on three Appalachian streams polluted by coal mining at the Big South Fork National River and Recreation Area, Tennessee and Kentucky. Results showed that sulfate was an excellent parameter for detecting the effects of coal mining and that sulfate analyses used in conjunction with conductivity readings provided the best detection index. Acidity and pH readings were relatively insensitive indicators, reflecting the mining pollution only after sulfate concentrations already indicated severe pollution levels.Hydrologist, Big South Fork NRRA, during the study; presently at Cape Lookout National SeashoreHydrologist, NPS, during the study; presently with USDA-Forest Service, Washington, DC.     

A study on the behaviour of pesticides and their transformation products in the Scheldt estuary using liquid chromatography-electrospray tandem mass spectrometry

Off-line solid-phase extraction (SPE) combined with liquid chromatography-electrospray tandem mass spectrometry (LC-ESI-MS-MS) was used to study the estuarine behaviour of the polar pesticides, atrazine, chloridazon, diuron and metolachlor, and their transformation products (TPs), hydroxyatrazine (HA), desisopropylatrazine (DIA), desethylatrazine (DEA), 3,4-dichlorophenylmethylurea (DPMU) and monuron. The compounds were identified by comparing their LC retention times and product-ion spectra with those of standard solutions. In all but one case the detection limits of the method were sufficient to determine the compounds of interest over the entire salinity range in the estuary. The concentrations of the dissolved pesticides ranged from 70 ng l-1 for chloridazon to 1350 ng l-1 for diuron. The levels of TPs were 3-8% of the levels of their parent pesticide. The mixing plots of polar pesticides and their TPs indicated that TPs, which are present in fresh river water, are conservatively transported to the sea and that no additional amounts of TPs are formed during their transport through the estuary. The one exception was HA, of which approximately 10% of the amount transported to the North Sea is formed in the lower part of the estuary by photochemical oxidation of atrazine. The latter was concluded from the ratios of each analyte over the sum total of the parent pesticide and all TPs along the salinity gradient, which proved to be a useful tool for identifying such estuarine transformations.     

Evaluating the environmental effects of the GM revolution

In the US, cradle of genetically modified crops, agricultural scientists and regulators are already tackling one environmental issue, and rushing to determine the magnitude of another.     

TPH-contaminated Mexican Refinery Soil: Health Risk Assessment and the First Year of Changes

The soil of a coastal Mexican refinery is quite contaminated, especially by hydrocarbons, with detected concentrations up to 130000 mg kg(-1) as TPHs (total petroleum hydrocarbons). The main sources of contamination are pipelines, valves, and old storage tanks, besides the land disposal of untreated hydrocarbon sediments derived from the cleaning of storage tanks. A health risk assessment (HRA) was carried out in order to measure the risk hazard indexes and clean-up standards for the refinery soil. HRA suggested the following actions to be taken: benzene concentrations must be reduced in eight of the 16 studied refinery zones to 0.0074-0.0078 mg kg(-1). Also, vanadium concentration must be reduced in two zones up to a concentration of 100 mg kg(-1). In only one of all of the studied zones, benzo(a)pyrene concentration must be reduced to 0.1 mg kg(-1). After 1 yr, TPHs showed a diminution of about 52%. Even though TPHs concentrations were variable, during 1999 the average concentrations were as much as 15.5 times the goal concentration. For year 2000, TPHs concentrations were only 7.4-fold the proposed value. For the 1999-2000 period, PAHs (polycyclic aromatic hydrocarbons) concentrations decreased by 82%. Some PAHs with 2, 3, 4, and 5 aromatic rings were removed up to 100% values.     

Paleolimnological assessment of Grove and Plow Shop Ponds, Ayer, Massachusetts, USA--a superfund site

Three sediment cores from each of severely polluted Grove and Plow Shop Ponds, Ayer, Massachusetts, USA, were dated using (210)Pb, characterized for plant macrofossil assemblages, and analyzed for H(2)O, loss-on-ignition, stable Pb isotopes, and concentrations of As, Ca, Cd, Cr, Cu, Fe, Hg, methyl-Hg, Ni, Pb, and Zn. A core from nearby kettle Spectacle Pond, Littleton, Massachusetts, was similarly characterized (except for plant macrofossil assemblages) to assess the regional air pollution signal in sediment for comparison with the six cores. Accumulation rates for metals (mass per area per year), the anthropogenic component (mass per area per year), and total accumulation of the anthropogenic component (mass per area) indicate that As, Cd, Cr, Cu, Hg, methyl-Hg, Ni, Pb, and Zn have accumulated in sediment as a consequence of point source pollution from within the drainage basins of Grove and Plow Shop Ponds. Three distinct sources of pollution are inferred. As is entering Plow Shop Pond via groundwater in the southwest. Cd, Ni, Pb, and Zn are entering the system predominantly at the eastern end of, or upstream from, Grove Pond. Pb also comes from the northwest corner of Grove Pond, the principal source of Cr, Cu, and Hg. These results are consistent with chemistry of modern surface sediments. The history of pollution extends back more than 100 years. Intra- and inter-core variability of concentrations and accumulation rates indicate that much of the pollution was likely in particulate form with little physical redistribution. Recently, concentrations and accumulation rates have generally decreased substantially for those elements present in excessive concentrations in the past. This is a consequence of accumulation of recent, less polluted sediment. In Spectacle Pond, the nearby reference lake, accumulation rates for As, Cd, Hg, and Pb, adjusted for background values and changes in sedimentation rate, increased above background starting in the late 19th century, peaked about 1980, and declined substantially to 2000. These decreases suggest that the anthropogenic (pollution) component of atmospheric deposition of these elements declined after 1980 by at least 50%(As), 80%(Cd), 80%(Hg), and 80%(Pb).     

Suggested protocol for collecting, handling and preparing peat cores and peat samples for physical, chemical, mineralogical and isotopic analyses

For detailed reconstructions of atmospheric metal deposition using peat cores from bogs, a comprehensive protocol for working with peat cores is proposed. The first step is to locate and determine suitable sampling sites in accordance with the principal goal of the study, the period of time of interest and the precision required. Using the state of the art procedures and field equipment, peat cores are collected in such a way as to provide high quality records for paleoenvironmental study. Pertinent field observations gathered during the fieldwork are recorded in a field report. Cores are kept frozen at -18 degree C until they can be prepared in the laboratory. Frozen peat cores are precisely cut into 1 cm slices using a stainless steel band saw with stainless steel blades. The outside edges of each slice are removed using a titanium knife to avoid any possible contamination which might have occurred during the sampling and handling stage. Each slice is split, with one-half kept frozen for future studies (archived), and the other half further subdivided for physical, chemical, and mineralogical analyses. Physical parameters such as ash and water contents, the bulk density and the degree of decomposition of the peat are determined using established methods. A subsample is dried overnight at 105 degree C in a drying oven and milled in a centrifugal mill with titanium sieve. Prior to any expensive and time consuming chemical procedures and analyses, the resulting powdered samples, after manual homogenisation, are measured for more than twenty-two major and trace elements using non-destructive X-Ray fluorescence (XRF) methods. This approach provides lots of valuable geochemical data which documents the natural geochemical processes which occur in the peat profiles and their possible effect on the trace metal profiles. The development, evaluation and use of peat cores from bogs as archives of high-resolution records of atmospheric deposition of mineral dust and trace elements have led to the development of many analytical procedures which now permit the measurement of a wide range of elements in peat samples such as lead and lead isotope ratios, mercury, arsenic, antimony, silver, molybdenum, thorium, uranium, rare earth elements. Radiometric methods (the carbon bomb pulse of (14)C, (210)Pb and conventional (14)C dating) are combined to allow reliable age-depth models to be reconstructed for each peat profile.