749 research outputs found

    Using 206/207Pb isotope ratios to estimate phosphorus sources in historical sediments of a lowland river system

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    Purpose Engineering and dredging strategies to manage sediment, along with river-scouring, can reveal older sediments. These present a unique opportunity to assess past sources of phosphorus (P) inputs into river sediments. We used the sediment concentrations of P, lead (Pb) and 206/207Pb isotopes to produce ‘first-order’ estimates of the source (diffuse agricultural or sewage treatment) of phosphorus. Materials and methods Sediment cores (n = 30) were collected from the length of the non-tidal River Nene, a lowland river in eastern England. Cores were analysed for sediment elemental concentrations and Pb isotopes. Principal component analysis and linear regression modelling were used to assess the relationships between P, Pb and Pb isotopes. Monte-Carlo simulations and boot-strapping were undertaken to estimate, with 95% confidence intervals, the source of P in these sediments. Results and discussion Analysis of the relationships between PTotal, PbTotal and 206/207Pb isotope ratios suggested that sediments were deposited largely prior to the phasing out of tetra-ethyl Pb (PbBHT) from petrol. Regression models showed positive correlations between PTotal and PbTotal (R2 = 0.85). Principal component analysis suggested a strong sewage treatment signal for Pb and P enrichment. In the rural upper three water bodies, little sewage treatment work (STW)-derived P was found in the sediment, a consequence of limited STW input and greater sediment transport. In the more urbanised water bodies 4–6, ‘first-order estimates’ of STW P suggest that median concentrations were 30–40% of PTotal. Conclusions The strong relationships between Pb and P concentrations in river water provided the opportunity to use 206/207Pb isotope ratios to calculate ‘first-order’ estimates of the proportion of P released from STWs in the historical sediment. Understanding the sources of historical sediment P can be used to assess the success of current sediment management strategies and to base further mitigation measures. Results suggest that whilst much recent sediment P is removed, the legacy sediment remains to contribute P to the water body. Thus, options regarding the practical removal of these sediments and the extent to which this would improve water P status need to be assessed and balanced against options such as further decreasing soil P or STW P stripping

    Iodine status of soils, grain crops, and irrigation waters in Pakistan

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    A study was carried out across 86 locations of the country to investigate iodine supply potential of soils, grains and underground waters for onward design of an environmental intervention in Pakistan. Wheat crops were the principal crop in this study since it supplies 75 % of calorific energy in an average Pakistani diet. TMAH-extractable iodine in soils provided a geometric mean of 0.66 µg g−1, far lower than the worldwide mean of 3.0 µg g−1 for soil iodine. Bioavailable (water-extractable) iodine concentration had a geometric mean of 2.4 % (of TMAH-extractable iodine). Median iodine concentrations in tube well sourced waters were 7.3 µg L−1. Median wheat grain-iodine concentrations were 0.01 µg g−1. In most of the grain samples, TMAH-extractable iodine was below detection limit of 0.01 µg g−1. The highest wheat grain iodine was measured on a soil having highest TMAH-extractable iodine. An iodine intake of 25.4 µg a day has been estimated based on median wheat grain iodine measured and groundwater consumption compared to world health organisation (WHO) recommendations of iodine intake of 150 µg a day. This nominal intake of iodine is alarming since 60 % of Pakistani households do not consume iodised salt

    Catchment-scale assessments of the effects of abandoned metal mines on groundwater quality and stream ecology

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    This paper presents an overview of a British Geological Survey catchment-scale research project designed to quantify catchment-derived metal loading on surface water quality. This work is focused on the Rookhope Burn, a tributary of the River Wear in the North Pennines, UK. The river has been identified in the Water Framework Directive (WFD) River Basin Management report as being at risk of failing to achieve Good Status due to mines and minewater pressures. Although geologically relatively simple, the catchment is hydrogeologically complex in that it comprises an area of entrenched karst, characterised by Lower Carboniferous Limestone exposed in the base of valleys overlain by Namurian strata, comprising interbedded shales, sandstones and limestones, which are capped by drained blanket peat. Metal loadings in this catchment result from lead and zinc mineralization and its historic exploitation and processing, which have resulted in both point source and diffuse impacts within the catchment. There have been three main phases of research: (i) collection of hydrological and water chemistry data to enable loading and mass balance calculations to be undertaken; (ii) development of a conceptual understanding of the hydrology and hydrogeology of the catchment, and (iii) application of the hydrological understanding to more recent baseline monitoring of ecological impacts. This work has identified previously unreported mine and groundwater contributions to the catchment, which may have significant implications for the design of remedial measures in the catchment

    Micro-scale geochemical and crystallographic analysis of Buccinum undatum statoliths supports an annual periodicity of growth ring deposition

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    The whelk Buccinum undatum is commercially important in the North Atlantic. However, monitoring the ontogenetic age and growth of populations has been problematic for fisheries scientists owing to the lack of a robust age determination method. We confirmed the annual periodicity of growth rings present in calcified statoliths located in the foot of field-collected and laboratory reared whelks using microscale measurements of trace element geochemistry. Using Secondary Ion Mass Spectrometry (SIMS), annual trace element profiles were quantified at 2 μm resolution in statoliths removed from whelks collected alive from three locations spanning the length of the UK; the Shetland Isles (North), the Menai Strait, North Wales (Mid) and Jersey (South). Clear cycles in the Mg/Ca ratio were apparent with minimum values corresponding with the visible dark statolith rings and comparatively higher ratios displayed in the first year of growth. Statoliths from one and two-year-old laboratory reared whelks of known age and life history contained one and two Mg/Ca cycles respectively and demonstrated that the statolith growth ring is formed during winter (February and March). Cycles of Na/Ca were found to be anti-correlated to Mg/Ca cycles, whilst ratios of Sr/Ca were inconsistent and showed an apparent ontogenetic increase, suggesting strong physiological control. Variability in elemental data will likely limit the usefulness of these structures as environmental recorders. The results obtained using SIMS for trace element analysis of statoliths confirms the robustness of the statolith rings in estimating whelk age. μXRD at 2 μm spatial resolution demonstrated the statoliths were wholly aragonitic and thus trace element variation was not the result of possible differences in CaCO3 polymorph within the statolith. Changing XRD patterns along with SEM imaging also reveal an ‘hourglass’ microstructure within each statolith. The validation of the annual periodicity of statolith growth rings now provides a robust and novel age determination technique that will lead to improved management of B. undatum stocks

    Lability of Pb in soil: effects of soil properties and contaminant source

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    Environmental Context: There is growing concern that lead (Pb) in the environment may cause adverse health effects in human populations. We investigated the combined use of isotopic abundance and isotopic dilution to show how the origins of soil Pb and soil characteristics affect lability. Soil pH and soil Pb content are the dominant controls on Pb lability; the lability of recent petrol-derived Pb is similar to that of other sources in urban soils but greater than geogenic Pb in rural roadside topsoils. Lability of lead (Pb) in soils is influenced by both soil properties and source(s) of contamination. We investigated factors controlling Pb lability in soils from (i) land adjacent to a major rural road, (ii) a sewage processing farm and (iii) an archive of the geochemical survey of London. We measured isotopically exchangeable Pb (E-values; PbE), phase fractionation of Pb by a sequential extraction procedure (SEP) and inferred source apportionment from measured Pb isotopic ratios. Isotopic ratios (206Pb/207Pb and 208Pb/207Pb) of total soil Pb fell on a mixing line between those of petrol and UK coal or Pb ore. The main determinant of the isotopically exchangeable Pb fraction (%E-value) was soil pH: %E-values decreased with increasing pH. In rural roadside topsoils and there was also evidence that, petrol-derived Pb remained more labile (35%) than Pb from soil parent material (27%). However, in biosolid-amended and London soils %E-values were low (c. 25%), covered a restricted range, and showed no clear evidence of source-dependent lability

    Determination of zeolite-group mineral compositions by electron probe microanalysis

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    A new protocol for the quantitative determination of zeolite-group mineral compositions by electron probe microanalysis (wavelength-dispersive spectrometry) under ambient conditions, is presented. The method overcomes the most serious challenges for this mineral group, including new confidence in the fundamentally important Si-Al ratio. Development tests were undertaken on a set of natural zeolite candidate reference samples, representing the compositional extremes of Na, K, Cs, Mg, Ca, Sr and Ba zeolites, to demonstrate and assess the extent of beam interaction effects on each oxide component for each mineral. These tests highlight the variability and impact of component mobility due to beam interaction, and show that it can be minimized with recommended operating conditions of 15 kV, 2 nA, a defocused, 20 μm spot size, and element prioritizing with the spectrometer configuration. The protocol represents a pragmatic solution that works, but provides scope for additional optimization where required. Vital to the determination of high-quality results is the attention to careful preparations and the employment of strict criteria for data reduction and quality control, including the monitoring and removal of non-zeolitic contaminants from the data (mainly Fe and clay phases). Essential quality criteria include the zeolite-specific parameters of R value (Si/(Si + Al + Fe3+), the ‘E%’ charge-balance calculation, and the weight percent of non-hydrous total oxides. When these criteria are applied in conjunction with the recommended analytical operating conditions, excellent inter-batch reproducibility is demonstrated. Application of the method to zeolites with complex solid-solution compositions is effective, enabling more precise geochemical discrimination for occurrence-composition studies. Phase validation for the reference set was conducted satisfactorily with the use of X-ray diffraction and laser-ablation inductively-coupled plasma mass spectroscopy

    Optimisation of a current generation ICP-QMS and benchmarking against MC-ICP-MS spectrometry for the determination of lead isotope ratios in environmental samples

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    © 2018 The Royal Society of Chemistry. Novel ANOVA methodology was used to benchmark ICP-QMS against MC-ICP-MS for Pb isotope ratios, demonstrating "fitness-for-purpose" in environmental source apportionment. The precision and accuracy of lead (Pb) isotope measurements obtained from quadrupole-based mass spectrometers (ICP-QMS) are considered to be limited by a number of factors originating in different components of the instruments. In this study, experimental and instrumental protocols were optimised for determining lead isotope ratios in urban soil digests. Experimental measures included individual dilution of all samples and isotopic standards (SRM-981, NIST) to a single Pb concentration intended to produce an intensity which was high enough to negate blanks and interferences but low enough to ensure the detector operated only in pulse counting mode. Instrumental protocols included batch dead time correction, optimisation of dwell time and the number of scans employed and correction of mass discrimination by sequential application of both internal ( 203 Tl/ 205 Tl ratio) and external (SRM-981, NIST) standards. This optimised methodology was benchmarked against multi-collector mass spectrometer (MC-ICP-MS) measurements of Pb isotope ratios using replicate digest solutions of the same soil; but after these had been subjected to Pb separation using an ion-exchange procedure. On the assumption that MC-ICP-MS measurements are more accurate, small additive and multiplicative differences were observed in only the 4 th decimal place. ANOVA was used to compare the precisions of the two techniques demonstrating equal precisions c. 0.08% for 207 Pb/ 206 Pb, suggesting a sample heterogeneity limitation. By contrast, for 207 Pb/ 204 Pb, the worst-case ratio, ICP-QMS had a 10-fold poorer precision, despite negligible interference from 204 Hg, implying an instrumental limitation. The study concludes that ICP-QMS can provide valuable source apportionment information for most Pb isotope ratios but further efforts should focus on improving assay of the 207 Pb/ 204 Pb ratio

    Calibration of shell δ18O from the common whelk Buccinum undatum highlights potential for environmental reconstruction

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    The common whelk, Buccinum undatum, is a commercially important gastropod found throughout the North Atlantic. One method of age and life history analysis for gastropod species is the use of oxygen isotope ratio (δ18O) measurements from their shells, which is a well-established technique for the reconstruction of historical seawater temperatures at the time of shell biomineralization. Palaeotemperature calibrations have been developed for different types of calcium carbonate as well as species-specific equations to produce the most accurate seawater temperature reconstructions. Here we investigate the four-layer internal structure of B. undatum shells and confirm an aragonite composition using Micro-Raman Spectroscopy (MRS). We then calibrate a species-specific palaeotemperature equation for this gastropod species. This was achieved through the isotopic analysis of shells from laboratory reared specimens of known provenance reared at specific seawater temperatures to produce the following: t(°C) = 14.96 (± 0.15) – 4.94 (± 0.22) x (δ18Oshell – δ18Owater) The calibrated equation differs significantly from previously published data derived from both aragonite and calcite. An offset of 1.04‰ (± 0.41‰) was discovered between observed δ18OShell values and those expected under equilibrium, suggesting a species-specific vital effect. The calibrated equation was used to reconstruct accurate, high resolution historical seawater temperatures from three sites across the U.K. (Shetland, the Menai Strait and Jersey). With this new accurate calibration, both modern and fossil B. undatum shells now have the potential to be employed as high-resolution archives of recent and historical seawater temperature
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