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Are mercury emissions from geologic sources significant? A status report.

Geologic sources of atmospheric mercury include areas of fossil and current geothermal activity, recent volcanic activity, precious and base metal deposits, and organic rich sedimentary rocks. Early estimates of emissions from these sources were not based on measurements of mercury fluxes but implied based on the difference between emissions from anthropogenic point sources and wet/dry deposition estimates. In the past approximately 7 years significant progress has been made in development of methods for the measurement of mercury emissions, definition of those parameters most important in controlling emissions and scaling up emissions from natural source areas. This paper summarizes the work done on scaling of emissions from discrete areas of natural enrichment and from the State of Nevada, which is situated within a global belt of mercury enrichment. Preliminary data indicate that elemental mercury is the predominant (>95%) form of mercury being emitted from these sources. Scaling results suggest that the value used in early models to represent emissions from global mercuriferous belts is too low by at least three times.

Air Pollutants↗

Determination of radium isotope ratios and abundances in geologic samples by thermal ionization mass spectrometry.

We describe chemical separation and mass spectrometric procedures for the measurement of radium isotopes in geologic samples. These methods provide 226Ra/228Ra ratio measurements for 1 g or less of rock sample containing subpicogram amounts of radium with precision better than 1.5% (95% confidence level). Radium-226 concentrations were measured by isotope dilution for smaller sample sizes (100-500 mg) containing as little as 1-10 fg of total 226Ra with similar high precision.

Geology↗

Deep sub-seafloor prokaryotes stimulated at interfaces over geological time.

The sub-seafloor biosphere is the largest prokaryotic habitat on Earth but also a habitat with the lowest metabolic rates. Modelled activity rates are very low, indicating that most prokaryotes may be inactive or have extraordinarily slow metabolism. Here we present results from two Pacific Ocean sites, margin and open ocean, both of which have deep, subsurface stimulation of prokaryotic processes associated with geochemical and/or sedimentary interfaces. At 90 m depth in the margin site, stimulation was such that prokaryote numbers were higher (about 13-fold) and activity rates higher than or similar to near-surface values. Analysis of high-molecular-mass DNA confirmed the presence of viable prokaryotes and showed changes in biodiversity with depth that were coupled to geochemistry, including a marked community change at the 90-m interface. At the open ocean site, increases in numbers of prokaryotes at depth were more restricted but also corresponded to increased activity; however, this time they were associated with repeating layers of diatom-rich sediments (about 9 Myr old). These results show that deep sedimentary prokaryotes can have high activity, have changing diversity associated with interfaces and are active over geological timescales.

Archaea↗

A review of scientific literature examining the mining history, geology, mineralogy, and amphibole asbestos health effects of the Rainy Creek igneous complex, Libby, Montana, USA.

This article reviews the past 90 yr of scientific research directed on multiple aspects of the unique geology and environmental health issues surrounding the vermiculite deposit found at Libby, MT. Hydrothermal alteration and extensive weathering of the ultramafic units resulted in the formation of a rich deposit of vermiculite that was mined for 67 yr and used in numerous consumer products in its expanded form. Later intrusions of alkaline units caused hydrothermal alteration of the pyroxenes, resulting in formation of amphiboles. Some of these amphiboles occur in the asbestiform habit and have been associated with pulmonary disease in former miners and mill workers. Identification of these amphibole asbestos minerals has received little attention in the past, but recent work shows that the majority of the amphibole mineral species present may not be any of the amphibole species currently regulated by government agencies. Epidemiological studies on former miners have, nevertheless, shown that the amphibole asbestos from the Rainy Creek igneous complex is harmful; also, a recent study by the Agency for Toxic Substances and Disease Registry shows that residents of Libby who had not been employed in the vermiculite mining or milling operations also appear to have developed asbestos-related pulmonary diseases at a higher rate than the general public elsewhere. Since November 1999, the U.S. Environmental Protection Agency has been involved in the cleanup of asbestos-contaminated sites in and around Libby associated with the mining and processing of vermiculite.

Aluminum Silicates↗

Validation of a physically based catchment model for application in post-closure radiological safety assessments of deep geological repositories for solid radioactive wastes.

The physically based river catchment modelling system SHETRAN incorporates components representing water flow, sediment transport and radionuclide transport both in solution and bound to sediments. The system has been applied to simulate hypothetical future catchments in the context of post-closure radiological safety assessments of a potential site for a deep geological disposal facility for intermediate and certain low-level radioactive wastes at Sellafield, west Cumbria. In order to have confidence in the application of SHETRAN for this purpose, various blind validation studies have been undertaken. In earlier studies, the validation was undertaken against uncertainty bounds in model output predictions set by the modelling team on the basis of how well they expected the model to perform. However, validation can also be carried out with bounds set on the basis of how well the model is required to perform in order to constitute a useful assessment tool. Herein, such an assessment-based validation exercise is reported. This exercise related to a field plot experiment conducted at Calder Hollow, west Cumbria, in which the migration of strontium and lanthanum in subsurface Quaternary deposits was studied on a length scale of a few metres. Blind predictions of tracer migration were compared with experimental results using bounds set by a small group of assessment experts independent of the modelling team. Overall, the SHETRAN system performed well, failing only two out of seven of the imposed tests. Furthermore, of the five tests that were not failed, three were positively passed even when a pessimistic view was taken as to how measurement errors should be taken into account. It is concluded that the SHETRAN system, which is still being developed further, is a powerful tool for application in post-closure radiological safety assessments.

Fresh Water↗

[A hygienic assessment of the noise and vibration from the machines and engines used in geological survey operations and the measures to decrease the adverse action of these factors on workers' bodies].

In the last 10 years, no decrease in noise and vibration conditions has been registered at a geological survey enterprise. On the contrary, the introduction of new, more productive equipment caused increase in the indices. The unfavourable labour conditions have resulted in higher occupational morbidity levels caused by the otic nerve neurites. The article sets forth a package of measures towards minimizing the hazardous influence of noise and vibration on the workers' health status.

Absenteeism↗

Instrumental neutron activation analysis of geological and biological reference materials using the ko-standardization method.

The ko-standardization method used in instrumental neutron activation analysis (INAA) was applied to the determination of some elements in geological and biological reference materials. We analyzed NBS SRM 1572 Citrus Leaves and SRM 1645 River Sediment and the CRM materials, IAEA Soil-7, SL-1, and MA-A-2. Comparison is made with reference values whenever available. Good agreement is found. The potential of the ko-standardization method in reactor INAA is discussed.

Animals↗

Highly sensitive and selective spectrophotometric method for determination of trace gold in geological samples with 5-(2-hydroxy-5-nitrophenylazo)rhodanine.

A excellent sensitive and selective method for spectrophotometric determination of trace gold has been developed, the method is based on the color reaction of gold(III) with new reagent 5-(2-hydroxy-5-nitrophenylazo)rhodanine (HNAR). Under optimal conditions, HNAR reacts with gold(III) to form a 1:5 orange complex, which has an maximum absorption peak at 480 nm. Maximum enhancement of the absorbance of the complex was obtained in the presence of the mixed surfactant of Triton X-100 and CTMAB; the reaction completed rapidly and the absorbance is stable for 5 h at least at 20 degrees C; 0-48 microg L(-1) Au(III) obeyed Beer's law. The apparent molar absorptivity of the complex, Sandell's sensitivity, the limit of quantification, the limit of detection and relative standard deviation were found to be 2.0x10(6) L mol(-1) cm(-1), 0.000,098,483 micro g cm(-2), 1.02 ng mL(-1), 0.35 ng mL(-1) and 1.09%, respectively. The effect of co-existing ions was studied seriously; most metal ions can be tolerated in considerable amounts. Its sensitivity and selectivity are remarkably superior to other reagents in the literature. The proposed method was used successfully to determine trace gold in geological samples. Moreover, the synthesis, characteristics and analytical reaction of HNAR with gold are also described in detail.

Journal Article↗

Extraction of U(VI), Th(IV), and La(III) from acidic streams and geological samples using AXAD-16-POPDE polymer.

A new chromatographic extraction method has been developed using Amberlite XAD-16 (AXAD-16) resin chemically modified with (3-hydroxyphosphinoyl-2-oxo-propyl)phosphonic acid dibenzyl ester (POPDE). The chemically modified polymer was characterized by 13C CPMAS and 31P solid-state NMR, Fourier Transform-NIR-FIR-Raman spectroscopy, CHNPS elemental analysis, and thermogravimetric analysis. Extraction studies performed for U(VI), Th(IV), and La(III) showed good distribution ratio ( D) values of approximately 10(3), even under high acidities (1-4 M). Various physiochemical parameters that influence the quantitative metal ion extraction were optimized by static and dynamic methods. Data obtained from kinetic studies revealed that a time duration of < or =10 min was sufficient to achieve complete metal ion extraction. Maximum metal sorption capacity values under optimum pH conditions were found to be 1.38, 1.33, and 0.75 mmol g(-1) for U(VI), Th(IV), and La(III), respectively. Interference studies performed in the presence of concentrated diverse ions and electrolyte species showed quantitative analyte recovery with lower limits of analyte detection being 10 and 20 ng cm(-3) for U(VI) and both Th(IV) and La(III), respectively. Sample breakthrough studies performed on the extraction column showed an enrichment factor value of 330 for U(VI) and 270 for Th(IV) and La(III), respectively. Analyte desorption was effective using 15 cm3 of 1 M (NH4)2CO3 with >99.8% analyte recovery. The analytical applicability of the developed resin was tested with synthetic mixtures mimicking nuclear spent fuels, seawater compositions and real water and geological samples. The rsd values of the data obtained were within 5.2%, thereby reflecting the reliability of the developed method.

Journal Article↗

Progress in multi-ion counting spark-source mass spectrometry (MIC-SSMS) for the analysis of geological samples.

Spark source mass spectrometry (SSMS) has experienced important and significant improvements in nearly all analytical features by the use of a multiple ion counting (MIC) system. Two procedures have recently been developed to further increase the analytical capabilities of MIC-SSMS in geochemistry. These are a mathematical correction of interferences, which is often necessary for the ultra trace element analysis of Nb, Ta, Zr, Hf and Y, and the development of an autospark system to hold the total ion beam constant. New analytical data for geological samples, especially international reference materials, are presented using the improved MIC-SSMS technique. The data set consists of high precision and low abundance data for Zr, Nb and Y in depleted reference materials. The MIC-SSMS results are compared with those of conventional SSMS using photoplates for ion detection. The precision of the MIC-SSMS isotope ratio measurements (about 1%) is more than a factor of 3 better than that of conventional SSMS, as demonstrated by analyses of Hawaiian samples. Total uncertainties of MIC-SSMS concentration data including all sources of error are generally between 2 and 5% for concentrations higher than about 0.3 microg/g and about 10% for trace element abundances in the ng/g range.

Journal Article↗

Populations of a Connecticut River midge structured by geological history and downstream gene flow.

Connecticut River midges in the genus Axarus are constrained to semi-isolated populations associated with submerged clay exposures, and gene flow between populations is restricted. I sampled larval midges from fifteen spatially separated sites in the Connecticut River and determined karyotypes for 3111 larvae in two closely related species. In one of these species, an undescribed species referred to as Axarus species varvestris, 5 chromosomal rearrangements were present as polymorphisms. Four of these are paracentric inversions, and the fifth is a terminal insertion or deletion. I used chromosomal rearrangement frequencies to calculate Nei's genetic distance measures for all pairwise population comparisons and I constructed a neighbor-joining phenetic tree for the populations using these distances. Genetic distance between populations of A. sp. varvestris increases with geographic separation, and tree structure indicates that restricted gene flow only occurs in a downstream direction. The effect of unidirectional (downstream) gene flow on population genetic structure in riverine midges is described here for the first time. A genetic break is apparent between populations associated with 12 000-year-old sediments originating in different ancient lakes. The geological break between lakes also coincides with a break in the species composition of the Axarus populations.

Animals↗

X-ray fluorescence analysis of geological samples: exploring the effect of sample thickness on the accuracy of results.

The accuracy of the simple quantitative method of elemental XRF analysis applied to thick and thin geological samples was investigated with certified reference materials. In the case of thick samples, the intensity of the calcium signal was used as a characteristic of the sample for the dark matrix correction, as it had been found to be inversely correlated with the intensity of the silicon signal. The results of the analysis of thick samples did not depend on the sample form (pressed disc or a powder in a cup), and the absorption factors were very high. In the analysis of thin samples, the detection limits, sensitivity, and accuracy have been improved, particularly for light elements. As the absorption factors are close to unity for thin samples, there is no need for a matrix-effect correction or certified reference materials.

Journal Article↗

The use of forensic botany and geology in war crimes investigations in NE Bosnia.

From 1997 to 2002 the United Nations International Criminal Tribune for the former Yugoslavia (ICTY) undertook the exhumation of mass graves in NE Bosnia as part of the war crimes investigations aimed at providing evidence for the prosecution of war criminals in The Hague. This involved the location and exhumation of seven former mass graves (primary sites) dug following the fall of Srebrenica in July 1995. These primary mass graves were secretly and hurriedly exhumed three months later and most of the bodies or body parts transported and reburied in a large number of secondary sites many of which were subsequently exhumed by ICTY. The aim of the pollen and soil/sediment studies was to provide an 'environmental profile' of the original site of the samples and use this to match the relocated bodies to the original mass graves. This was part of completing the chain of evidence, providing evidence of the scale and organization of the original atrocities and the subsequent attempts to conceal the evidence related to them. All the primary sites were located in areas of contrasting geology, soils and vegetation, and this allowed matching of the sediment transported in intimate contact with the bodies to the original burial sites, which in some cases were also the execution sites. In all, over 24 sites were investigated, over 240 samples collected and analyzed under low power microscopy and 65 pollen sub-samples fully analyzed. The pollen and sediment descriptions were used in conjunction with the mineralogy (using XRD) of primary and secondary sites in order to provide matches. These matches were then compared with matching evidence from ballistic studies and clothing. The evidence has been used in court and is now in the public domain. It is believed this is the first time 'environmental profiling' techniques have been used in a systematic manner in a war crimes investigation.

Bosnia and Herzegovina↗

A temperature-profile method for estimating flow in geologic heat pipes.

Above-boiling temperature conditions, as encountered, for example, in geothermal reservoirs and in geologic repositories for the storage of heat-producing radioactive wastes, may induce strong liquid and gas flow processes in porous subsurface environments. The magnitude of these flow processes is extremely hard to measure in the field. We therefore propose a simple temperature-profile method that uses high-resolution temperature data for deriving such information. The energy that is transmitted with the vapor and water flow creates a nearly isothermal zone maintained at about the boiling temperature, referred to as a heat pipe. Characteristic features of measured temperature profiles, such as the differences in the gradients inside and outside of the heat-pipe regions, are used to derive the approximate magnitude of the liquid and gas fluxes in the subsurface.

Air Movements↗

On-line preconcentration of niobium(V) and tantalum(V) as 4-(2-pyridylazo) resorcinol-citrate ternary complexes in geological samples by ion interaction high-performance liquid chromatography.

4-(2-Pyridylazo) resorcinol (PAR) and citrate were used as pre-column complexing agents for the determination of Nb(V) and Ta(V) as ternary complexes in geological samples. Aliquots of 2 ml of the standard and sample solutions containing the Nb(V) and Ta(V) complexes were loaded onto a concentrator column (C18, 0.4 cm x 4.6 mm) with a carrier mobile phase comprising 20% (v/v) methanol and containing 5 mM acetic acid, 5 mM citric acid and 10 mM tetrabutylammonium bromide (TBABr), pH 6.5 at 2 ml/min for 2 min, with the effluent being directed to waste. An automatic switching valve was then switched to flush both complexes from the concentrator column onto a C18 analytical column using a mobile phase comprising 32% (v/v) methanol and containing 5 mM acetic acid, 5 mM citric acid and 3 mM TBABr, pH 6.5 for 2.5 min. The switching valve was then switched back to the original position, and cleaned with methanol for 7 min to eliminate unwanted species still adsorbed to the concentrator column. This procedure prevented later eluting compounds from reaching the analytical column, which reduced the overall run time. The detection limits of Nb(V) and Ta(V) (determined at a signal-to-noise ratio of 3, detection wavelength of 540 nm and a 2-ml sample volume) were 0.012 and 0.039 ppb for Nb(V) and Ta(V), respectively. Recoveries of Nb(V) and Ta(V) were 99.4 and 96.2%, respectively. The HPLC results obtained from the reference granite and basalt samples agreed well with inductively coupled plasma MS and certified values, but the HPLC method yielded slightly low values of the Nb/Ta ratio.

Chromatography, High Pressure Liquid↗

On the determination of 226Ra in environmental and geological samples by alpha-spectrometry using 225Ra as yield tracer

A method for the determination of 226Ra in environmental and geological samples by alpha-spectrometry is described. The method is based on the use of 225Ra, in radioactive equilibrium with its parent 229Th, as yield tracer. This tracer permits the incorporation of 226Ra determination into the radiochemical procedure commonly used for the determination of U and Th isotopes in the same sample. Estimation of 225Ra in the alpha-spectra is made via measurement of its alpha-emitting daughters, 217At being the most suitable to this purpose. In order to achieve it, several requirements need to be fulfilled in the radiochemical procedure, which will be discussed.

Journal Article↗

Steady neutron source measurement method for sigma(a) and sigma(s) in geological samples

An improved experimental method, using a steady neutron source in a moderating medium, has been developed to determine thermal neutron absorption and scattering cross sections for bulk geological media using discrete samples. The system design has been optimized and experimental results have been benchmarked using Monte Carlo simulation. Studies have been performed to improve the measurement sensitivity and reproducibility over previous designs. A semi-empirical model has been developed for determining both absorption and scattering cross sections of the sample.

Journal Article↗

Comparison of uranium determination in some Syrian geologic samples using three reactor based methods

A set of 25 samples of soil, sediments, carbonate and phosphate rocks from Syria were analysed for uranium, using three reactor based methods; instrumental neutron activation analysis (INAA), delayed neutron counting (DNC) and one cycle of irradiation utilizing the cyclic activation system (CAS). Although the three methods are capable of irradiation samples, the last method is the least established for U determination in rocks. The measurements obtained by the three methods are compared. The results show good agreement, with a distinct linear relationship and significant positive correlation coefficients. It was concluded that the CAS method could reliably be used to rapidly determine uranium in geological samples.

Journal Article↗