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Comparison of hot hydroxylamine hydrochloride and oxalic acid leaching of stream sediment and coated rock samples as anomaly enhancement techniques

A hot hydroxylamine hydrochloride (H-Hxl) extraction in 25% acetic acid is compared with the commonly used oxalic acid extraction as a method of anomaly enhancement for Cu and Zn in samples from two very different metal deposits and climatic environments. Results obtained on minus-80-mesh stream sediments from an area near the Magruder massive sulfide deposit in Lincoln County, Georgia, where the climate is humid subtropical, indicate that H-Hxl enhances the anomaly for Cu by a factor of 2 and for Zn by a factor of 1.5, compared to the oxalic method. Analyses of Fe oxide-coated rock samples from outcrops overlying the North Silver Bell porphyry copper deposit near Tucson, Arizona, where the climate is semi-arid to arid, indicate that both techniques effectively outline the zones of hydrothermal alteration. The H-Hxl extraction can also perform well in high-carbonate or high-clay environments, where other workers have suggested that oxalic acid is not very effective. Therefore, the H-Hxl method is recommended for general exploration use.

Journal of Geochemical Exploration

A comparison of iron oxide-rich joint coatings and rock chips as geochemical sampling media in exploration for disseminated gold deposits

We evaluated the effectiveness of iron oxide-rich fracture coatings as a geochemical sampling medium for disseminated gold deposits, as compared with conventional lithogeochemical methods, for samples from the Pinson mine and Preble prospect in southeastern Humboldt County, Nevada. That disseminated gold mineralization is associated with Hg, As, and Sb is clearly demonstrated in these deposits for both fracture coatings and rock chip samples. However, the relationship is more pronounced for fracture coatings. Fracture coatings at Pinson contain an average of 3.61, 5.13, 14.37, and 3.42 times more Au, As, Sb and Hg, respectively, than adjacent rock samples. At Preble, fracture coatings contain 3.13, 9.72, 9.18, and 1.85 times more Au, As, Sb and Hg, respectively, than do adjacent rock samples. Geochemical anomalies determined from fracture coatings are thus typically more intense than those determined from rock samples for these elements. The sizes of anomalies indicated by fracture coatings are also somewhat larger, but this is less obvious. In both areas, Sb anomalies are more extensive in fracture coatings. At Preble, some Hg and Au anomalies are also more extensive in fracture coatings. In addition to halos formed by the Hg, As and Sb, high values for Au/Ag and Zn/(Fe + Mn) are closely associated with gold mineralization at the Pinson mine. The large enhancement in geochemical response afforded by fracture coatings indicates a definite potential in the search for buried disseminated gold deposits.

Journal of Geochemical Exploration

A comparative study of stream water and stream sediment as geochemical exploration media in the Rio Tanama porphyry copper district, Puerto Rico

To test the relative effectiveness of stream water and sediment as geochemical exploration media in the Rio Tanama porphyry copper district of Puerto Rico, we collected and subsequently analyzed samples of water and sediment from 29 sites in the rivers and tributaries of the district. Copper, Mo, Pb, Zn, SO 4 2− , and pH were determined in the waters; Cu, Mo, Pb, and Zn were determined in the sediments. In addition, copper in five partial extractions from the sediments was determined. Geochemical contrast (anomaly-to-background quotient) was the principal criterion by which the effectiveness of the two media and the five extractions were judged. Among the distribution patterns of metals in stream water, that of copper most clearly delineates the known porphyry copper deposits and yields the longest discernable dispersion train. The distribution patterns of Mo, Pb, and Zn in water show little relationship to the known mineralization. The distribution of SO 4 2− in water delineates the copper deposits and also the more extensive pyrite alteration in the district; its recognizable downstream dispersion train is substantially longer than those of the metals, either in water or sediment. Low pH values in small tributaries delineate areas of known sulfide mineralization. The distribution patterns of copper in sediments clearly delineate the known deposits, and the dispersion trains are longer than those of copper in water. The partial determinations of copper related to secondary iron and manganese oxides yield the strongest geochemical contrasts and longest recognizable dispersion trains. Significantly high concentrations of molybdenum in sediments were found at only three sites, all within one-half km downstream of the known copper deposits. The distribution patterns of lead and zinc in sediments are clearly related to the known primary lead-zinc haloes around the copper deposits. The recognizable downstream dispersion trains of lead and zinc are shorter than those of copper.

Journal of Geochemical Exploration

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

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

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

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

Matrix modification with silver for the electrothermal atomization of arsenic and selenium

Silver as a matrix modifier is shown to improve the carbon-rod atomization of both arsenic and selenium for atomic absorption spectrometry. Compared to nickel, the efficiency of silver is greater for arsenic and about the same for selenium. Silver fulfils two functions in its reaction, namely stabilization during the ashing stage and enhancement of absorbance in the final atomization.

Analytica Chimica Acta