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Determination of trace amounts of tin in geological materials by atomic absorption spectrometry

An atomic absorption method is described for the determination of traces of tin in rocks, soils, and stream sediments. A dried mixture of the sample and ammonium iodide is heated to volatilize tin tetraiodide -which is then dissolved in 5 % hydrochloric acid, extracted into TOPO-MIBK, and aspirated into a nitrous oxide-acetylene flame. The limit of determination is 2 p.p.m. tin and the relative standard deviation ranges from 2 to 14 %. Up to 20 % iron and 1000 p.p.m. Cu, Pb, Zn, Mn, Hg, Mo, V, or W in the sample do not interfere. As many as 50 samples can be easily analyzed per man-day.

Analytica Chimica Acta

Determination of arsenic in geological materials by electrothermal atomic-absorption spectrometry after hydride generation

Rock and soil samples are decomposed with HClO 4 —HNO 3 ; after further treatment, arsine is generated and absorbed in a dilute silver nitrate solution. Aliquots of this solution are injected into a carbon rod atomizer. Down to 1 ppm As in samples can be determined and there are no significant interferences, even from chromium in soils. Good results were obtained for geochemical reference samples.

Analytica Chimica Acta

Isotopic identification of the source of methane in subsurface sediments of an area surrounded by waste disposal facilities

The major source of methane (CH4) in subsurface sediments on the property of a former hazardous waste treatment facility was determined using isotopic analyses measured on CH4 and associated groundwater. The site, located on an earthen pier built into a shallow wetland lake, has had a history of waste disposal practices and is surrounded by landfills and other waste management facilities. Concentrations of CH4 up to 70% were found in the headspace gases of several piezometers screened at 3 different depths (ranging from 8 to 17 m) in lacustrine and glacial till deposits. Possible sources of the CH4 included a nearby landfill, organic wastes from previous impoundments and microbial gas derived from natural organic matter in the sediments. Isotopic analyses included ??13C, ??D, 14C, and 3H on select CH4 samples and ??D and ??18O on groundwater samples. Methane from the deepest glacial till and intermediate lacustrine deposits had ??13C values from -79 to -82???, typical of natural 'drift gas' generated by microbial CO2-reduction. The CH4 from the shallow lacustrine deposits had ??13C values from -63 to -76???, interpreted as a mixture between CH4 generated by microbial fermentation and the CO2-reduction processes within the subsurface sediments. The ??D values of all the CH4 samples were quite negative ranging from -272 to -299???. Groundwater sampled from the deeper zones also showed quite negative ??D values that explained the light ??D observed for the CH4. Radiocarbon analyses of the CH4 showed decreasing 14C activity with depth, from a high of 58 pMC in the shallow sediments to 2 pMC in the deeper glacial till. The isotopic data indicated the majority of CH4 detected in the fill deposits of this site was microbial CH4 generated from naturally buried organic matter within the subsurface sediments. However, the isotopic data of CH4 from the shallow piezometers was more variable and the possibility of some mixing with oxidized landfill CH4 could not be completely ruled out.

Applied Geochemistry

High voltage: The molecular properties of redox-active dissolved organic matter in northern high-latitude lakes

Redox-active functional groups in dissolved organic matter (DOM) are crucial for microbial electron transfer and methane emissions. However, the extent of aquatic DOM redox properties across northern high-latitude lakes and their relationships with DOM composition have not been thoroughly described. We quantified electron donating capacity (EDC) and electron accepting capacity (EAC) in lake DOM from Canada to Alaska and assessed their relationships with parameters from absorbance, fluorescence, and ultrahigh resolution mass spectrometry (FT-ICR MS) analyses. EDC and EAC are strongly tied to aromaticity and negatively related to aliphaticity and protein-like content. Redox-active formulae spanned a range of aromaticity, including highly unsaturated phenolic formulae, and correlated negatively with many aliphatic N and S-containing formulae. This distribution illustrates the compositional diversity of redox-sensitive functional groups and their sensitivity to ecosystem properties such as local hydrology and residence time. Finally, we developed a reducing index ( RI ) to predict EDC in aquatic DOM from FT-ICR MS spectra and assessed its robustness using riverine DOM. As the hydrology of the northern high-latitudes continues to change, we expect differences in the quantity and partitioning of EDC and EAC within these lakes, which have implications for local water quality and methane emissions.

Environmental Science & Technology

De facto water reuse: Investigating the fate and transport of chemicals of emerging concern from wastewater discharge through drinking water treatment using non-targeted analysis and suspect screening

Wastewater is a source for many contaminants of emerging concern (CECs), and surface waters receiving wastewater discharge often serve as source water for downstream drinking water treatment plants. Nontargeted analysis and suspect screening methods were used to characterize chemicals in residence-time-weighted grab samples and companion polar organic chemical integrative samplers (POCIS) collected on three separate hydrologic sampling events along a surface water flow path representative of de facto water reuse. The goal of this work was to examine the fate of CECs along the study flow path as water is transported from wastewater effluent through drinking water treatment. Grab and POCIS samples provided a comparison between residence-time-weighted single-point and integrative sample results. This unique and rigorous study design, coupled with advanced analytical chemistry tools, provided important insights into chemicals found in drinking water and their potential sources, which can be used to help prioritize chemicals for further study. K -means clustering analysis was used to identify patterns in chemical occurrences across both sampling sites and sampling events. Chemical features that occurred frequently or survived drinking water treatment were prioritized for identification, resulting in the probable identification of over 100 CECs in the watershed and 28 CECs in treated drinking water.

Environmental Science & Technology

Turbulence effects on volatilization rates of liquids and solutes

Volatilization rates of neat liquids (benzene, toluene, fluorobenzene, bromobenzene, ethylbenzene, m-xylene, o-xylene, o-dichlorobenzene, and 1-methylnaphthalene) and of solutes (phenol, m-cresol, benzene, toluene, ethylbenzene, o-xylene, and ethylene dibromide) from dilute water solutions have been measured in the laboratory over a wide range of air speeds and water-stirring rates. The overall transfer coefficients (KL) for individual solutes are independent of whether they are in single- or multi-solute solutions. The gas-film transfer coefficients (kG) for solutes in the two-film model, which have hitherto been estimated by extrapolation from reference coefficients, can now be determined directly from the volatilization rates of neatliquids through anew algorithm. The associated liquid-film transfer coefficients (KL) can then be obtained from measured KL and kG values and solute Henry law constants (H). This approach provides a novel means for checking the precision of any kL and kG estimation methods for ultimate prediction of KL. The improved kG estimation enables accurate K L predictions for low-volatility (i.e., low-H) solutes where K L and kGH are essentially equal. In addition, the prediction of KL values for high-volatility (i.e., high-H) solutes, where KL ??? kL, is also improved by using appropriate reference kL values.

Environmental Science & Technology

Plan for living on a restless planet sets NASA's solid Earth agenda

What are the most important challenges facing solid Earth science today and over the next two decades? And what is the best approach for NASA, in partnership with other agencies, to address those challenges? A new report, Living on a Restless Planet, provides a blueprint for answering these questions. The top priority for a new spacecraft mission in the area of solid Earth science over the next 5 years, according to this report, is a satellite dedicated to Interferometric Synthetic Aperture Radar (InSAR). At the request of NASA, the Solid Earth Science Working Group (SESWG) developed a strategy for the highest priority objectives in solid Earth science for the space agency over the next 25 years. The strategy addresses six challenges that are of fundamental scientific importance, have strong implications for society, and are amenable to substantial progress through a concerted series of scientific observations from space.

Eos Science News

Inhibition of grain boundary sliding creep in fine-grained ice by inter-granular particles: Implications for planetary ice masses

Ice in both terrestrial and planetary settings often contains rock particles. Here we present an experimental investigation of the influence of intergranular particles on the rheological behavior of ice. Experiments were performed on samples fabricated from 10‐μm ice powders +1‐μm graphite or 0.8‐μm alumina particles and subjected to elevated confining pressures. A critical particle fraction, ∼6%, was observed, below which samples behave like pure ice and deform by both grain boundary sliding (GBS) and dislocation creep, and above which GBS creep is impeded. Above this critical fraction, ice grains occur in particle‐free clusters surrounded by bands of particles mixed with fine‐grained ice, resulting in the impedance of GBS in the bands as well as sliding between the ice clusters. Our results imply that South Polar Layered Deposits and midlatitude lobate debris aprons on Mars must contain >94% ice and that the shallow subsurface of Ceres could contain >90% ice.

Geophysical Research Letters

The importance of lake emergent aquatic vegetation for estimating Arctic-boreal methane emissions

Areas of lakes that support emergent aquatic vegetation emit disproportionately more methane than open water but are under-represented in upscaled estimates of lake greenhouse gas emissions. These shallow areas are typically less than ∼1.5 m deep and can be detected with synthetic aperture radar (SAR). To assess the importance of lake emergent vegetation (LEV) zones to landscape-scale methane emissions, we combine airborne SAR mapping with field measurements of vegetated and open-water methane flux. First, we use Uninhabited Aerial Vehicle SAR data from the NASA Arctic-Boreal Vulnerability Experiment to map LEV in 4,572 lakes across four Arctic-boreal study areas and find it comprises ∼16% of lake area, exceeding previous estimates, and exhibiting strong regional differences (averaging 59 [50–68]%, 22 [20–25]%, 1.0 [0.8–1.2]%, and 7.0 [5.0–12]% of lake areas in the Peace-Athabasca Delta, Yukon Flats, and northern and southern Canadian Shield, respectively). Next, we account for these vegetated areas through a simple upscaling exercise using paired methane fluxes from regions of open water and LEV. After excluding vegetated areas that could be accounted for as wetlands, we find that inclusion of LEV increases overall lake emissions by 21 [18–25]% relative to estimates that do not differentiate lake zones. While LEV zones are proportionately greater in small lakes, this relationship is weak and varies regionally, underscoring the need for methane-relevant remote sensing measurements of lake zones and a consistent criterion for distinguishing wetlands. Finally, Arctic-boreal lake methane upscaling estimates can be improved with more measurements from all lake zones.

Journal of Geophysical Research: Biogeosciences

Hydrologic and landscape controls on dissolved organic matter composition across western North American Arctic lakes

Northern high-latitude lakes are hotspots for cycling dissolved organic carbon (DOC) inputs from allochthonous sources to the atmosphere. However, the spatial distribution of lake dissolved organic matter (DOM) is largely unknown across Arctic-boreal regions with respect to the surrounding landscape. We expand on regional studies of northern high-latitude DOM composition by integrating DOC concentrations, optical properties, and molecular-level characterization from lakes spanning the Canadian Taiga to the Alaskan Tundra. Lakes were sampled during the summer from July to early September to capture the growing season. DOM became more optically processed and molecular-level aromaticity increased northward across the Canadian Shield to the southern Arctic and from interior Alaska to the Tundra, suggesting relatively greater DOM incorporation from allochthonous sources. Using water isotopes (δ 18 O-H 2 O), we report a weak overall trend of increasing DOC and decreasing aromaticity in lakes that were hydrologically isolated from the landscape and enriched in δ 18 O-H 2 O, while within-region trends were stronger and varied depending on the landscape. Finally, DOC correlated weakly with chromophoric dissolved organic matter (CDOM) across the study sites, suggesting that autochthonous and photobleached DOM were a major component of the DOC in these regions; however, some of the northernmost and wetland-dominated lakes followed pan-Arctic riverine DOC-CDOM relationships, indicating strong contributions from allochthonous inputs. As many lakes across the North American Arctic are experiencing changes in temperature and precipitation, we expect the proportions of allochthonous and autochthonous DOM to respond with aquatic optical browning with greater landscape connectivity and more internally produced DOM in hydrologically isolated lakes.

Global Biogeochemical Cycles

Apatite geo-thermochronology and geochemistry constrain Oligocene-Miocene growth and geodynamics of the northeastern Tibetan Plateau

Understanding the geodynamics of plateau evolution requires examining the spatial and temporal aspects of mountain building in the northeastern Tibetan Plateau, which are still under debate. Here we integrate apatite geo-thermochronological and geochemical data from the Oligocene-Miocene succession of the Xunhua Basin to elucidate the evolution of the regional topography. The results suggest sediment provenance changes, at ca. 28, 20 and 12 Ma, indicating topographic growth of the West Qinling, Laji Shan, and Jishi Shan source areas, respectively. Our findings reveal Oligocene-Miocene stepwise deformation and middle Miocene stress reorganization within the northeastern Tibetan Plateau. We attribute this to Oligocene lithospheric foundering beneath the south-central Tibetan Plateau and the middle Miocene initiation of sinistral strike-slip faults due to the underthrusting of India and North China. This study highlights the roles of lithospheric removal and continental underthrusting in plateau growth, and the value of multi-proxy apatite analyses in provenance studies.

Northeastern Tibetan Plateau

Functional restructuring of the global soil microbiome under multiple stressors

Microbes, as the planet’s most abundant and diverse organisms, drive soil functions globally and are vulnerable to environmental stressors triggered by global change. Yet, knowledge regarding the impacts of multiple environmental stressors on their functional profiles as well as the consequences for soil functionality largely remains unknown. Here, we analyze two global-scale datasets including information on soil metagenomics and multiple environmental stressors. We find that across terrestrial ecosystems worldwide, up to 60% of all functional genes significantly shift when soil microbes experience the high-level of concurrent stressors. In this regard, the relative abundances of genes involved in microbial growth are negatively linked to the increasing number of stressors. Conversely, those genes linked to stress resistance and energy production exhibit positive responses. Taken together, our findings highlight a significant restructuring of global soil functional microbiomes in response to multiple environmental stressors. Consequently, such restructuring drives community-level shifts in matter and energy reallocations, thereby impacting the maintenance of soil functionality under the projected global change.

Nature Communications

Explosive 2018 eruptions at Kīlauea driven by a collapse-induced stomp-rocket mechanism

Explosive volcanic eruptions produce hazardous atmospheric plumes composed of tephra particles, hot gas and entrained air. Such eruptions are generally driven by magmatic fragmentation or steam expansion. However, an eruption mechanism outside this phreatic–magmatic spectrum was suggested by a sequence of 12 explosive eruptions in May 2018 at Kīlauea, Hawaii, that occurred during the early stages of caldera collapse and produced atmospheric plumes reaching 8 km above the vent. Here we use seismic inversions for reservoir pressure as a source condition for three-dimensional simulations of transient multiphase eruptive plume ascent through a conduit and stratified atmosphere. We compare the simulations with conduit ascent times inferred from seismic and infrasound data, and with plume heights from radar data. We find that the plumes are consistent with eruptions caused by a stomp-rocket mechanism involving the abrupt subsidence of reservoir roof rock that increased pressure in the underlying magma reservoir. In our model, the reservoir was overlain by a pocket of accumulated high-temperature magmatic gas and lithic debris, which were driven through a conduit approximately 600 m long to erupt particles at rates of around 3,000 m 3 s −1 . Our results reveal a distinct collapse-driven type of eruption and provide a framework for integrating diverse geophysical and atmospheric data with simulations to gain a better understanding of unsteady explosive eruptions.

Hawaii

Determination of sub-microgram amounts of selenium in geological materials by atomic-absorption spectrophotometry with electrothermal atomisation after solvent extraction

An atomic-absorption spectrophotometric method with electrothermal atomisation has been developed for the determination of selenium in geological materials. The sample is decomposed with a mixture of nitric, perchloric and hydrofluoric acids and heated with hydrochloric acid to reduce selenium to selenium(IV). Selenium is then extracted into toluene from a hydrochloric acid-hydrobromic acid medium containing iron. A few micro-litres of the toluene extract are injected into a carbon rod atomiser, using a nickel solution as a matrix modifier. The limits of determination are 0.2–200 p.p.m. of selenium in a geological sample. For concentrations between 0.05 and 0.2 p.p.m., back-extraction of the selenium into dilute hydrochloric acid is employed before atomisation. Selenium values for reference samples obtained by replicate analysis are in general agreement with those reported by other workers, with relative standard deviations ranging from 4.1 to 8.8%. Recoveries of selenium spiked at two levels were 98–108%. Major and trace elements commonly encountered in geological materials do not interfere. Arsenic has a suppressing effect on the selenium signals, but only when its concentration is greater than 1 000 p.p.m. Nitric acid interferes seriously with the extraction of selenium and must be removed by evaporation in the sample-digestion step.

The Analyst

Atomic-absorption determination of mercury in geological materials by flame and carbon-rod atomisation after solvent extraction and using co-extracted silver as a matrix modifier

Based on modifications and expansion of the original Tindall's solvent extraction flame atomic-absorption procedure, an atomic-absorption spectrophotometric method has been developed for the determination of mercury in geological materials. The sample is digested with nitric and hydrochloric acids in a boiling water-bath. The solution is made ammoniacal and potassium iodide and silver nitrate are added. The mercury is extracted into isobutyl methyl ketone as the tetraiodomercurate(ll). Added silver is co-extracted with mercury and serves as a matrix modifier in the carbon-rod atomiser. The mercury in the isobutyl methyl ketone extract may be determined by either the flame- or the carbon-rod atomisation method, depending on the concentration level. The limits of determination are 0.05-10 p.p.m. of mercury for the carbon-rod atomisation and 1 -200 p.p.m. of mercury for the flame atomisation. Mercury values for reference samples obtained by replicate analyses are in good agreement with those reported by other workers, with relative standard deviations ranging from 2.3 to 0.9%. Recoveries of mercury spiked at two levels were 93-106%. Major and trace elements commonly found in geological materials do not interfere.

The Analyst

How organisms do the right thing: The attractor hypothesis

Neo-Darwinian theory is highly successful at explaining the emergence of adaptive traits over successive generations. However, there are reasons to doubt its efficacy in explaining the observed, impressively detailed adaptive responses of organisms to day-to-day changes in their surroundings. Also, the theory lacks a clear mechanism to account for both plasticity and canalization. In effect, there is a growing sentiment that the neo-Darwinian paradigm is incomplete, that something more than genetic structure, mutation, genetic drift, and the action of natural selection is required to explain organismal behavior. In this paper we extend the view of organisms as complex self-organizing entities by arguing that basic physical laws, coupled with the acquisitive nature of organisms, makes adaptation all but tautological. That is, much adaptation is an unavoidable emergent property of organisms' complexity and, to some a significant degree, occurs quite independently of genomic changes wrought by natural selection. For reasons that will become obvious, we refer to this assertion as the attractor hypothesis. The arguments also clarify the concept of "adaptation." Adaptation across generations, by natural selection, equates to the (game theoretic) maximization of fitness (the success with which one individual produces more individuals), while self-organizing based adaptation, within generations, equates to energetic efficiency and the matching of intake and biosynthesis to need. Finally, we discuss implications of the attractor hypothesis for a wide variety of genetical and physiological phenomena, including genetic architecture, directed mutation, genetic imprinting, paramutation, hormesis, plasticity, optimality theory, genotype-phenotype linkage and puncuated equilibrium, and present suggestions for tests of the hypothesis. ?? 1998 American Institute of Physics.

Chaos

Comparative assessment of groundwater quality in the Tangshan region of the People's Republic of China and similar areas in the U.S.

Groundwater quality with respect to nitrate, major inorganic constituents, stable isotopes, and tritium was assessed in the agricultural Tangshan region in the Hai He River Basin of the People's Republic of China and compared with three regions in the U.S.: the Delmarva Peninsula of Delaware, Maryland, and Virginia; the San Joaquin Valley of California; and the Sacramento Valley of California. The China and U.S. regions are similar in size and land use, but have different climatic conditions and patterns of water use for irrigation. The Tangshan region has been in agricultural production for a much longer time, probably several centuries, than the three U.S. regions; however, the widespread use of synthetic fertilizers and other soil amendments probably started at a similar time in all four regions. In all four regions, median nitrate concentrations were generally below the U.S. drinking water standard of 10 mg/l of nitrate as nitrogen. However, higher concentrations and a greater range were evident for the Tangshan region. In the water samples collected from a shallow aquifer in the Tangshan region (over 25% of all samples), nitrate concentrations exceeded the Chinese standard of 20 mg/l, whereas few comparative samples (2.6%) collected in the U.S. exceeded 20 mg/l. In Tangshan, relatively low nitrate, which is indicative of uncontaminated background concentrations, was measured in older water of deeper wells. Recently recharged water was detected in wells drilled as deep as 150 m. Nitrate concentrations above background levels were also measured in water samples from these wells. In addition to nitrate, the agricultural area of the Tangshan region has been affected by elevated total dissolved solids and iron, the latter attributed to widespread application of animal wastes and sewage deposited on the land surface, which lead to oxygen depletion in the subsurface environment and dissolution of iron. The elevated total dissolved solids of the Tangshan study area could not be attributed to any one process.

Scientific World Journal