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The (4 + 3) cycloaddition of 2-trialkylsilyl-4-alkylbutadienes with an N-methyloxidopyridinium ion affords cycloadducts with high regioselectivity and excellent endo selectivity.

The acid-base relevant molecules carbon dioxide (CO2 ), protons (H+ ), and bicarbonate (HCO3 - ) are substrates and end products of some of the most essential physiological functions including aerobic and anaerobic respiration, ATP hydrolysis, photosynthesis, and calcification. The structure and function of many enzymes and other macromolecules are highly sensitive to changes in pH, and thus maintaining acid-base homeostasis in the face of metabolic and environmental disturbances is essential for proper cellular function. On the other hand, CO2 , H+ , and HCO3 - have regulatory effects on various proteins and processes, both directly through allosteric modulation and indirectly through signal transduction pathways. Life in aquatic environments presents organisms with distinct acid-base challenges that are not found in terrestrial environments. These include a relatively high CO2 relative to O2 solubility that prevents internal CO2 /HCO3 - accumulation to buffer pH, a lower O2 content that may favor anaerobic metabolism, and variable environmental CO2 , pH and O2 levels that require dynamic adjustments in acid-base homeostatic mechanisms. Additionally, some aquatic animals purposely create acidic or alkaline microenvironments that drive specialized physiological functions. For example, acidifying mechanisms can enhance O2 delivery by red blood cells, lead to ammonia trapping for excretion or buoyancy purposes, or lead to CO2 accumulation to promote photosynthesis by endosymbiotic algae. On the other hand, alkalinizing mechanisms can serve to promote calcium carbonate skeletal formation. This nonexhaustive review summarizes some of the distinct acid-base homeostatic mechanisms that have evolved in aquatic organisms to meet the particular challenges of this environment.

Coral calcification is intricately linked to the chemical composition of the fluid in the extracellular calcifying medium (ECM), which is situated between the calcifying cells and the skeleton. Here we demonstrate that the acid-base sensing enzyme soluble adenylyl cyclase (sAC) is expressed in calcifying cells of the coral Stylophora pistillata. Furthermore, pharmacological inhibition of sAC in coral microcolonies resulted in acidification of the ECM as estimated by the pH-sensitive ratiometric indicator SNARF, and decreased calcification rates, as estimated by calcein labeling of crystal growth. These results indicate that sAC activity modulates some of the molecular machinery involved in producing the coral skeleton, which could include ion-transporting proteins and vesicular transport. To our knowledge this is the first study to directly demonstrate biological regulation of the alkaline pH of the coral ECM and its correlation with calcification.

The calcium carbonate skeletons of corals provide the underlying structure of coral reefs; however, the cellular mechanisms responsible for coral calcification remain poorly understood. In osteoblasts from vertebrate animals, a Na+/Ca2+ exchanger (NCX) present in the plasma membrane transports Ca2+ to the site of bone formation. The aims of this study were to establish whether NCX exists in corals and its localization within coral cells, which are essential first steps to investigate its potential involvement in calcification. Data mining identified genes encoding for NCX proteins in multiple coral species, a subset of which were more closely related to NCXs from vertebrates (NCXA). We cloned NCXA from Acropora yongei (AyNCXA), which, unexpectedly, contained a peptide signal that targets proteins to vesicles from the secretory pathway. AyNCXA subcellular localization was confirmed by heterologous expression of fluorescently tagged AyNCXA protein in sea urchin embryos, which localized together with known markers of intracellular vesicles. Finally, immunolabeling of coral tissues with specific antibodies revealed AyNCXA was present throughout coral tissue. AyNCXA was especially abundant in calcifying cells, where it exhibited a subcellular localization pattern consistent with intracellular vesicles. Altogether, our results demonstrate AyNCXA is present in vesicles in coral calcifying cells, where potential functions include intracellular Ca2+ homeostasis and Ca2+ transport to the growing skeleton as part of an intracellular calcification mechanism.

From 1994 onwards, radiocarbon discharges from the Sellafield nuclear fuel reprocessing plant have been made largely to the northeast Irish Sea. They represent the largest contributor to UK and European populations of the collective dose commitment derived from the entire nuclear industry discharges. Consequently, it is important to understand the long-term fate of 14C in the marine environment. Research undertaken in 2000 suggested that the carbonate component of northeast Irish Sea sediments would increase in 14C activity as mollusk shells, which have become enriched in Sellafield-derived 14C, are broken down by physical processes including wave action and incorporated into intertidal and subtidal sediments. The current study, undertaken in 2011, tested this hypothesis. The results demonstrate significant increases in 14C enrichments found in whole mussel shells compared to those measured in 2000. Additionally, in 2000, there was an enrichment above ambient background within only the largest size fraction (>500 μm) of the intertidal inorganic sediment at Nethertown and Flimby (north of Sellafield). In comparison, the present study has demonstrated 14C enrichments above ambient background in most size fractions at sites up to 40 km north of Sellafield, confirming the hypothesis set out more than a decade ago.

Oxidizing conditions normally prevail in surface waters and near-surface groundwaters, but there is usually a change to reducing conditions in groundwater at greater depth. Dissolved O2 originally present is consumed through biogenic and inorganic reactions along the flow paths. Fracture minerals participate in these reactions and the fracture mineralogy and geochemistry can be used to trace the redox front. An important task in the safety assessment of a potential repository for the disposal of nuclear waste in crystalline bedrock, at an approximate depth of 500 m in Sweden, is to demonstrate that reducing conditions can be maintained for a long period of time. Oxygen may damage the Cu canisters that host nuclear waste; additionally, in the event of a canister failure, oxidizing conditions may increase the mobility of some radionuclides. The present study of the near-surface redox front is based on mineralogical (redox-sensitive minerals), geochemical (redox-sensitive elements) and U-series disequilibrium investigations of mineral coatings along open fractures. The fractures have been sampled along drill cores from closely spaced, 100 m deep boreholes, which were drilled during the site investigation work in the Laxemar area, south-eastern Sweden, carried out by the Swedish Nuclear Fuel and Waste Management Co. (SKB). The distribution of the redox-sensitive minerals pyrite and goethite in open fractures shows that the redox front (switch from mainly goethite to mainly pyrite in the fractures) generally occurs at about 15–20 m depth. Calcite leaching by recharging water is indicated in the upper 20–30 m and positive Ce-anomalies suggest oxidation of Ce down to 20 m depth. The U-series radionuclides show disequilibrium in most of the samples, indicating mobility of U during the last 1 Ma. In the upper 20 m, U is mainly removed (due to oxidation) or has experienced complex removal and/or deposition. At depths of 35–55 m, both deposition and removal of U are indicated. Below 55 m, recent deposition of U is generally indicated which suggests removal of U near surface (oxidation) and deposition of U below the redox front. Scattered goethite occurrences below the general redox front (down to ca 80 m) and signs of U removal at 35–55 m mostly correlate with sections of high transmissivity (and/or high fracture frequencies). This shows that highly transmissive fractures are generally required to allow oxygenated groundwaters at depth greater than ca 30 m. Removal of U (oxidation) below 55 m within the last 300 ka is not observed. Although penetration of glacial waters to great depths has been confirmed in the study area, their potential O2 load seems to have been reduced near the surface.

River sediment at a disused lead–zinc mine was analysed to provide an understanding of the chemical nature of the source term for contaminated sediment exported from the site. Changes in concentration and geochemical associations of Pb and Zn were measured using aqua regia digestion and the BCR sequential extraction procedure. Sediment in the immediate vicinity of the mine was highly contaminated with Pb (max. c. 11,000 mg kg −1 ) and Zn (max. c. 30,000 mg kg −1 ), but these values declined rapidly within 1 km of the mine due to dilution and hydraulic sorting. Lead fractionation changed from being predominantly in the reducible fraction to being in the acetic acid-extractable fraction, whereas Zn was predominantly in the residual fraction. This material is transported as fine sediment in the river system.

The well characterised temporal trend in the 206 Pb/ 207 Pb atom ratio of atmospheric lead deposition in Scotland during the 20th century was used to investigate the surface integrity of several cores collected by different methods from Flanders Moss ombrotrophic peat bog, central Scotland, during 1996–2001. Based on 206 Pb/ 207 Pb profile comparisons, in conjunction with identified 210 Pb radionuclide inventory deficits for two of the cores, it was deduced that 25 ± 7 yrs worth of material was missing from the more seriously affected core. After allowing for an appropriate vertical offset based on 206 Pb/ 207 Pb profile matching, the subsequent matching of profiles of titanium, lead, sulfur, arsenic, iron, phosphorus and manganese in three cores for which total concentration data were available was excellent. Without such offset correction, erroneous conclusions could have been drawn concerning the recent historical record of anthropogenic lead and arsenic deposition, the position of the redox boundary, which controls geochemical cycling and enrichment of iron, and the nutrient recycling status of manganese and phosphorus in the near-surface vegetation. Topographic, vegetative and coring (both device and operator) influences may have been responsible, thus endorsing the use of reliable, multiple core sampling and the use of lead isotope ratio profiles, supplemented by appropriate radionuclide data, in both assessing and ensuring the surface integrity of peat cores.

Data from the Tono Uranium Deposit of central Japan were used to develop an improved approach for simulating uranium migration and retardation, while taking into account both long-term environmental changes and uncertainties in data. Based upon extensive field and laboratory investigations, conceptual and numerical models for environmental perturbations, including uplift, subsidence and faulting, were constructed. Model development was based on a novel adaptation of a safety assessment methodology that previously has been applied to radioactive waste repositories. A ‘reference scenario’ was developed using a systems analysis approach. This scenario is a best estimate of how the geological system and the uranium deposit reached their present states and includes descriptions of all major environmental perturbations. Uranium is mobilized from the uppermost Toki granite under relatively oxidizing conditions, and is then transported by groundwater into overlying sedimentary rocks. There, reducing conditions promote uranium deposition. A specially designed numerical model simulated the main features of this scenario. Many simulations were performed to identify key uncertainties to which the timing of ore deposition and uranium distribution are sensitive. A key finding is that retardation of U by processes other than precipitation of discrete U minerals, most probably sorption on solid phases, contributes significantly to the stability of the ore deposit. Sorption could potentially be important for confining the U within the sedimentary rocks in spite of environmental changes such as exhumation and seismic pumping. The approach could be used elsewhere, to assess the safety of deep geological high-level radioactive waste (HLW) disposal. A related application would be at potential future waste disposal sites, to prioritize site characterization so that the most safety-relevant uncertainties are reduced. There are also possible applications in other fields, most notably to assess the implications of alternative ore genetic models.

In response to the increased use of catalytic convertors in motor vehicle exhausts systems, recent studies, employing GF–AAS or ICP–MS analysis of platinum group elements (PGEs), have identified a significant increase of Pt and Pd concentrations in road dust and roadside soils leading to concern over potential effects on human health. After deposition, the PGEs are subject to various physical and chemical transformations, potentially resulting in migration into other environmental compartments i.e. soils, the aquatic system and biota. However, the processes involved are poorly understood and the reactivity, bioavailability, and speciation of the PGEs are ill defined. In contrast to environmental studies, in geochemical research, Isotope Dilution ICP–MS (ID ICP–MS) has primarily been used for the quantification of Pt, providing a significant improvement in accuracy by allowing removal from the analyte solution of elements which could potentially give isobaric interference in the mass spectra. In the present work, an ID ICP–MS analytical technique with a detection limit of 0.1 μg kg−1 has been used for determination of concentrations of Pt in road dust samples from west central Scotland. The study highlights potential interference problems that may occur in analysis of Pt in environmental matrices using ICP–MS. Initial application of ID ICP–MS in a study of roadside environments in west central Scotland has revealed significantly enhanced concentrations of Pt, within the range 13–335 μg kg−1, in road dust samples from a trunk road and motorway, representing a significant increase relative to surface soils in this area that are remote from roads, which have Pt concentrations of less than 1.0 μg kg−1. In contrast, lower levels of contamination of 1.8–11.8 μg kg−1 were observed for dust samples from residential areas, in the town of East Kilbride.

In recent years, the most common technique for radiocarbon dating of deep-ocean sediments has been accelerator mass spectrometry (AMS) analysis of hand-picked planktonic foraminifera (forams). Some studies have exposed age offsets between different sediment size fractions from the same depth within a core and this has important implications when establishing a chronological framework for palaeoceanographic records associated with a particular sediment component. The mechanisms generating the age offsets are not fully understood, a problem compounded by the fact that the fraction defined as “large” varies between different studies. To explore this problem, we dated samples of hand-picked forams from two Biogeochemical Ocean Flux Study (BOFS) cores, for which the presence of an offset between the bulk carbonate and >150 μm foraminiferal calcite had already been demonstrated. The presence of a constant age offset between bulk carbonate and coarse fraction material at the two BOFS sites has been confirmed, but the magnitude of the offset is dependent on whether a simple size-separation technique or hand-picking of well-preserved forams is applied. This may be explained if the selection of well preserved forams biases the sample towards those specimens that have spent least time in the surface mixed layer (SML) or have undergone less size selective mixing. Modeling of the 14C profiles demonstrates that SML depth and sediment accumulation rates are the same for both the bulk and coarse sediment fractions, which is consistent with the hypothesis that size-selective mixing is responsible for the age offset.

Radiocarbon age offsets between foraminifera and bulk carbonate samples were investigated in a sediment core from the western Rockall Plateau in the North East Atlantic. Within the surface mixed layer (SML), foraminifera (forams) ages were significantly younger than those of the bulk sediment at corresponding depths. Below the SML, no significant offset was observed between the two, which is in contrast to previous studies. The absence of an offset below the SML may be the result of advective biological mixing dominating over diffusive mixing in the SML, or the foram size fraction being below the threshold at which size selective mixing becomes active. Within the SML, the sampling strategy may bias the collection of forams towards the youngest specimens at each depth.

An ombrotrophic peat core from west-central Scotland was subjected to multi-element analysis and 210Pb dating in order to estimate historical trends in atmospheric deposition of contaminants. The inferred depositional flux of ash (total inorganic material) exhibited small, transient increases from as early as the mid 18th century, followed by a larger increase from the mid 19th century to a pronounced maximum approx. 1960. A significant decrease was observed from the peak ash deposition of 29.2 g m−2 year−1 to the contemporary level of 11 g m−2 year−1, although this is still an order of magnitude greater than the pre-industrial value of 1 g m−2 year−1. Depositional fluxes of a wide range of elements (scandium, copper, arsenic, antimony, samarium, cobalt, bromine, lanthanum and lead) also exhibited major increases from the mid 19th century and peak values in the mid 20th century (approx. 1940–1950). Aluminium, cerium and bromine also showed evidence of transiently increased deposition as early as the mid 18th century. Normalisation of the concentrations of individual elements to that of aluminium confirmed that the peak depositional fluxes in the mid 20th century were not due to increased re-deposition of soil minerals from the atmosphere, but were attributable to other sources of contamination including heavy industry, coal burning and vehicle exhaust emission. Nevertheless, re-deposited soil minerals were estimated to constitute an important fraction of the ash, with peak input at the start of the 20th century and subsequent deposition at a relatively constant level, about half that of the maximum flux. Excellent agreement was observed between the inferred trends in contaminant deposition and the known history of industrial development of the area.

This paper describes a study of the geochemical associations of Sellafield waste radionuclides in saltmarsh sediments from south-west s]Scotland. The contaminant radionuclides are transported to this environment in association with particulate material and 137Cs was found to be predominantly (80-98%) non-extractable. In the case of 239+240Pu there was a redistribution from the oxalate extractable oxide fraction to the pyrophosphate extractable organic fraction as a consequence of on-shore transfer of contaminated sediment. The relatively aggressive nature of the chemical extractants required to remove the radionuclides from the sediments suggests that they were in a form which was unlikely to result in their being released into the aquatic environment or taken up by plants. Plutonium had a greater potential mobility or bioavailability than Cs. Values of KD for the desorption of 137Cs from the sediment by freshwater, groundwater and seawater were all approximately 105 L kg-1, confirming its immobility in this environment. The desorption KD values for stable 133Cs were all approximately 106 L kg-1, so the stable Cs did not have a significant influence on the radiocaesium in this sediment.

Alpha/beta separation is achieved by the use of pulse shape discrimination (PSD), calibrated by quantifying event misclassification at any given setting for pure α and β emitters. Previous studies have shown that the degree of misclassification is affected by quenching, but with no attempt made to understand the causes for this phenomenon. This study examines the potential effects of β energy and quench on PSD calibration. PSD was shown to be energy dependent, with misclassification increasing with β event energy. Therefore, PSD calibration requires the use of a β emitter with the same energy distribution as is present in the sample, or a restricted region of interest should be employed. For gross α/gross β analysis of samples containing unknown β emitters, a stepwise calibration procedure is proposed for both PSD and efficiency calibration. Quenching by carbon tetrachloride, nitromethane and 9 M hydrochloric acid was shown to affect PSD by suppression of the delayed component of the scintillation pulse, although to variable extents, and therefore having a range of effects on misclassification. Acetone quenching had little impact on PSD. Standard quench calibration procedures using either carbon tetrachloride or nitromethane are inappropriate for applications utilising α/β separation by PSD. Instead, a quench calibration procedure based on overspiking samples encompassing a range of quench conditions is recommended. The influence of oxygen quenching on PSD was investigated through purging samples with either oxygen or nitrogen. PSD was found to be unaffected by the small amounts of oxygen normally dissolved in the diisopropylnaphthalene based cocktail used in this study.

Plutonium-239,240 activities in seawater from the north-east Irish Sea, collected in January 1992, were in the range of 0.17–4.30 mBq l−1 in solution and 7.2–62.3 Bq kg−1 in suspended particulates. The 238Pu:239,240Pu activity ratios for the soluble fraction were consistent with those of the underlying sediments but inconsistent with contemporary discharges from Sellafield, indicating that most of the plutonium in solution was derived from re-dissolution from the sediment. The activity ratios for the particle associated material were more variable, but again, on average, typical of the sediments. The annual loss of 239,240Pu from the north-east Irish Sea in solution was estimated to be 1.19 TBq and that associated with suspended particulates to be 0.11 TBq. From this, a halving time of 350 years for the loss of 239,240Pu activity from the sediment by dissolution was determined. A similar treatment of 137Cs data yielded an annual loss of 86 TBq in solution and a halving time of 23 years. Calculations using a numerical model of the Irish Sea yielded similar estimates of current loss rates and permitted the estimation of total cumulative losses from the Irish Sea by advection through the North Channel of 7.9 TBq of 238Pu, 48 TBq of 239,240Pu 2.6 × 104 TBq of 137Cs.

Radiocarbon is an important constituent of the low level, liquid, radioactive effluent discharged from the Sellafield nuclear fuel reprocessing plant in northwest England, but despite the fact that it gives the highest collective dose commitment of all the nuclides in the waste, its behavior in the Irish Sea is poorly defined. There is therefore a clear requirement for an improved understanding of 14C behavior in the Irish Sea, to assist with dose evaluation modeling and definition of the mixing and accumulation characteristics of the sediment in this area. In this context, results are presented here for a temporal study of 14C activities in four geochemical fractions of seawater and in a sediment core from the vicinity of the Sellafield effluent outfall. Clear 14C enrichments in the dissolved inorganic carbon (DIC) and particulate organic carbon (POC) components of seawater were observed, with temporal trends in activity that were related to variations in the Sellafield discharge. Smaller, but nevertheless detectable, enrichments were also observed for particulate inorganic carbon (PIC) and dissolved organic carbon (DOC) in the seawater. The distribution of 137Cs and 241Am revealed that the sediment core could be classified into three zones in which the intensity of mixing decreased discontinuously with depth. Bulk carbonate 14C analyses of the core demonstrated the presence of glacial or pre-glacial carbonate in the system, but failed to show any evidence of contaminant 14C input or provide information on sediment accumulation processes. In contrast, analysis of bulk organic matter from the sediment provided clear evidence of the recent perturbation of a well mixed system by input of younger material, consistent with the recent input of contaminant 14C from Sellafield and possibly weapons testing fallout.

We compared accelerator mass spectrometry (AMS) 14C ages of large (>150 μm) pelagic foraminifera with radiometric bulk carbonate 14C ages in two northeastern Atlantic cores. The foraminiferal ages are consistently older than those of the bulk sediment (by + 0.76 ka in Core 11881 and by + 1.1 ka in Core 11886), whereas corresponding fine (−1 in Core 11881 and 5.9 cm ka−1 in Core 11886). Consideration of various factors that might produce such offsets leads us to believe that they are not artifacts, but were most probably caused by differential bioturbation of the different size-fractions in the sediment surface mixed layer. The importance of this finding is that many paleoceanographic records, such as the oxygen isotope record, also derive from analyses of large foraminifera, so that these records must be offset in time from the bulk of the sediments that they characterize.

The mean 206pb/207pb ratio of 1.131 ± 0.015 (range 1.112–1.150) found for lead in the teeth of ‘low‐lead exposure’ children in Edinburgh is intermediate between the observed ratios for leaded petrol (1.075 ± 0.013) and tap water in contact with lead pipes (1.160 ± 0.012) and comparable with that reported for food in the UK. Quantitative source apportionment on the basis of one lead isotopic ratio, however, may well be hindered by the wide range of 206Pb/207 Pb values (1.098–1.183; mean 1.142 ± 0.031) found for old, high‐lead (> 1.0%) paint and the similarity of the mean ratio (1.159 ± 0.011) for high‐lead (> 0.1%) dust in older houses to that for tap water. The potential benefit of using more than one stable lead isotopic ratio in such investigations is endorsed by the identification of two distinct groups of children close to the excellent best‐fit line (r = ‐0.976) through the 208Pb/206Pb versus 206Pb/207Pb plot for the extensive series of environmental (petrol, atmospheric particulates, street...

A liquid scintillation spectrometry method for the determination of (234)Th in seawater with (230)Th as the yield tracer has been developed and validated. (234)Th is separated from the dissolved phase by an Fe(OH)(3) precipitation and is then purified using ion exchange chromatography. The counting source is prepared by taking the sample to dryness in a vial, redissolving in acid, and mixing with a scintillation cocktail. The instrument employed has a relatively low background (11 cpm) and the ability to separate α from β activity on the basis of pulse shapes. The (234)Th + (234m)Pa counting efficiency is 50% over the counting window employed. The limit of detection, using the above parameters, a 20 L sample, and a 400 min count is found to be 0.04 dpm L(-)(1). It was also demonstrated that less advanced instruments, without α/β separation, can also be used effectively.

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.

Scintillation cocktail components were studied with regard to their impact on pulse decay discimination (PDD) and hence the separation of alpha from beta activity, using a Packard 2250 CA α/β. Di-isopropyl naphthalene (DIN) was found to be the most suitable solvent, both from safety considerations and also the fact that it acts in a very similar manner to naphthalene in stretching the pulses produced at the photomultiplier tube anode and hence enhancing the separation. Increasing the surfactant concentration and the use of dimethylanthracene (DMA) as secondary fluor degraded the cocktail's performance. PMT anode pulse shapes were found to be a useful indicator of PDD efficiency but could not give a quantitative guide.

Cores from four Scottish ombrotrophic peat bogs were used to reconstruct the historical record of atmospheric vanadium (V) deposition in Scotland over the last 150 years. The general similarity of V and Pb concentration profile trends in Pb-210-dated cores from each of the sites strongly suggested that V, like Pb, is essentially immobile in ombrotrophic peat. After allowance via use of the conservative element Ti for the contribution of soil dust V, the deposition of anthropogenic V was found to be greatest (similar to 1.3 to 2.0 mg m(-2) y(-1)) in the mid-20(th) century before decreasing to 0.1-0.3 mg m(-2) y(-1) in the early years of the 21(st) century. The latter values were in good agreement with directly measured atmospheric V fluxes at nearby sites, a finding also observed in the case of Pb. The decline in peat-core-derived fluxes for both V and Pb from 1970 to 2004, however, was not as large as the decline in official UK emission estimates for the two metals during this period. This, along with an order of magnitude discrepancy between the anthropogenic V/Pb ratios at the peat core surface and the higher values of the ratio for UK emissions in the early 2000s, suggests that the recently revised UK emissions data for V may perhaps still be overestimated and/or that some previously deposited Pb is being resuspended in the atmosphere.

Uranium associations with colloidal and truly dissolved soil porewater components from two Ministry of Defence Firing Ranges in the UK were investigated. Porewater samples from 2-cm depth intervals for three soil cores from each of the Dundrennan and Eskmeals ranges were fractionated using centrifugal ultrafiltration (UF) and gel electrophoresis (GE). Soil porewaters from a transect running downslope from the Dundrennan firing area towards a stream (Dunrod Burn) were examined similarly. Uranium concentrations and isotopic composition were determined using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) and Multi-Collector-Inductively Coupled Plasma-Mass Spectrometry (MC-ICP-MS), respectively. The soils at Dundrennan were Fe- and Al-rich clay-loam soils whilst at Eskmeals, they were Fe- and Al-poor sandy soils; both, however, had similar organic matter contents due to the presence of a near-surface peaty layer at Eskmeals. These compositional features influenced the porewater composition and indeed the associations of U (and DU). In general, at Dundrennan, U was split between large (100kDa-0.2μm) and small (3-30kDa) organic colloids whilst at Eskmeals, U was mainly in the small colloidal and truly dissolved fractions. Especially below 10cm depth, association with large Fe/Al/organic colloids was considered to be a precursor to the removal of U from the Dundrennan porewaters to the solid phase. In contrast, the association of U with small organic colloids was largely responsible for inhibiting attenuation in the Eskmeals soils. Lateral migration of U (and DU) through near-surface Dundrennan soils will involve both large and small colloids but, at depth, transport of the smaller amounts of U remaining in the porewaters may involve large colloids only. For one of the Dundrennan cores the importance of redox-related processes for the re-mobilisation of DU was also indicated as Mn(IV) reduction resulted in the release of both Mn(II) and U(VI) into the truly dissolved phase.

A mathematical model is set up to describe the evolution in time of the activity ratios of the long lived members of the 238U decay series following alteration of the initial state of secular equilibrium in the rock by a rock-water interaction. Both sudden (that is to say, of duration very much shorter than any of the half-lives involved) and continuously acting disturbances are considered. Continuous processes may involve either the removal or the deposition of uranium and these are represented in the formalism as first and zero order effects respectively. Difficulties of principle are identified, but in spite of these an attempt is made to show that the predictions of the model are useful in the interpretation of activity ratios obtained for suites of samples under circumstances in which complementary geochemical information is available.

Possible postdepositional As migration in ombrotrophic peat bogs was investigated by comparing depth profiles of As with those of Sb and Pb, two elements considered to be essentially immobile in peat, and those of redox-sensitive, potentially mobile nutrient elements such as Mn, Fe, P, and S in 210Pb-dated cores from four Scottish bogs. Concentration profiles of As were similar to those of Sb and Pb rather than these other elements, indicating that As is bound strongly to organic matter and is relatively immobile in ombrotrophic peat. Historical records of atmospheric anthropogenic As, Sb, and Pb deposition during the industrial and postindustrial periods were derived, site-specific maxima (up to 1.55, 1.33, and 45 mg m(-2) y(-1), respectively) occurring between the late 1890s and 1960s, reflecting emissions from diverse sources such as mining and smelting, coal combustion, and also, in the case of Pb, exhaust emissions from the use of leaded gasoline. Since the mid-1980s, fluxes of Pb decreased (4-7 fold) more rapidly than those of As and Sb (2-3 fold), attributable to both the gradual elimination of leaded gasoline and recent new sources of the latter elements. Relative trends in derived anthropogenic As, Sb, and Pb deposition largely agreed with other Scottish peat and moss archive records, direct measurements of deposition, and UK emissions, i.e., four different types of data source.

The historical accumulation rates of mercury resulting from atmospheric deposition to four Scottish ombrotrophic peat bogs, Turclossie Moss (northeast Scotland), Flanders Moss (west-central), Red Moss of Balerno (east-central) and Carsegowan Moss (southwest), were determined via analysis of (210)Pb- and (14)C-dated cores up to 2000 years old. Average pre-industrial rates of mercury accumulation of 4.5 and 3.7 microg m(-2) y(-1) were obtained for Flanders Moss (A.D. 1-1800) and Red Moss of Balerno (A.D. 800-1800), respectively. Thereafter, mercury accumulation rates increased to typical maximum values of 51, 61, 77 and 85 microg m(-2) y(-1), recorded at different times possibly reflecting local/regional influences during the first 70 years of the 20th century, at the four sites (TM, FM, RM, CM), before declining to a mean value of 27+/-15 microg m(-2) y(-1) during the late 1990s/early 2000s. Comparison of such trends for mercury with those for lead and arsenic in the cores and also with direct data for the declining UK emissions of these three elements since 1970 suggested that a substantial proportion of the mercury deposited at these sites over the past few decades originated from outwith the UK, with contributions to wet and dry deposition arising from long-range transport of mercury released by sources such as combustion of coal. Confidence in the chronological reliability of these core-derived trends in absolute and relative accumulation of mercury, at least since the 19th century, was provided by the excellent agreement between the corresponding detailed and characteristic temporal trends in the (206)Pb/(207)Pb isotopic ratio of lead in the (210)Pb-dated Turclossie Moss core and those in archival Scottish Sphagnum moss samples of known date of collection. The possibility of some longer-term loss of volatile mercury released from diagenetically altered older peat cannot, however, be excluded by the findings of this study.

The mobility and bioavailability of depleted uranium (DU) in soils at a UK Ministry of Defence (UK MoD) weapons testing range were investigated. Soil and vegetation were collected near a test-firing position and at eight points along a transect line extending approximately 200 m down-slope, perpendicular to the firing line, toward a small stream. Earthworms and porewaters were subsequently separated from the soils and both total filtered porewater (

Methods for the fractionation of aquatic colloids require careful application to ensure efficient, accurate and reproducible separations. This paper describes the novel combination of mild colloidal fractionation and characterisation methods, namely centrifugal ultrafiltration, gel electrophoresis and gel filtration along with spectroscopic (UV-visible) and elemental (Inductively Coupled Plasma-Optical Emission Spectroscopy, Inductively Coupled Plasma-Mass Spectrometry) analysis, an approach which produced highly consistent results, providing improved confidence in these methods. Application to the study of the colloidal and dissolved components of soil porewaters from one soil at a depleted uranium (DU)-contaminated site revealed uranium (U) associations with both large (100 kDa-0.2 microm) and small (3-30 kDa) humic colloids. For a nearby soil with lower organic matter content, however, association with large (100 kDa-0.2 microm) iron (Fe)-aluminium (Al) colloids in addition to an association with small (3-30 kDa) humic colloids was observed. The integrated colloid fractionation approach presented herein can now be applied with confidence to investigate U and indeed other trace metal migration in soil and aquatic systems.

Depleted uranium (DU) weapons testing programmes have been conducted at two locations within the UK. An investigation was therefore carried out to assess the extent of any environmental contamination arising from these test programmes using both alpha spectrometry and mass spectrometry techniques. Uranium isotopic signatures indicative of DU contamination were observed in soil, plant and earthworm samples collected in the immediate vicinity of test firing points and targets, but contamination was found to be localised to these areas. This paper demonstrates the superiority of the (235)U : (238)U ratio over the (234)U : (238)U ratio for identifying and quantifying DU contamination in environmental samples, and also describes the respective circumstances under which alpha spectrometry or mass spectrometry may be the more appropriate analytical tool.

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., with95% 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.

The distribution of contaminant radionuclides from the Sellafield nuclear fuel reprocessing plant was used to establish chronologies for three saltmarsh sediment cores from south west Scotland. delta(13)C and (14)C analyses indicated that the cores provided a useful archive record of variations in input of organic matter and carbonate. The results imply that prior to major releases of contaminant (14)C from Sellafield, the (14)C specific activity of organic matter in Irish Sea offshore sediments was about 24 Bq kg(-1) C, while that of the carbonate component was below the limit of detection. These results provide baseline data for modelling the uptake of contaminant (14)C by the Irish Sea sediment system. The study confirmed that small(13)C analyses provide a sensitive means of apportioning the origin of saltmarsh organic matter between C(3) terrigenous plants, C(4) terrigenous plants and suspended particulate marine organic matter. For the2 mm fraction of sediment, a clear pattern of decreasing marine organic input was observed in response to increasing elevation of the marsh surface as a result of sediment accumulation. Bulk sediment, including detrital vegetation, had a dominant input from terrigenous plants. The combined use of delta(13)C and (14)C data revealed that organic matter in the marine organic component of the2 mm fraction of contemporary surface sediments of the saltmarshes is dominated by recycled old organic material.

Uranium is a redox-sensitive element which occurs naturally in the bedrock and groundwaters in Fennoscandia, and can be used, in conjunction with its decay series descendants, to indicate groundwater redox conditions. Not only can contemporary conditions be characterised, but evidence of past changes (e.g. during the last glaciation some 10 ka ago) can be preserved in minerals which coat the fracture walls along groundwater pathways. Uranium decay series data for groundwaters and solid fracture phases from the site of the Äspö Hard Rock Laboratory and its near vicinity are presented and discussed in the context of redox conditions.

A novel method has been developed for determining the natural decay series radionuclides (NDS), 210 Pb, 210 Bi, and 210 Po, in seawater by way of state-of-the-art liquid scintillation spectrometry. For 210 Pb analysis, the method makes use of a 212 Pb yield tracer, prepared by ion exchange separation from aged Th(NO 3 ) 4 . 210 Bi recovery is determined using 207 Bi as the yield tracer, and 210 Po is determined using the conventional 208 Po yield tracer. The limits of detection for this method are 0.32, 0.34, and 0.004 mBq l -1 for 210 Pb, 210 Bi, and 210 Po, respectively. The analysis can be completed within 10 days, as compared with up to one year for traditional methods. Results are presented for a preliminary study of 210 Pb, 210 Bi, and 210 Po in the dissolved and particle-bound phases of Irish Sea water.

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.

The reaction of hydrazoic acid, HN3, with trimethylgallium to produce thin-film gallium nitride under very-low-pressure chemical vapour deposition (VLPCVD) conditions is described. Data are presented which show that at 10–6 mbar the product GaN is crystalline and strongly oriented on the substrate sapphire (0001) crystal face. Some potential advantages of using HN3 rather than the conventional precursor NH3, for nitride film production, are mentioned.

Using a volatile precursor, namely copper(II)hexafluoroacetylacetonate, it has been possible to prepare by the process of low temperature normal pressure metalorganic chemical vapor deposition, thin films of copper(II) oxide. These polycrystalline films were characterized by X-ray powder diffraction, scanning electron microscopy, energy dispersive X-ray analysis and by thermoelectric methods.

In the MOCVD production of oxide thin films, the use of oxygen saturated with water has been largely to reduce residual carbon and fluorine content. In this paper, the influence of water-saturated oxygen on the morphology of thin films of Cu(II)O produced by low temperature metalorganic chemical vapor deposition onto quartz, magnesium oxide and cubic zirconia substrates is described. The Cu(II)O films were characterized by scanning electron microscopy, energy dispersive X-ray microanalysis, optical transmission spectrophotometry and X-ray powder diffraction.

The concentrations of Th in samples of crystalline rock from three drillcore sections were analysed independently by instrumental neutron activation analysis and by chemical separation and alpha spectroscopy. The two methods show good general agreement over an approximate concentration range of 1 to 100 ppm Th. Variations in results between the two methods are not of a systematic nature and probably arise from sample heterogeneity. The results confirm the reliability of both methods and provide a useful comparison of the standards and reference materials used. The study indicates that, in cases where Th isotopic information is not required, the simpler and more rapid neutron activation analysis provides a satisfactory method.

Concentrations and isotope ratios of natural decay series radionuclides have been studied in three contrasting crystalline rock drillcore sections intersecting water-conducting fractures deep in the bedrock. Radioactive disequilibria resulting from rock-water interactions were observed in two of the cores. These indicated uranium migration along distances of 40 cm or more on a timescale of 106 years in conjunction with thorium immobility under the same conditions. Fracture surface minerals showed a high affinity for radionuclide retardation and a limit of about 3 cm is suggested for the migration of radionuclides from fracture fluids into the saturated rock. This limit may correspond to enhanced matrix porosities resulting from earlier hydrothermal activity along the same channels.