Urinary stones as a novel matrix for human biomonitoring of toxic and essential elements

Monitoring of body burden of toxic elements is usually based on analysis of concentration of particular elements in blood, urine and/or hair. Analysis of these matrices, however, predominantly reflects short- or medium-term exposure to trace elements or pollutants. In this work, urinary stones were investigated as a matrix for monitoring long-term exposure to toxic and essential elements. A total of 431 samples of urinary calculi were subjected to mineralogical and elemental analysis by infrared spectroscopy and inductively coupled plasma mass spectrometry. The effect of mineralogical composition of the stones and other parameters such as sex, age and geographical location on contents of trace and minor elements is presented. Our results demonstrate the applicability of such approach and confirm that the analysis of urinary calculi can be helpful in providing complementary information on human exposure to trace metals and their excretion. Analysis of whewellite stones (calcium oxalate monohydrate) with content of phosphorus <0.6 % has been proved to be a promising tool for biomonitoring of trace and minor elements.

     

The value of Seasonal Correction Factors in assessing the health risk from domestic radon: a case study in Northamptonshire, UK

Following an intensive survey of domestic radon levels in the United Kingdom (UK), the former National Radiological Protection Board (NRPB), now the Radiation Protection Division of the Health Protection Agency (HPA-RPD), established a measurement protocol and promulgated Seasonal Correction Factors applicable to the country as a whole. Radon levels in the domestic built environment are assumed to vary systematically and repeatably during the year, being generally higher in winter. The Seasonal Correction Factors therefore comprise a series of numerical multipliers, which convert a 1-month or 3-month radon concentration measurement, commencing in any month of the year, to an effective annual mean radon concentration. In a recent project undertaken to assess the utility of short-term exposures in quantifying domestic radon levels, a comparative assessment of a number of integrating detector types was undertaken, with radon levels in 34 houses on common geology monitored over a 12-month period using dose-integrating track-etch detectors exposed in pairs (one upstairs, one downstairs) at 1-month and 3-month resolution. Seasonal variability of radon concentrations departed significantly from that expected on the basis of the HPA-RPD Seasonal Correction Factor set, with year-end discontinuities at both 1-month and 3-month measurement resolutions. Following this study, monitoring with electrets was continued in four properties, with weekly radon concentration data now available for a total duration in excess of three and a half years. Analysis of this data has permitted the derivation of reliable local Seasonal Correction Factors. Overall, these are significantly lower than those recommended by HPA-RPD, but are comparable with other results from the UK and from abroad, particularly those that recognise geological diversity and are consequently prepared on a regional rather than a national basis. This finding calls into question the validity of using nationally aggregated Seasonal Correction Factors, especially for shorter exposures, and the universal applicability of these corrections is discussed in detail.     

Direct evidence of trophic interactions among apex predators in the Late Triassic of western North America

Hypotheses of feeding behaviors and community structure are testable with rare direct evidence of trophic interactions in the fossil record (e.g., bite marks). We present evidence of four predation, scavenging, and/or interspecific fighting events involving two large paracrocodylomorphs (=‘rauisuchians’) from the Upper Triassic Chinle Formation (～220–210 Ma). The larger femur preserves a rare history of interactions with multiple actors prior to and after death of this ～8–9-m individual. A large embedded tooth crown and punctures, all of which display reaction tissue formed through healing, record evidence of a failed attack on this individual. The second paracrocodylomorph femur exhibits four unhealed bite marks, indicating the animal either did not survive the attack or was scavenged soon after death. The combination of character states observed (e.g., morphology of the embedded tooth, ‘D’-shaped punctures, evidence of bicarination of the marking teeth, spacing of potentially serial marks) indicates that large phytosaurs were actors in both cases. Our analysis of these specimens demonstrates phytosaurs targeted large paracrocodylomorphs in these Late Triassic ecosystems. Previous distinctions between ‘aquatic’ and ‘terrestrial’ Late Triassic trophic structures were overly simplistic and built upon mistaken paleoecological assumptions; we show they were intimately connected at the highest trophic levels. Our data also support that size cannot be the sole factor in determining trophic status. Furthermore, these marks provide an opportunity to start exploring the seemingly unbalanced terrestrial ecosystems from the Late Triassic of North America, in which large carnivores far outnumber herbivores in terms of both abundance and diversity.     

Ensuring the continued success of a mulch biowall at a trichloroethylene-contaminated superfund site: Lessons learned

Trichloroethylene (TCE) is a toxic organic compound, which can adversely affect human health. The chemical is one of the most frequently found contaminants in groundwater in the United States and around the world. A landfill in Maryland contaminated with high levels of TCE decades ago was added to the U.S. Environmental Protection Agency's National Priority List (NPL) in 1994. A biowall was installed on the site in 2013 to promote the bioremediation of TCE and subsequently of its degradation products. Six-year monitoring data indicated a steady removal of >99% groundwater TCE at the wall since installation. However, a concurrent buildup of intermediate byproducts was observed downgradient of the wall. An examination of the entire system was necessary to find the reason behind the inefficiency of the biowall. In this study, the background of the site, remediation plan, and installation were assessed. Monitoring data, including the concentration of TCE and its degradation byproducts, and geochemical and physical characteristics were evaluated to understand the conditions and challenges facing decision-makers of this project and possible options to improve biowall efficacy.     

Biogeochemical consequences of a changing Arctic shelf seafloor ecosystem

Unprecedented and dramatic transformations are occurring in the Arctic in response to climate change, but academic, public, and political discourse has disproportionately focussed on the most visible and direct aspects of change, including sea ice melt, permafrost thaw, the fate of charismatic megafauna, and the expansion of fisheries. Such narratives disregard the importance of less visible and indirect processes and, in particular, miss the substantive contribution of the shelf seafloor in regulating nutrients and sequestering carbon. Here, we summarise the biogeochemical functioning of the Arctic shelf seafloor before considering how climate change and regional adjustments to human activities may alter its biogeochemical and ecological dynamics, including ecosystem function, carbon burial, or nutrient recycling. We highlight the importance of the Arctic benthic system in mitigating climatic and anthropogenic change and, with a focus on the Barents Sea, offer some observations and our perspectives on future management and policy.     

The effect of sodium chloride on the dissolution of calcium silicate hydrate gels

The use of cement based materials will be widespread in the long-term management of radioactive materials in the United Kingdom. One of the applications could be the Nirex reference vault backfill (NRVB) as an engineered barrier within a deep geological repository. NRVB confers alkaline conditions, which would provide a robust chemical barrier through the control of the solubility of some key radionuclides, enhanced sorption and minimised corrosion of steel containers. An understanding of the dissolution of C-S-H gels in cement under the appropriate conditions (e.g., saline groundwaters) is necessary to demonstrate the expected evolution of the chemistry over time and to provide sufficient cement to buffer the porewater conditions for the required time. A programme of experimental work has been undertaken to investigate C-S-H gel dissolution behaviour in sodium chloride solutions and the effect of calcium/silicon ratio (C/S), temperature and cation type on this behaviour. Reductions in calcium concentration and pH values were observed with samples equilibrated at 45 degrees C compared to those prepared at 25 degrees C. The effect of salt cation type on salt-concentration dependence of the dissolution of C-S-H gels was investigated by the addition of lithium or potassium chloride in place of sodium chloride for gels with a C/S of 1.0 and 1.8. With a C/S of 1.0, similar increases in dissolved calcium concentration with increasing ionic strength were recorded for the different salts. However, at a C/S of 1.8, anomalously high calcium concentrations were observed in the presence of lithium.     

Effects of the forced ventilation on composting of a solid olive-mill by-product ("alperujo") managed by mechanical turning

The evaluation of the most suitable aeration technology for olive-mill by-product "alperujo" (AL) composting was carried out by using two identical piles prepared by mixing AL with a bulking agent (fresh cow bedding) and a mature compost (as inoculant). Forced ventilation was employed in conjunction with mechanical turning in one of the piles, whereas only mechanical turning was used in the other pile. These two treatment methods were evaluated by assessing process efficiency and end-product quality. The results show that the composting process was completed in less time when forced ventilation was coupled with mechanical turning. A slight delay in the evolution of pH, C/N ratio, and biodegradation of fats and organic matter was observed when only turning was employed. However, the recommended method for composting AL was mechanical turning without forced ventilation since the composition of the end-product in this case was comparable to the composted AL using forced ventilation coupled with mechanical turning. Furthermore, there were substantial economic savings by selecting mechanical turning alone, which included capital costs for equipment.     

Modelling Phosphorus Retention in Lakes and Reservoirs

Steady-state models for the prediction of P retention coefficient (R) in lakes were evaluated using data from 93 natural lakes and 119 reservoirs situated in the temperate zone. Most of the already existing models predicted R relatively successfully in lakes while it was seriously under-estimated in reservoirs. A statistical analysis indicated the main causes of differences in R between lakes and reservoirs: (a) distinct relationships between P sedimentation coefficient, depth, and water residence time; (b) existence of significant inflow–outflow P concentration gradients in reservoirs. Two new models of different complexity were developed for estimating R in reservoirs: , where τ is water residence time (year), was derived from the Vollenweider/Larsen and Mercier model by adding a calibrated parameter accounting for spatial P non-homogeneity in the water body, and is applicable for reservoirs but not lakes, and , where [P_in] is volume-weighted P concentration in all inputs to the water body (μg l⁻¹), was obtained by re-calibrating the OECD general equation, and is generally applicable for both lakes and reservoirs. These optimised models yield unbiased estimates over a large range of reservoir types.     

Nitrate and sediment fluxes from a California rangeland watershed

Long-term water quality records for assessing natural variability, impact of management, and that guide regulatory processes to safeguard water resources are rare for California oak woodland rangelands. This study presents a 20-yr record (1981-2000) of nitrate-nitrogen (NO(3)-N) and suspended sediment export from a typical, grazed oak woodland watershed (103 ha) in the northern Sierra Nevada foothills of California. Mean annual precipitation over the 20-yr period was 734 mm yr(-1) (range 366-1205 mm yr(-1)). Mean annual stream flow was 353 mm y(-1) (range 87-848 mm yr(-1)). Average annual stream flow was 48.1 +/- 16% of precipitation. Mean annual NO(3)-N export was 1.6 kg ha(-1) yr(-1) (range 0.18-3.6 kg ha(-1) yr(-1)). Annual NO(3)-N export significantly (P < 0.05) increased with increasing annual stream flow and precipitation. Mean daily NO(3)-N export was 0.004 kg ha(-1) d(-1) (range 10(-5) to 0.55 kg ha(-1) d(-1)). Mean annual suspended sediment export was 198 kg ha(-1) yr(-1) (range 23-479 kg ha(-1) yr(-1)). There was a positive relationship (P < 0.05) between annual suspended sediment export, annual stream flow and precipitation. Mean daily suspended sediment export was 0.54 kg ha(-1) d(-1) (range 10(-4) to 155 kg ha(-1) d(-1)). Virtually no sediment was exported during the dry season. The large variation in daily and annual fluxes highlights the necessity of using long-term records to establish quantitative water quality targets for rangelands and demonstrates the difficulty of designing a water quality monitoring program for these ecosystems.     

micro-XANES and micro-XRF investigations of metal binding mechanisms in biosolids

Micro-X-ray fluorescence (micro-XRF) microprobe analysis and micro-X-ray absorption near-edge structure (micro-XANES) spectroscopy were employed to identify Fe and Mn phases and their association with selected metals in two biosolids (limed composted [LC] and Nu-Earth) before and after treatment to remove organic carbon (OC). Spatial correlations derived from elemental mapping of XRF images showed strong correlations between Fe and Cd, Cr, Pb, or Zn (r2= 0.65-0.92) before and after removal of most of the OC. The strong correlation between Fe and Cu that was present in intact samples disappeared after OC removal, suggesting that Cu was associated with OC coatings that may have been present on Fe compounds. Except for Fe and Cr, the spatial correlations of metals with Mn were improved after treatment to remove OC, indicating that the treatment may have altered more than the OC in the system. The Fe micro-XANES spectra of the intact biosolids sample showed that every point had varying mixtures of Fe(II and III) species and no two points were identical. The lack of uniformity in Fe species in the biosolids sample illustrates the complexity of the materials and the difficulty of studying biosolids using conventional analytical tools or chemical extraction techniques. Still, these microscopic observations provide independent information supporting the previous laboratory and field hypothesis that Fe compounds play a major role in retention of environmentally important trace elements in biosolids. This could be due to co-precipitation of the metals with Fe, adsorption of metals by Fe compounds, or a combination of both mechanisms.