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Biomedical subjects

John G Farmer

Publications and source records attributed to John G Farmer.

11 recordsLinked to original sources

Using size fractionation and Pb isotopes to study Pb transport in the waters of an organic-rich upland catchment.

Processes controlling Pb release from a small organic-rich upland catchment in northeast Scotland were investigated via measurement of Pb concentrations and 206Pb/207Pb ratios in rainwater, throughflow, surface flow, and receiving streamwaters under storm and baseflow conditions. For this catchment, the output of Pb via streams was only 2.0 +/- 1.2 kg year(-1) (11.4 +/- 6.8 g ha(-1) year(-1)), much lower than the input of 7.5 +/- 2.0 kg year(-1) (42.6 +/- 11.4 g ha(-1) year(-1)), and so the catchment is still a sink for anthropogenic Pb. Most (68-87%) of the output, however, occurred under storm conditions. Size fractionation revealed that 50-60% was in large particulate form (>25 microm) with a 206Pb/ 207Pb ratio of approximately 1.16, similar to that of the surface soils. Some 30-40% of the storm Pb output was associated with dissolved organic matter in the <0.45 microm fraction and had a lower 206Pb/207Pb ratio of approximately 1.14, close to the value obtained for near-surface throughflow. Future extreme weather conditions such as prolonged dry or wet periods will increase transport of Pb to receiving waters. Although particulate forms could then rapidly be removed under low flow conditions, Pb associated with dissolved organic matter will persist longer in aquatic systems and may also be more bioavailable.

Environmental Monitoring↗

Identifying source correlation parameters for hydrocarbon wastes using compound-specific isotope analysis.

A preliminary evaluation of compound-specific isotope analysis (CSIA) as a novel, alternative method for identifying source correlation compounds in soils contaminated with residual heavy or weathered petroleum wastes is presented. Oil-contaminated soil microcosms were established using soil (sandy-loam, non-carbonaceous cley) amended with ballast-, crude- or No.6 fuel oil. Microcosms were periodically sampled over 256 days and delta(13)C values (which express the ratio of (13)C to (12)C) determined at each time point for five n-alkanes and the isoprenoid norpristane using gas chromatography-isotope ratio mass spectrometry (GC-IRMS). Although some temporal variation was observed, no significant temporal shifts in the delta(13)C values for the five n-alkanes were measured in all three oils. Isoprenoid isotope ratios (delta(13)C) appeared to be least affected by biotransformation, especially in the No.6 fuel oil. The research suggests that the delta(13)C of isoprenoids such as norpristane, may be of use as source correlation parameters.

Biodegradation, Environmental↗

Calcium polysulfide remediation of hexavalent chromium contamination from chromite ore processing residue.

Past disposal of high-lime chromite ore processing residue (COPR) from a chemical works in S.E. Glasgow, UK, has led to continuing release of toxic and carcinogenic hexavalent chromium (Cr(VI)) to groundwaters which are highly contaminated with Cr(VI)O4(2-). Traditional methods of remediating Cr(VI)-contaminated land, e.g. using ferrous sulfate and organic matter, have had limited success in converting Cr(VI) to less harmful and insoluble Cr(III). This paper describes the first application of calcium polysulfide (CaS(x)) to the remediation of contaminated groundwater and high-lime COPR in a series of laboratory experiments, which have demonstrated the effectiveness of the treatment in quantitatively and rapidly reducing Cr(VI) to Cr(III) over the pH range (8-12.5) typically found at the sites. Cr(III)-organic complexes, present in groundwater at one location, were also effectively precipitated upon treatment with CaS(x). The potential for large-scale use of CaS(x) in the remediation of Cr(VI) from COPR is also discussed.

Calcium Compounds↗

A stable lead isotopic investigation of the use of sycamore tree rings as a historical biomonitor of environmental lead contamination.

The validity of the use of sycamore (Acer pseudoplatanus) tree-rings for the reconstruction of atmospheric lead pollution histories was investigated. Tree cores spanning 1892-2003 were collected from several sycamores from the eastern shore of Loch Lomond, Scotland, an area with no local point sources of lead emission. The lead concentration and 206Pb/207Pb profiles of the Loch Lomond region cores were compared with corresponding data for the 210Pb-dated loch sediment, and also with data for moss of known age from a Scottish herbarium collection. Two of the seven sycamore cores showed the same lead concentration trend as the lead flux to the loch, the rest having no similarity to either each other or the loch sediment record. Two further sycamore cores showed some similarity in their temporal 206Pb/207Pb trends to those seen in the sediment and moss records, but only in part of their profiles, whilst the 206Pb/207Pb ratios of the other sycamore cores remained relatively unchanged for the majority of the time covered, or exhibited an opposite trend. The 206Pb/207Pb ratios of the tree cores were also mostly higher than those of the previously established records for any given time period. Tree cores covering 1878-2002 were also collected along transects from Wanlockhead and Tyndrum, two areas of former lead mining and smelting associated with distinct 206Pb/207Pb ratios of 1.170 and 1.144, respectively. The Wanlockhead tree cores exhibited a generally decreasing trend in lead concentration with both time and distance from the lead mine. The characteristic 206Pb/207Pb ratio of 1.170 was observed in samples close to the mine but a decrease in the influence of the mine-derived lead was observed in more distant samples. The tree sampled at Tyndrum showed elevated lead concentrations, which decreased with time, and a fairly constant 206Pb/207Pb ratio of 1.15 reflecting input from the mine, features not observed in any other trees along the transect. Overall the data suggest that sycamore tree-ring analysis is an unsuitable method for obtaining records of historical lead deposition in areas with no large local lead input, although it can reveal some information about the temporal and spatial influence of point source emitters. The unsuitability probably arises from the number of active annual rings in a single year, the post-uptake radial translocation of elements, the relative importance of the different routes of uptake, and the soil depth(s) from which trees draw nutrients.

Acer↗

A comparison of antimony and lead profiles over the past 2500 years in Flanders Moss ombrotrophic peat bog, Scotland.

Two cores collected in 2001 and 2004 from Flanders Moss ombrotrophic peat bog in central Scotland were dated (14C, 210Pb) and analysed (ICP-OES, ICP-MS) to derive and compare the historical atmospheric deposition records of Sb and Pb over the past 2500 years. After correction, via Sc, for contributions from soil dust, depositional fluxes of Sb and Pb peaked from ca. 1920-1960 A.D., with >95% of the anthropogenic inventories deposited post-1800 A.D. Over the past two centuries, trends in Sb and Pb deposition have been broadly similar, with fluctuations in the anthropogenic Sb/Pb ratio reflecting temporal variations in the relative input from emission sources such as the mining and smelting of Pb ores (in which Sb is commonly present, as at Leadhills/Wanlockhead in southern Scotland), combustion of coal (for which the Sb/Pb ratio is approximately an order of magnitude greater than in Pb ores) and exhaust emissions (Pb from leaded petrol) and abrasion products from the brake linings (Sb from heat-resistant Sb compounds) of automobiles. The influence of leaded petrol has been most noticeable in recent decades, firstly through the resultant minima in Sb/Pb and 206Pb/207Pb ratios (the latter arising from the use of less radiogenic Australian Pb in alkylPb additives) and then, during its phasing out and the adoption of unleaded petrol, complete by 2000 A.D., the subsequent increase in both Sb/Pb and 206Pb/207Pb ratios. The extent of the 20th century maximum anthropogenic enrichment of Sb and Pb, relative to the natural Sc-normalised levels of the Upper Continental Crust, was similar at approximately 50- to 100-fold. Prior to 1800 A.D., the influence of metallurgical activities on Sb and Pb concentrations in the peat cores during both the Mediaeval and Roman/pre-Roman periods was discernible, small Sb and Pb peaks during the latter appearing attributable, on the basis of Pb isotopic composition, to the mining/smelting of Pb ores indigenous to Britain.

Antimony↗

Sequential extraction combined with isotope analysis as a tool for the investigation of lead mobilisation in soils: application to organic-rich soils in an upland catchment in Scotland.

Sequential extraction (modified BCR procedure) combined with isotope analysis has been investigated as a tool for assessing mobilisation of lead into streams at an upland catchment in NE Scotland. The maximum lead concentrations (up to 110 mg kg(-1) in air-dried soil) occurred not at the surface but at about 10 cm depth. The lowest (206)Pb/(207)Pb ratios in any profile occurred, with one exception, at 2.5-5 cm depth. In the one exception, closest to the only road in the area, significantly lower (206)Pb/(207)Pb ratios in the surface soil together with much increased chloride concentrations (in comparison to other surface waters) indicated the possible mobilisation of roadside lead and transfer to the stream. The (206)Pb/(207)Pb ratios in extractable fractions tended at depth towards the ratio measured in the residual phase but the ratios in the oxidizable fraction increased to a value higher than that of the residual phase.

Environmental Monitoring↗

Investigation of the concentration and isotopic composition of inputs and outputs of Pb in waters at an upland catchment in NE Scotland.

As a consequence of the accumulation of anthropogenic Pb in upland catchments, there has been much recent concern about the potential mobilisation and transport of Pb from the soils to receiving waters and also the possible harmful effects that this might have on aquatic biota. This paper presents the findings of a two-year study of Pb behaviour in an organic-rich upland catchment at Glensaugh in NE Scotland. Pb inputs to the catchment were characterised by direct measurements of Pb concentration and (206)Pb/(207)Pb ratios in rain water and interception. Pb outputs from the catchment were calculated from measurements on stream water samples taken from the two main streams, the Cairn Burn and Birnie Burn. The relative contribution of Pb from groundwater and throughflow, under different flow conditions (base flow and high flow), to stream waters was investigated via analysis of springs sourced from groundwater and of waters flowing through the various soil horizons (S (surface), A, B, C, and D), respectively. The outcome of intensive sampling and analysis over the two-year time period was that, even with marked reduction in Pb inputs over the past two decades, the catchment was still acting as a net sink for the current atmospheric deposition. Although the Pb isotopic signature for stream water is very similar to that for the contemporaneous rain water ((206)Pb/(207)Pb approximately 1.15-1.16), only a small portion of the rain water is transferred directly to stream water. Instead, the Pb input is transferred to the stream waters mainly via groundwater and it was also confirmed that the latter had a similar Pb isotopic signature. From the Pb isotopic measurements on throughflow waters, however, Pb being removed via the streams contained some previously deposited Pb, i.e. mobilisation of a small portion of soil-derived anthropogenic Pb was occurring. These findings are important not only with respect to the source/sink status of the catchment but also for calculation of the extent of retention of the current atmospheric Pb inputs, which must take account of the release of previously deposited Pb from the catchment soils, a process occurring mainly under high flow conditions.

Air Pollutants↗

Lake sediments record sensitivity of two hydrologically closed upland lakes in Mexico to human impact.

We provide evidence of rapid, recent environmental change in two lakes in the highlands of central Mexico. Multiple sediment cores were obtained from Lago de Zirahuén (Michoacán) and Laguna de Juanacatlán (Jalisco). Analysis of diatom assemblages, magnetic susceptibility, and metal concentrations was carried out, with the chronology provided by 210Pb dating, 14C dating, and tephrochronology. There is evidence of catchment disturbance during the colonial period in both basins, but the most striking feature at both sites is the rapid change in diatom assemblages during the last 20 y, indicating the onset of eutrophication. Limnological data from Lago de Zirahuén support this interpretation, although none are available from Laguna de Juanacatlán. Paleolimnology is a powerful tool in tracking recent change, particularly in the absence of regular limnological monitoring programs. These lakes appear to be highly sensitive to changes in catchment exploitation, which must be considered in future drainage basin management.

Environmental Exposure↗

Chromium remediation or release? Effect of iron(II) sulfate addition on chromium(VI) leaching from columns of chromite ore processing residue.

Chromite ore processing residue (COPR), derived from the so-called high lime processing of chromite ore, contains high levels of Cr(III) and Cr(VI) and has a pH between 11 and 12. Ferrous sulfate, which is used for remediation of Cr(VI) contamination in wastewater and soils via reduction to Cr(III) and subsequent precipitation of iron(III)/chromium(III) hydroxide, has also been proposed for remediation of Cr(VI) in COPR. Instead, however, addition of FeSO4 to the infiltrating solution in column experiments with COPR greatly increased leaching of Cr(VI). Leached Cr(VI) increased from 3.8 to 12.3 mmol kg(-1) COPR in 25 pore volumes with 20 mM FeSO4, reaching solution concentrations as high as 1.6 mM. Fe(II) was ineffective in reducing Cr(VI) to Cr(III) because it precipitated when it entered the column due to the high pH of COPR, while Cr(VI) in solution was transported away with the infiltrating solution. The large increase in leaching of Cr(VI) upon infiltration of sulfate, either as FeSO4 or Na2SO4, was caused by anion exchange of sulfate for chromate in the layered double hydroxide mineral hydrocalumite, a process for which scanning electron microscopy with energy-dispersive X-ray microanalysis provided direct evidence.

Anions↗

Historical trends in the lead isotopic composition of archival Sphagnum mosses from Scotland (1838-2000).

The analysis of almost 200 Scottish Sphagnum moss samples collected over the past 170 years has revealed trends in the isotopic composition of lead similar to those previously established for dated Scottish lake sediments and peat bogs, lending credibility to these proxy records of atmospheric lead contamination and deposition. The effect of temporal variations in contributions from sources such as smelting of indigenous lead ores (206Pb/207Pb approximately 1.16-1.18), coal combustion (206Pb/207Pb approximately 1.17-1.19), and the use of imported Australian lead (206Pb/207Pb approximately 1.04) was clearly seen in the Scottish moss 206Pb/207Pb record. This showed some differences from the corresponding archival herbage record for the south of England, where the initial influence of Australian lead occurred earlier, at the end of the 19th century. A significant decline from a 206Pb/ 207Pb value of approximately 1.17 in the Scottish moss record began in the 1920s and continued until the 1980s (206Pb/207Pb approximately 1.12). The success of measures to reduce lead emissions to the atmosphere over the past 20 years in the U.K., in particular from petrol-engined vehicles using alkyl lead additives manufactured primarily from Australian lead, is evident in both the increasing 206Pb/207Pb ratio and falling lead concentration data for Scottish moss.

Bryopsida↗

Chromium speciation and fractionation in ground and surface waters in the vicinity of chromite ore processing residue disposal sites.

Chromium concentrations of up to 91 mg l(-1) were found by ICP-OES for ground water from nine boreholes at four landfill sites in an area of S.E. Glasgow/S. Lanarkshire where high-lime chromite ore processing residue (COPR) from a local chemical works had been deposited from 1830 to 1968. Surface water concentrations of up to 6.7 mg l(-1) in a local tributary stream fell to 0.11 mg l(-1) in the River Clyde. Two independent techniques of complexation/colorimetry and speciated isotope dilution mass spectrometry (SIDMS) showed that Cr was predominantly (>90%) in hexavalent form (CrVI) as CrO4(2-), as anticipated at the high pH (7.5-12.5) of the sites. Some differences between the implied and directly determined concentrations of dissolved CrIII, however, appeared related to the total organic carbon (TOC) content. This was most significant for the ground water from one borehole that had the highest TOC concentration of 300 mg l(-1) and at which < 3% of Cr was in the form of CrVI. Subsequent ultrafiltration produced significant decreases in Cr concentration with decreasing size fractions, e.g. <0.45 microm, < 100 kDa, <30 kDa and < 1 kDa by the tangential-flow method. As this appeared related more to concentrations of humic substances than of TOC per se, horizontal bed gel electrophoresis of freeze-dried ultrafilter retentates was carried out to further characterise the CrIII-organic complex. This showed for the main Cr-containing fraction, 100 kDa-0.45 microm, that the Cr was associated with a dark brown band characteristic of organic (humic) matter. Comparison of gel electrophoresis and FTIR results for ultrafilter retentates of ground water from this borehole with those for a borehole at another site where CrVI predominated suggested the influence of carboxylate groups, both in reducing CrVI and in forming soluble CrIII-humic complexes. The implications of this for remediation strategies (especially those based on the addition of organic matter) designed to reduce highly mobile and carcinogenic Cr(VI)O4(2-) to the much less harmful CrIII as insoluble Cr(OH)3 are discussed.

Carcinogens, Environmental↗