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Decomposition techniques

Sample decomposition is a fundamental and integral step in the procedure of geochemical analysis. It is often the limiting factor to sample throughput, especially with the recent application of the fast and modern multi-element measurement instrumentation. The complexity of geological materials makes it necessary to choose the sample decomposition technique that is compatible with the specific objective of the analysis. When selecting a decomposition technique, consideration should be given to the chemical and mineralogical characteristics of the sample, elements to be determined, precision and accuracy requirements, sample throughput, technical capability of personnel, and time constraints. This paper addresses these concerns and discusses the attributes and limitations of many techniques of sample decomposition along with examples of their application to geochemical analysis. The chemical properties of reagents as to their function as decomposition agents are also reviewed. The section on acid dissolution techniques addresses the various inorganic acids that are used individually or in combination in both open and closed systems. Fluxes used in sample fusion are discussed. The promising microwave-oven technology and the emerging field of automation are also examined. A section on applications highlights the use of decomposition techniques for the determination of Au, platinum group elements (PGEs), Hg, U, hydride-forming elements, rare earth elements (REEs), and multi-elements in geological materials. Partial dissolution techniques used for geochemical exploration which have been treated in detail elsewhere are not discussed here; nor are fire-assaying for noble metals and decomposition techniques for X-ray fluorescence or nuclear methods be discussed.

Journal of Geochemical Exploration↗

Host-rock controlled epigenetic, hydrothermal metasomatic origin of the Bayan Obo REEFe-Nb ore deposit, Inner Mongolia, P.R.C.

Bayan Obo, a complex rare earth element (REE) Fe Nb ore deposit, located in Inner Mongolia, P.R.C. is the world's largest known REE deposit. The deposit is chiefly in a marble unit (H8), but extends into an overlying unit of black shale, slate and schist unit (H9), both of which are in the upper part of the Middle Proterozoic Bayan Obo Group. Based on sedimentary structures, the presence of detrital quartz and algal fossil remains, and the 16-km long geographic extent, the H8 marble is a sedimentary deposit, and not a carbonatite of magmatic origin, as proposed by some previous investigators. The unit was weakly regionally metamorphosed (most probably the lower part of the green schist facies) into marble and quartzite prior to mineralization. Tectonically, the deposit is located on the northern flank of the Sino-Korean craton. Many hypotheses have been proposed for the origin of the Bayan Obo deposit; the studies reported here support an epigenetic, hydrothermal, metasomatic origin. Such an origin is supported by field and laboratory textural evidence; 232 Th/ 208 Pb internal isochron mineral ages of selected monazite and bastnaesite samples; 40 Ar/ 39 Ar incremental heating minimum mineral ages of selected alkali amphiboles; chemical compositions of different generations of both REE ore minerals and alkali amphiboles; and evidence of host-rock influence on the various types of Bayan Obo ores. The internal isochron ages of the REE minerals indicate Caledonian ages for various episodes of REE and Fe mineralization. No evidence was found to indicate a genetic relation between the extensive biotite granitic rocks of Hercynian age in the mine region and the Bayan Obo are deposit, as suggested by previous workers.

Applied Geochemistry↗

Eutrophication study at the Panjiakou-Daheiting Reservoir system, northern Hebei Province, People's Republic of China: Chlorophyll-a model and sources of phosphorus and nitrogen

Concentrations, loads, and sources of nitrate and total phosphorus were investigated at the Panjiakou and Daheiting Reservoir system in northern Hebei Province, People's Republic of China. The Luan He River is the primary source of water to these reservoirs, and the upstream watershed has a mix of land uses including agriculture, forest, and one large urban center. The reservoirs have a primary use for storage of drinking water and partially supply Tianjin City with its annual needs. Secondary uses include flood control and aqua culture (fish cages). The response of the reservoir system from phosphorus input, with respect to chlorophyll- a production from algae, was fitted to a model of normalized phosphorus loading that regresses the average summer-time chlorophyll- a concentration to the average annual phosphorus concentration of the reservoir. Comparison of the normalized phosphorus loading and chlorophyll- a response of this system to other reservoirs throughout the world indicate a level of eutrophication that will require up to an approximate 5–10-fold decrease in annual phosphorus load to bring the system to a more acceptable level of algal productivity. Isotopes of nitrogen and oxygen in dissolved nitrate were measured from the headwater streams and at various locations along the major rivers that provide the majority of water to these reservoirs. Those isotopic measurements indicate that the sources of nitrate change from natural background in the rivers to animal manure and septic waste upstream of the reservoir. Although the isotopic measurements suggest that animal and septic wastes are a primary source of nutrients, measurements of the molar ratio of nitrogen to phosphorus are more indicative of row-cropping practices. Options for reduction of nutrient loads include changing the management practices of the aqua culture, installation of new sewage treatment systems in the large urbanized area of the upper watershed, and agricultural management practices that would reduce the loading of nutrients and soil erosion from that land use.

Agricultural Water Management↗

Short-term nitrogen additions can shift a coastal wetland from a sink to a source of N 2 O

Coastal salt marshes sequester carbon at high rates relative to other ecosystems and emit relatively little methane particularly compared to freshwater wetlands. However, fluxes of all major greenhouse gases (N 2 O, CH 4 , and CO 2 ) need to be quantified for accurate assessment of the climatic roles of these ecosystems. Anthropogenic nitrogen inputs (via run-off, atmospheric deposition, and wastewater) impact coastal marshes. To test the hypothesis that a pulse of nitrogen loading may increase greenhouse gas emissions from salt marsh sediments, we compared N 2 O, CH 4 and respiratory CO 2 fluxes from nitrate-enriched plots in a Spartina patens marsh (receiving single additions of NaNO 3 equivalent to 1.4 g N m −2 ) to those from control plots (receiving only artificial seawater solutions) in three short-term experiments (July 2009, April 2010, and June 2010). In July 2009, we also compared N 2 O and CH 4 fluxes in both opaque and transparent chambers to test the influence of light on gas flux measurements. Background fluxes of N 2 O in July 2009 averaged −33 μmol N 2 O m −2 day −1 . However, within 1 h of nutrient additions, N 2 O fluxes were significantly greater in plots receiving nitrate additions relative to controls in July 2009. Respiratory rates and CH 4 fluxes were not significantly affected. N 2 O fluxes were significantly higher in dark than in transparent chambers, averaging 108 and 42 μmol N 2 O m −2 day −1 respectively. After 2 days, when nutrient concentrations returned to background levels, none of the greenhouse gas fluxes differed from controls. In April 2010, N 2 O and CH 4 fluxes were not significantly affected by nitrate, possibly due to higher nitrogen demands by growing S. patens plants, but in June 2010 trends of higher N 2 O fluxes were again found among nitrate-enriched plots, indicating that responses to nutrient pulses may be strongest during the summer. In terms of carbon equivalents, the highest average N 2 O and CH 4 fluxes observed, exceeded half the magnitude of typical daily net carbon sequestration rates by salt marshes. Thus, anthropogenic additions of nitrate to coasts can substantially alter N 2 O fluxes from marshes, although substantial temporal variation in these fluxes was observed. To better assess the climatic roles of salt marshes, greenhouse gas emissions need to be studied in the context of chronic nitrogen loads that impact many coastal ecosystems.

Atmospheric Environment↗

Large fires or small fires, will they differ in affecting shifts in species composition and distributions under climate change?

Climate change is expected to increase fire activity, which has the potential to accelerate climate-induced shifts in species composition and distribution in the boreal-temperate ecotone. Wildfire can kill resident trees, and thus provide establishment opportunities for migrating tree species. However, the role of fire size and its interactions with tree species with varied life-history attributes in driving climate-induced shifts is not understood. Future fire regimes could be characterized by many small fires or a few large fires. Large and small fires create and regulate distinct burn patterns, which may influence tree-species responses and post-fire successional trajectories. Here we investigated the effects of future fire-regime variability on the boreal-temperate ecotone of northeastern China under climate change using a coupled forest dynamic model (LANDIS PRO) and ecosystem process model (LINKAGES). We simulated fire regimes using the LANDIS PRO fire module. We designed two fire scenarios (frequent, small fires and infrequent, large fires) to represent different fire regimes in terms of fire size. Results showed fire-catalyzed, climate-induced transitions from boreal to pioneer and temperate forest communities. Frequent, small fires resulted in 13% and 23% higher increases in pioneer and temperate species respectively, relative to infrequent, large fires. Therefore, species composition shifts were faster following frequent, small fires than infrequent, large fires. The results can help policymakers and forest managers determine tradeoffs among strategies to mitigate or adapt to climate change under altered fire regimes.

Great Xing'an Mountains↗

Clay-catalyzed reactions of coagulant polymers during water chlorination

The influence of suspended clay/solid particles on organic-coagulant reactions during water chlorination was investigated by analyses of total product formation potential (TPFP) and disinfection by-product (DBP) distribution as a function of exchanged clay cation, coagulant organic polymer, and reaction time. Montmorillonite clays appeared to act as a catalytic center where the reaction between adsorbed polymer and disinfectant (chlorine) was mediated closely by the exchanged clay cation. The transition-metal cations in clays catalyzed more effectively than other cations the reactions between a coagulant polymer and chlorine, forming a large number of volatile DBPs. The relative catalytic effects of clays/solids followed the order Ti-Mont > Fe-Mont > Cu-Mont > Mn-Mont > Ca-Mont > Na-Mont > quartz > talc. The effects of coagulant polymers on TPFP follow the order nonionic polymer > anionic polymer > cationic polymer. The catalytic role of the clay cation was further confirmed by the observed inhibition in DBP formation when strong chelating agents (o-phenanthroline and ethylenediamine) were added to the clay suspension. Moreover, in the presence of clays, total DBPs increased appreciably when either the reaction time or the amount of the added clay or coagulant polymer increased. For volatile DBPs, the formation of halogenated methanes was usually time-dependent, with chloroform and dichloromethane showing the greatest dependence. ?? 2003 Elsevier Inc. All rights reserved.

Journal of Colloid and Interface Science↗

A lacustrine record from Lop Nur, Xinjiang, China: Implications for paleoclimate change during Late Pleistocene

Climate variability during the Late Pleistocene is studied from the proxies in core CK-2 drilled from the Luobei Depression (91??03???E, 40??47???N), Lop Nur in the eastern Tarim Basin, Xinjiang, China. Geophysical and geochemical properties, including magnetic susceptibility, granularity, chroma, carbonate content, loss on ignition and trace elements, have been determined to reconstruct the environmental evolution of the area during 32-9 ka BP. The chronology is established by uranium-thorium disequilibrium dating techniques. Our data suggest four paleoclimate stages, indicating glacial variations between cold-humid and warm-arid environments. A period of extreme humidity occurred during 31,900-19,200 yr BP is attributed the last glacial maximum (LGM). The period was followed by a warm-arid episode during 19,200-13,500 yr BP. Then a cold-humid interval during 13,500-12,700 yr BP may correspond to another cooling phases at high latitudes of the Northern Hemisphere. The last stage from 12,700 to 9000 yr BP has a trend that the climate turned warm and arid. The Lop Nur region is characterized by particularly humid stadials and arid interstadials. The climate variability in Lop Nur was constrained by global climate change because it is correlated with Dansgaard-Oeschger and Heinrich events, which were observed at the northern high latitudes. The synchroneity of the palaeoclimatic events suggested that cold air activity at the northern high latitudes was the most important factor that influenced the climate evolution in the Lop Nur region. A probable mechanism that involves the migration of westerly winds is proposed to interpret this synchroneity. ?? 2008 Elsevier Ltd.

Journal of Asian Earth Sciences↗

Insights on gas hydrate formation and growth within an interbedded sand reservoir from well logging at the Qiongdongnan Basin, South China Sea

Although variable well log resolution and its control on saturation estimation has been studied, it has not been directly applied to a specific location to explore the nature of gas hydrate within a sand reservoir. We applied in-situ measurements of resistivities, neutron porosity, and gamma ray at two sites in the Qiongdongnan Basin, South China Sea (QDN-W05–2021 and QDN-W08–2021) to investigate the reservoir parameters of a hydrate-bearing sand reservoir. Our results show that gas hydrate is distributed in 5 zones with a total thickness of 10.7 m and an average saturation of 69% at the QDN-W05–2021 site, while they are distributed in 2 zones with a total thickness of 4.3 m and an average saturation of 49% at the QDN-W08–2021 site. We found that variances in saturations estimated from lateral-extra deep button (RX), phase shift (P40H-P40L), and attenuation (A40H-A40L) resistivities within the laterally mapped continuous sand body were affected by the nature of gas hydrate occurrences. Results indicate gas hydrate forms and accumulates at the center of the sand layer and tends to be less or not present toward the top and base. Integrated with seismic data, the in-situ measurements provide insights in the evolution of a mushroom-shaped, hydrate-gas reservoir system. In the system, free gas is likely horizontally transported from the top-center of the gas chimney to the surrounding areas in the early stage dominated by a warm-gas environment, whereas hydrate forms in the opposite pathway starting from the surrounding areas in the following stage with temperature reducing. Our study suggests that high-resolution in-situ measurements not only are a tool to identify the physical properties, but also can be used to help explain the physical process of hydrate growth and accumulation.

Marine Geology↗

Quantification of wetland vegetation communities features with airborne AVIRIS-NG, UAVSAR, and UAV LiDAR data in Peace-Athabasca Delta

Arctic-boreal wetlands, important ecosystems for biodiversity and ecological services, are experiencing hydrological changes including permafrost thaw, earlier snowmelt, and increased wildfire susceptibility. These changes are affecting wetland productivity, species diversity, and biogeochemical cycles. However, given the diverse forms and structures of wetland vegetation communities, traditional wetland maps generated from lower spatial and spectral resolution satellite imagery lack community-level vegetation classification and miss spatially complex patterns. In this study, we built a cloud-based workflow to map wetland vegetation community of the Peace-Athabasca Delta (PAD), Canada, by leveraging high-resolution (5-m) airborne multi-sensor datasets, namely NASA's Airborne Visible/Infrared Imaging Spectrometer-Next Generation (AVIRIS-NG) and Uninhabited Aerial Vehicle Synthetic Aperture Radar (UAVSAR), and a historical LiDAR archive. Validation of our classifications using ground references indicates that classifications derived from AVIRIS-NG have higher accuracies (≥87.9%) than either UAVSAR (65.6%) or LiDAR (75.9%) for mapping wetland vegetation communities. We also show improved classification accuracy when combining information from multiple sensors. In particular, incorporating AVIRIS-NG and UAVSAR datasets substantially reduced omission errors of wet graminoid and wet shrub classes from 29.6% to 20.5% and from 10.8% to 7.5%, respectively. Combining AVIRIS-NG and LiDAR datasets further improves overall accuracy (+2.2%) for most classifications, especially emergent vegetation, wet graminoid, and wet shrub. The best performing model, using features derived from all three sensors, achieved an overall accuracy of 93.5%. The framework established here can be used to leverage extensive airborne AVIRIS-NG and UAVSAR datasets collected across Alaska and northwest Canada to understand the spatial distribution of Arctic-Boreal wetland vegetation communities.

Remote Sensing of Environment↗

Contrasting distributions of groundwater arsenic and uranium in the western Hetao basin, Inner Mongolia: Implication for origins and fate controls

Although As concentrations have been investigated in shallow groundwater from the Hetao basin, China, less is known about U and As distributions in deep groundwater, which would help to better understand their origins and fate controls. Two hundred and ninety-nine groundwater samples, 122 sediment samples, and 14 rock samples were taken from the northwest portion of the Hetao basin, and analyzed for geochemical parameters. Results showed contrasting distributions of groundwater U and As, with high U and low As concentrations in the alluvial fans along the basin margins, and low U and high As concentrations downgradient in the flat plain. The probable sources of both As and U in groundwater were ultimately traced to the bedrocks in the local mountains (the Langshan Mountains). Chemical weathering of U-bearing rocks (schist, phyllite, and carbonate veins) released and mobilized U as UO 2 (CO 3 ) 2 2 − and UO 2 (CO 3 ) 3 4 − species in the alluvial fans under oxic conditions and suboxic conditions where reductions of Mn and NO 3 − were favorable (OSO), resulting in high groundwater U concentrations. Conversely, the recent weathering of As-bearing rocks (schist, phyllite, and sulfides) led to the formation of As-bearing Fe(III) (hydr)oxides in sediments, resulting in low groundwater As concentrations. Arsenic mobilization and U immobilization occurred in suboxic conditions where reduction of Fe(III) oxides was favorable and reducing conditions (SOR). Reduction of As-bearing Fe(III) (hydr)oxides, which were formed during palaeo-weathering and transported and deposited as Quaternary aquifer sediments, was believed to release As into groundwater. Reduction of U(VI) to U(IV) would lead to the formation of uraninite, and therefore remove U from groundwater. We conclude that the contrasting distributions of groundwater As and U present a challenge to ensuring safe drinking water in analogous areas, especially with high background values of U and As.

Hetao Basin, Inner Mongolia↗

Investigating the chemical space coverage of multiple chromatographic and ionization methods using non-targeted analysis on surface and drinking water collected using passive sampling

Multiple non-targeted analysis tools were used to look for a broad range of possible chemical contaminants present in surface and drinking water using liquid chromatography separation and high-resolution mass spectrometry detection, including both quadrupole time of flight (Q-ToF) and Orbitrap instruments. Two chromatographic techniques were evaluated on an LC-Q-ToF with electrospray ionization in both positive and negative modes: (1) the traditionally used reverse phase C18 and (2) the hydrophilic interaction liquid chromatography (HILIC) aimed to capture more polar contaminants that may be present in water. Multiple ionization modes were evaluated with an LC-Orbitrap, including electrospray (ESI) and atmospheric pressure chemical ionization (APCI), also in both positive and negative modes. A suspect screening library of over 1300 possible environmental contaminants, including pesticides, pharmaceuticals, personal care products, illicit drugs/drugs of abuse, and various anthropogenic markers was made with experimentally collected data with the LC-Q-ToF with both column types, with 227 chemicals being retained by the HILIC column. The non-targeted methods using multiple chromatographic and ionization modes were applied to environmental water samples collected with polar organic chemical integrative samplers (POCIS), including surface water upstream and downstream from wastewater effluent discharge, and the downstream drinking water intake and treated drinking water for three distinct sampling events. For the LC-Q-ToF, 442 chemical features were detected on the C18 column and 91 with the HILIC column in the POCIS extracts, while 556 features were found on the Orbitrap workflow by ESI and 131 features detected by APCI. Over 100 chemicals were tentatively identified by suspect screening and database searching. The comprehensive and systematic evaluation of these methods serve as a step in characterizing the chemical space covered when utilizing different chromatography and ionization methods, or different instrument workflows on complex environmental mixtures.

Science of the Total Environment↗

Climate change in southern Illinois, USA, based on the age and δ 13 C of organic matter in cave sediments

Matrix-supported diamicton and uniform to laminated, silty, fine-grained sediment deposited from about 42,500 to 27,600 cal yr B.P. under slackwater conditions nearly filled two caves in southwestern Illinois. At some point, most of the sediment was flushed from the caves and from about 22,700 to 4000 cal yr B.P., floods deposited a drape of sandy and silty sediment on remnant slackwater successions, cobbly alluvium, and bedrock (especially from 7700 to 4000 cal yr B.P.). Clay mineral analyses of the slackwater cave sediment reveal a provenance of chiefly Petersburg Silt, a smectite- and illite-rich proglacial lacustrine unit present in the overlying Illinois Episode glacial succession. Today, remnants of the ancient subterranean slackwater deposits nearly fill several secondary passages and, in at least two locations, cover a cobble-mantled strath terrace 1.3 to 1.5 m above active stream channels. Slumping and sinkhole formation appear to have been important mechanisms for deposition of the ancient subterranean deposits. Slumping of these surficial deposits and associated vegetation can occur along the flanks of sinkholes (in addition to sinkhole formation) and enter caves; however, the finer organics, some of them comminuted during transport into the caves, become part of the cave alluvium. This finer organic fraction is the modern analog of the humified organic matter disseminated in slackwater sediment dated in this investigation by radiocarbon methods. Twenty-four 14C ages on humified organic matter provide chronologic control. The ??13C values of the organic matter reflect the proportion of C4-type to C3-type vegetation growing in and around swallets and sinkholes at the time of redeposition. Drought-tolerant C4-type vegetation was more prevalent relative to C3-type vegetation from 42,500 to 31,200 cal yr B.P. compared to conditions from 28,800 cal yr B.P. to the present. The ??13C values are consistent with the results from other investigations of speleothems and organic matter from loessial paleosols. ?? 2004 University of Washington. All rights reserved.

Quaternary Research↗

Determination of indium in geological materials by electrothermal-atomization atomic absorption spectrometry with a tungsten-impregnated graphite furance

The sample is fused with lithium metaborate and the melt is dissolved in 15% (v/v) hydrobromic acid. Iron(III) is reduced with ascorbic acid to avoid its coextraction with indium as the bromide into methyl isobutyl ketone. Impregnation of the graphite furnace with sodium tungstate, and the presence of lithium metaborate and ascorbic acid in the reaction medium improve the sensitivity and precision. The limits of determination are 0.025–16 mg kg −1 indium in the sample. For 22 geological reference samples containing more than 0.1 mg kg −1 indium, relative standard deviations ranged from 3.0 to 8.5% (average 5.7%). Recoveries of indium added to various samples ranged from 96.7 to 105.6% (average 100.2%).

Analytica Chimica Acta↗

Determination of silver in soils, sediments, and rocks by organic-chelate extraction and atomic absorption spectrophotometry

A useful method for the determination of silver in soil, sediment, and rock samples in geochemical exploration has been developed. The sample is digested with concentrated nitric acid, and the silver extracted with triisooctyl thiophosphate (TOTP) in methyl isobutyl ketone (MIBK) after dilution of the acid digest to approximately 6 M . The extraction of silver into the organic extractant is quantitative and not affected by the nitric acid concentration from 4 M to 8 M , or by different volumes of TOTP-MIBK. The extracted silver is stable and remains in the organic phase up to several days. The silver concentration is determined by atomic absorption spectrophotometry.

Analytica Chimica Acta↗

Atomic absorption spectrometric determination of copper, zinc, and lead in geological materials

An atomic absorption spectrometric method is described for the determination of copper, zinc, and lead in geological materials. The sample is digested with HF—HCl—H 2 O 2 ; the final solution for analysis is in 10 % (v/v) HCl. Copper and zinc are determined directly by aspirating the solution into an air—acetylene flame. A separate aliquot of the solution is used for determination of lead; lead is extracted into TOPO-MIBK from the acidic solution in the presence of iodide and ascorbic acid. For a 0.50-g sample, the limits of determination are 10–2000 p.p.m. for Cu and Zn, and 5–5000 p.p.m. for Pb. As much as 40 % Fe or Ca. and 10 % Al, Mg, or Mn in the sample do not interfere. The proposed method can be applied to the determination of copper, zinc, and lead in a wide range of geological materials including iron- and manganese-rich, calcareous and carbonate samples.

Analytica Chimica Acta↗

Flame and flameless atomic-absorption determination of tellurium in geological materials

The sample is digested with a solution of hydrobromic acid and bromine and the excess of bromine is expelled. After dilution of the solution to approximately 3 M in hydrobromic acid, ascorbic acid is added to reduce iron(III) before extraction of tellurium into methyl isobutyl ketone (MIBK). An oxidizing air-acetylene flame is used to determine tellurium in the 0.1–20 ppm range. For samples containing 4–200 ppb of tellurium, a carbon-rod atomizer is used after the MIBK extract has been washed with 0.5 M hydrobromic acid to remove the residual iron. The flame procedure is useful for rapid preliminary monitoring, and the flameless procedure can determine tellurium at very low concentrations.

Analytica Chimica Acta↗

Atomic-absorption spectrometric determination of cobalt, nickel, and copper in geological materials with matrix masking and chelation-extraction

An atomic-absorption spectrometric method is reported for the determination of cobalt, nickel, and copper in a variety of geological materials including iron- and manganese-rich, and calcareous samples. The sample is decomposed with HP-HNO 3 and the residue is dissolved in hydrochloric acid. Ammonium fluoride is added to mask iron and 'aluminum. After adjustment to pH 6, cobalt, nickel, and copper are chelated with sodium diethyl-dithiocarbamate and extracted into methyl isobutyl ketone. The sample is set aside for 24 h before analysis to remove interferences from manganese. For a 0.200-g sample, the limits of determination are 5–1000 ppm for Co, Ni, and Cu. As much as 50% Fe, 25% Mn or Ca, 20% Al and 10% Na, K, or Mg in the sample either individually or in various combinations do not interfere. Results obtained on five U.S. Geological Survey rock standards are in general agreement with values reported in the literature.

Analytica Chimica Acta↗