Analytical and sampling constraints in ²¹°Pb dating.

²¹°Pb dating provides a valuable, widely used means of establishing recent chronologies for sediments and other accumulating natural deposits. The Constant Rate of Supply (CRS) model is the most versatile and widely used method for establishing ²¹°Pb chronologies but, when using this model, care must be taken to account for limitations imposed by sampling and analytical factors. In particular, incompatibility of finite values for empirical data, which are constrained by detection limit and core length, with terms in the age calculation, which represent integrations to infinity, can generate erroneously old ages for deeper sections of cores. The bias in calculated ages increases with poorer limit of detection and the magnitude of the disparity increases with age. The origin and magnitude of this effect are considered below, firstly for an idealized, theoretical ²¹°Pb profile and secondly for a freshwater lake sediment core. A brief consideration is presented of the implications of this potential artefact for sampling and analysis.

Human teeth as historical biomonitors of environmental and dietary lead: some lessons from isotopic studies of 19th and 20th century archival material.

The lead isotopic composition of various sections (crown, crown base, root) of teeth was determined in specimens collected from 19th century skulls preserved in museum collections and, upon extraction or exfoliation, from humans of known ages residing in Scotland in the 1990s. For most 20th century samples, calculation of accurate crown-complete or root-complete dates of tooth formation ranging from the 1920s to the 1990s enabled comparison of (206)Pb/(207)Pb ratios for teeth sections (crown base root) with corresponding decadally averaged data for archival herbarium Sphagnum moss samples. This showed that the teeth sections had been significantly influenced by incorporation of non-contemporaneous (more recent) lead subsequent to the time of tooth formation, most probably via continuous uptake by dentine. This finding confirmed that separation of enamel from dentine is necessary for the potential of teeth sections as historical biomonitors of environmental (and dietary) lead exposure at the time of tooth formation to be realised. Nevertheless, the mean 19th century value of 1.172+/-0.007 for the (206)Pb/(207)Pb ratio in teeth was very similar to the corresponding mean value of 1.173+/-0.004 for 19th century archival moss, although relative contributions from environmental sources - whether direct, by inhalation/ingestion of dust contaminated by local lead smelting ((206)Pb/(207)Pb~1.17) and coal combustion ((206)Pb/(207)Pb~1.18) emissions, or indirect, through ingestion of similarly contaminated food - and drinking/cooking water contaminated by lead pipes of local origin, cannot readily be determined. In the 20th century, however, the much lower values of the (206)Pb/(207)Pb ratio (range 1.100-1.166, mean 1.126+/-0.013, median 1.124) for the teeth collected from various age groups in the 1990s reflect the significant influence of imported Australian lead of lower (206)Pb/(207)Pb ratio (~1.04) and released to the environment most notably through car-exhaust emissions arising from the use of alkyl lead additives ((206)Pb/(207)Pb~1.06-1.09) in petrol in the U.K. from ca. 1930 until the end of the 20th century.

The implications of integrated assessment and modelling studies for the future remediation of chromite ore processing residue disposal sites.

Chromite ore processing residue (COPR) waste from a former chromium chemical works (1830-1968) is still contaminating groundwater in Glasgow, Scotland, with carcinogenic hexavalent chromium, Cr(VI). An integrated analytical, experimental and modelling approach has identified and accounted for mineral phases and processes responsible for the retention and release of Cr(VI) under prevailing field conditions. Both the nature of mineral phase retention and the buffered high pH of the sites, however, militate against direct remediative treatment of the source material, for example by the application of generic methods (e.g. FeSO4) that have been successfully employed elsewhere for the reduction of Cr(VI) to Cr(III) in other matrices. The interception and treatment of groundwater to remove Cr(VI) and the capping of sites to reduce human exposure to airborne Cr(VI)-contaminated dust may well be more realistic and effective, at least in the short to medium term.

Investigation of extraction and clean-up procedures used in the quantification and stable isotopic characterisation of PAHs in contaminated urban soils.

Four different extraction methods, soxhlet, soxtherm, sonication and accelerated solvent extraction (ASE), were used to isolate the 16 priority pollutant PAHs from a certified reference soil (LGC 6140) and from a contaminated soil (BG CLR 17). Based on SIM-GC-MS results, all methods were found to give accurate and highly reproducible concentration data. There was, however, significant between-method and sometimes within-method variability in the stable carbon isotope signatures obtained for individual PAHs from the contaminated soil (BG CLR 17) using GC-C-IRMS. When two clean-up procedures, silica/dichloromethane and alumina/hexane/toluene, were used to remove co-extracted material, however, it was found that ASE gave the more consistent and reproducible stable carbon isotope data. These findings are likely to be of importance for the characterisation of natural and anthropogenic organic matter and, in particular, in source identification and apportionment studies.

Isotopic characterisation of the historical lead deposition record at Glensaugh, an organic-rich, upland catchment in rural N.E. Scotland.

As part of a wider investigation of the biogeochemistry and fate of Pb deposited from the atmosphere at Glensaugh, a rural upland catchment in N.E. Scotland, the concentration and isotopic composition of Pb were determined in four thinly sectioned monolith cores (25 cm) of peat collected at altitudes of 426--434 m from different faces of Thorter Hill and in a series of 21 10-cm unsectioned cores of peat and organic-rich soil along a transect from near the top (434 m) to the bottom (224 m) of the catchment. Depth profiles of Pb concentration and (206)Pb/(207)Pb ratio were similar for the longer cores. Subsurface Pb maxima (238--489 mg kg(-1)) typically occurred below (206)Pb/(207)Pb minima (1.123-1.134). One core was (210)Pb-dated and had a fairly constant (206)Pb/(207)Pb value of 1.170 from mid-19th century to ca. 1930, followed by a decline (attributable to the increasing influence of Australian Pb of much lower (206)Pb/(207)Pb ratio) to 1.134 by the early 1990s, and then a rapid increase to 1.160 by 2002, after the phased withdrawal of leaded petrol. The fluxes of Pb increased from 15 mg m(-2) year(-1) in the late 19th century to a peak of 60 mg m(-2) year(-1) ca. 1960, before declining steadily to 3.6 mg m(-2) year(-1) by the beginning of the 21st century. Some 40% of the anthropogenic Pb in the core had been deposited prior to 1900. The mean anthropogenic Pb inventory of the four longer cores was 7.4+/-1.5 g m(-2), of which approximately 70% occurred in the top 10 cm, in good agreement with the inventories of the shorter cores collected above 400 m. These inventories are higher than those of the industrial central belt of Scotland, probably because of enhanced deposition at altitude. This is consistent with the derived average (210)Pb flux of 198+/-11 Bq m(-2) year(-1), which is twice that of typical UK (210)Pb deposition and the rainfall for the site. The past deposition of Pb at Glensaugh, including that from sources (e.g., smelting, coal combustion) other than leaded petrol, has clearly been considerable. Even since the introduction of leaded petrol ca. 1930, car-exhaust emissions may have accounted for no more than 35% of the Pb deposited.

Over one hundred years of trace metal fluxes in the sediments of the Pearl River Estuary, South China.

The rapid economic development in the Pearl River Delta (PRD) region in South China in the last three decades has had a significant impact on the local environment. Estuarine sediment is a major sink for contaminants and nutrients in the surrounding ecosystem. The accumulation of trace metals in sediments may cause serious environmental problems in the aquatic system. Thirty sediment cores were collected in the Pearl River Estuary (PRE) in 2000 for a study on trace metal pollution in this region. Heavy metal concentrations and Pb isotopic compositions in the four 210Pb-dated sediment cores were determined to assess the fluxes in metal deposits over the last one hundred years. The concentrations of Cu, Pb and Zn in the surface sediment layers were generally elevated when compared with the sub-surface layers. There has been a significant increase in inputs of Cu, Pb and Zn in the PRE since the 1970s. The results also showed that different sampling locations in the estuary received slightly different types of inputs. Pb isotopic composition data indicated that the increased Pb in the recent sediments was of anthropogenic origin. The results of trace metal influxes showed that about 30% of total Pb and 15% of total Zn in the sediments in the 1990s were from anthropogenic sources. The combination of trace metal analysis, Pb isotopic composition and 210Pb dating in an estuary can provide vital information on the long-term accumulation of metals in sediments.

Development of an ombrotrophic peat bog (low ash) reference material for the determination of elemental concentrations.

Given the increasing interest in using peat bogs as archives of atmospheric metal deposition, the lack of validated sample preparation methods and suitable certified reference materials has hindered not only the quality assurance of the generated analytical data but also the interpretation and comparison of peat core metal profiles from different laboratories in the international community. Reference materials play an important role in the evaluation of the accuracy of analytical results and are essential parts of good laboratory practice. An ombrotrophic peat bog reference material has been developed by 14 laboratories from nine countries in an inter-laboratory comparison between February and October 2002. The material has been characterised for both acid-extractable and total concentrations of a range of elements, including Al, As, Ca, Cd, Cr, Cu, Fe, Hg, Mg, Mn, Na, Ni, P, Pb, Ti, V and Zn. The steps involved in the production of the reference material (i.e. collection and preparation, homogeneity and stability studies, and certification) are described in detail.

Role of quantitative mineralogical analysis in the investigation of sites contaminated by chromite ore processing residue.

A range of techniques, normally associated with mineralogical studies of soils and sediments, has been used to characterise the solid materials found on sites contaminated with chromite ore processing residue (COPR). The results show that a wide range of minerals are present, many of which are found extensively in high-temperature synthetic systems such as cements and clinkers and their low temperature hydration products. Thus, the minerals in COPR can be divided into three main categories: unreacted feedstock ore (chromite); high temperature phases produced during chromium extraction (brownmillerite, periclase and larnite); and finally, minerals formed under ambient weathering conditions on the disposal sites (brucite, calcite, aragonite, ettringite, hydrocalumite, hydrogarnet). Apart from chromite, chromium occurs in brownmillerite, ettringite, hydrocalumite and hydrogarnet. Detailed study of the chemistry and stoichiometry of chromium-bearing phases in conjunction with phase abundance provides a quantitative description of the solid state speciation of Cr(III) and Cr(VI) in and amongst these minerals and in the COPR as a whole. Of the total chromium present in the samples most, approximately 60-70% is present as Cr(III) in chromite, whilst brownmillerite also represents a significant reservoir of Cr(III) which is approximately 15% of the total. The remaining chromium, between 20 and 25%, is present as Cr(VI) and resides mainly in hydrogarnet, and to a slightly lesser extent in hydrocalumite. In the latter, it is present principally in an exchangeable anionic form. Chromium (VI) is also present in ettringite, but quantitatively ettringite is a much less important reservoir of Cr(VI), accounting for approximately 3% of total chromium in one sample, but less than 1% in the other two. This description provides insight into the processes likely to control the retention and release of Cr(VI) from COPR-contaminated sites. Such information is of particular value in chemical modelling of the system, in risk assessment and in the development of methods of informed remediation.

Stable lead isotopic characterisation of the historical record of environmental lead contamination in dated freshwater lake sediment cores from northern and central Scotland.

Sediment cores from three Scottish freshwater lakes, Loch Ness in the remote north and Loch Lomond and the Lake of Menteith, much closer to the heavily populated and industrialised central belt were analysed for 210Pb, 137Cs, Pb and stable Pb isotopic composition (206Pb/207Pb). The radionuclide data were used to establish chronologies for the Loch Ness and Loch Lomond cores, but a chronology could not be developed for the Lake of Menteith core, in which the surface sediment had been subject to intense mixing. Although Pb concentrations generally started increasing during the mid-17th Century, a small peak occurred for Loch Ness in the early 16th Century, perhaps attributable to the influence of medieval mining and smelting in mainland Europe. Temporal trends in the pattern of Pb accumulation were similar for Loch Ness and both sites in Loch Lomond, with 40-50% of the anthropogenic Pb deposited prior to the 20th Century. Fluxes of anthropogenic Pb to the lake sediments peaked during the 1950s at all locations where chronologies could be established. The 5-fold increase in anthropogenic Pb inventory for the southern basin of Loch Lomond relative to Loch Ness reflected geographical proximity to the main polluting sources. The 206Pb/207Pb data for anthropogenic Pb in the sediments from Loch Ness and Loch Lomond exhibited largely similar trends related to five different time periods. Pre-1820, the 206Pb/207Pb ratio was close to that for coal (1.181). From 1820 to 1900, a fairly constant 206Pb/207Pb ratio of approximately 1.17 probably resulted from a combination of emissions from the smelting of indigenous Pb ore (1.170) and coal burning (1.181) in Scotland, and industrial activity to the south in England, where Australian Pb of characteristically low 206Pb/207Pb ratio (1.04) was already in use. From 1901 to 1930, the 206Pb/207Pb ratio declined by <0.01, due to the increasing influence of Australian Pb. From 1931 to 1975/1985, the 206Pb/207Pb ratio of anthropogenic Pb declined by a further 0.03 to 0.04, to minimum values from approximately 1975 to 1985, primarily a consequence of car-exhaust emissions of Pb arising from the introduction of alkyl Pb petrol additives (206Pb/207Pb approximately 1.06-1.09). From 1975/1985 to the mid-1990s, the 206Pb/207Pb ratio of anthropogenic Pb increased by up to 0.015, a consequence of a reduction in car-exhaust emissions of Pb, resulting from reductions in the maximum permitted concentration of Pb in petrol, and the introduction and increasing uptake of unleaded petrol. Source apportionment calculations, on the basis of 206Pb/207Pb values in surface sediment, suggested that the contribution of Pb emissions from the use of leaded petrol was 27-40% of the atmospheric burden by the mid-1990s, in line with estimates from rainwater 206Pb/207Pb data.

Matrix effects in applying mono- and polyclonal ELISA systems to the analysis of weathered oils in contaminated soil.

Commercial mono- and polyclonal enzyme-linked immunosorbent assay (ELISA) systems were applied to the on-site analysis of weathered hydrocarbon-contaminated soils at a former integrated steelworks. Comparisons were made between concentrations of solvent extractable matter (SEM) determined gravimetrically by Soxhlet (dichloromethane) extraction and those estimated immunologically by ELISA determination over a concentration range of 2000-330,000 mg SEM/kg soil dry weight. Both ELISA systems tinder-reported for the more weathered soil samples. Results suggest this is due to matrix effects in the sample rather than any inherent bias in the ELISA systems and it is concluded that, for weathered hydrocarbons typical of steelworks and coke production sites, the use of ELISA requires careful consideration as a field technique. Consideration of the target analyte relative to the composition of the hydrocarbon waste encountered appears critical.

The changing nature of the 206Pb/207Pb isotopic ratio of lead in rainwater, atmospheric particulates, pine needles and leaded petrol in Scotland, 1982-1998.

The inductively coupled plasma-mass spectrometry (ICP-MS)-determined 206Pb/207Pb ratio of 145 samples of rainwater collected at 25 locations around Scotland during December 1997 and January 1998 and at three longterm monitoring stations in the northeast, central belt and southeast of the country from November 1997 to December 1998 averaged 1.144+/-0.017 (1 s). This represents a significant increase from the mean value of 1.120+/-0.016 recorded for the long-term sites in 1989 1991, only partly attributable to a concomitant increase in the 206Pb/207Pb ratio of leaded petrol from 1.075+/-0.013 to 1.088+/-0.007. The rainwater 206Pb/207Pb data for the late 1990s also contrast markedly with the lower 206Pb/207Pb ratios found for pine needle and atmospheric particulate samples from Scotland (e.g. Glasgow: 1.085+/-0.012 in 1985-1986, 1.099+/-0.007 in 1991-1992), England and Western Europe in this study for the period 1982-1992 when emissions of lead to the atmosphere from petrol-engined vehicles in the UK were approximately 2-9 times higher. The observed change in the lead isotopic signature of rainwater predominantly reflects the impact of measures, such as the introduction and growing uptake of unleaded petrol, to reduce car exhaust emissions of lead to the atmosphere in the UK. Based on the rainwater data, source apportionment calculations suggest a general decline in the contribution of leaded petrol to atmospheric lead in Scotland from 53-61% in 1989-1991 to 32-45% in 1997-1998, with a corresponding decline in the urban environment from 84-86% to 48-58%.

Isotopic ratios of lead in contemporary environmental material from Scotland.

Lead emitted into the environment, primarily from the combustion of leaded petrol and industrial activities, retains the isotopic signature of the ore(s) from which it is derived. Leaded petrol, atmospheric particulates and street dust sampled in central Edinburgh between February 1989 and December 1991 had mean(206)Pb/(207)Pb ratios of 1.082 ± 0.024, 1.092 ± 0.011 and 1.109 ± 0.016 respectively. These isotope ratios were found to be depleted in(206)Pb compared with a mean of 1.160 ± 0.012 for tap water in contact with lead pipes and %typical ratios of 1.17-1.19 for British lead ore deposits and coal. Paint, with an observed wide range of 20 Pb(207) Pb ratios (1.083-1.183), appears to have significantly influenced house dust and some street dust(206)Pb(207) values. Such overlaps and influences may hinder the quantitative apportionment, via isotope data, of source and route in general population surveys of human exposure to lead.

Distribution and behaviour of radiocaesium in Scottish freshwater loch sediments.

The distribution and behaviour of radiocaesium have been studied in the sediments of two contrasting freshwater lochs: Round Loch of Glenhead, an acidified loch in south-west Scotland, with organic-rich sediments (≈20%C) and Loch Lomond, 35 km north-west of Glasgow, where sediments are low in organic matter (1-6%C, southern basin), but with a relatively high clay content.In the sediments of Scottish freshwater lochs,(137)Cs [half life (t1/2) = 30.23 yr] originates from fallout from nuclear weapons' testing (1950s and 1960s) and from the Chernobyl reactor accident in 1986, which is also the source of the shorter-lived(134)Cs [half life (t1/2) = 2.05 yr]. Use of the characteristic(134)Cs/(137)Cs activity ratio of radiocaesium emitted from Chernobyl enables resolution of sedimentary radiocaesium profiles into the two component sources.In the organic-rich sediment of Round Loch, downward diffusion of radiocaesium in porewaters obscures its pattern of input to the loch. In the more clay-rich sediments of Loch Lomond, separate radiocaesium concentration peaks, related to atmospheric deposition maxima, are clearly discernible, although an influence of partial mixing is apparent. While the derived Chernobyl fallout inventory of radiocaesium in Round Loch sediments is broadly comparable with that for Loch Lomond, the corresponding weapons testing inventory is an order of magnitude lower than in Loch Lomond. Although Round Loch is situated in an area of known elevated Chernobyl deposition, the inventory is much lower than literature values of atmospheric deposition, indicating significant loss of radiocaesium from this loch. The weapons testing inventory in Round Loch is also lower than reported estimates, whereas in Loch Lomond the established inventories from both sources are similar to, or greater than, fallout deposition. The differences between the distribution and inventories in the two lakes confirms that radiocaesium is much less efficiently bound and is correspondingly much more mobile in the organic sediments of Round Loch of Glenhead than in the more clay-rich sediments of Loch Lomond.

Relative changes in salivary Na+ and K+ concentrations relating to stress induction.

Three independent studies are reported in which periods of "relaxation" (A) and presumed stressors (B) were given to female students in an ABA design. The "stressors" were: (1) obligatory time-wasting activity; (2) a mental "IQ" test; and (3) delivering a speech. Saliva was collected immediately after "relaxation" and "stress" periods. "Stress" and "arousal" state were retrospectively assessed in experiments (1) and (2) by subject self-rating and in experiment 1 also by trained observers for the periods A and B. The molar [K+/Na+] ratio was determined for each saliva sample. The prediction that [K+/Na+] would increase with stress induction was supported by statistically significant results with stressors 1 and 2 (p less than 0.01), but speech delivery (3) resulted in a significant rise of [K+/Na+] after the stressor period. Correlations between [K+/Na+] and "stress" and "arousal" ratings also substantiated the prediction.

Successful use of cisplatin to treat metastatic seminoma during cisplatin-induced acute renal failure.

A chemotherapeutic regimen including cisplatin was administered to a man with extragonadal seminoma and cisplatin-induced acute renal failure. Three doses of cisplatin (30, 50, and 100 mg/m2) were given in conjunction with hemodialysis. Pharmacokinetic data for free and total plasma platinum were obtained. The patient also received one dose of carboplatin and a course of radiation therapy. Complete remission was achieved, and useful renal function returned. Cisplatin can be used successfully during acute renal failure.

The perturbation of historical pollution records in aquatic sediments.

It is often claimed that coastal marine and freshwater lake sediments preserve temporal records of anthropogenic input of heavy metals to the environment since the onset of the Industrial Revolution. Growing evidence of perturbatory factors such as physical and biological mixing, other redistributional processes and the early post-depositional diagenetic release and mobility of some elements is reviewed. Fundamental requirements of future studies are outlined.

Aluminium leaching and fluoride.

Aluminium leaching from cooking utensils is a source of dietary aluminium and there are differing reports in the literature concerning the effects of fluoride ions on aluminium leaching. This paper reports that aluminium leaching may be increased by around 5% when fluoride ion at 1 mg/litre is present. More dramatic increases in aluminium leaching occur if the fluoride ion concentration is increased to 20 mg/litre, but this would rarely, if ever, be found in a culinary situation. At fluoride ion concentrations likely to be encountered in cooking, the increased leaching due to fluoride is very small in relation to the effects of pH on aluminium leaching.