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At least 145 records · Page 8Linked to original sources

Arsenate adsorption mechanisms at the allophane: Water interface

We investigated arsenate (As(V)) reactivity and surface speciation on amorphous aluminosilicate mineral (synthetic allophane) surfaces using batch adsorption experiments, powder X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS). The adsorption isotherm experiments indicated that As(V) uptake increased with increasing [As(V)] o from 50 to 1000 μM (i.e., Langmuir type adsorption isotherm) and that the total As adsorption slightly decreased with increasing NaCl concentrations from 0.01 to 0.1 M. Arsenate adsorption was initially (0−10 h) rapid followed by a slow continuum uptake, and the adsorption processes reached the steady state after 720 h. X-ray absorption spectroscopic analyses suggest that As(V) predominantly forms bidentate binuclear surface species on aluminum octahedral structures, and these species are stable up to 11 months. Solubility calculations and powder XRD analyses indicate no evidence of crystalline Al−As(V) precipitates in the experimental systems. Overall, macroscopic and spectroscopic evidence suggest that the As(V) adsorption mechanisms at the allophane−water interface are attributable to ligand exchange reactions between As(V) and surface-coordinated water molecules and hydroxyl and silicate ions. The research findings imply that dissolved tetrahedral oxyanions (e.g., H 2 PO 4 2 - and H 2 AsO 4 2 - ) are readily retained on amorphous aluminosilicate minerals in aquifer and soils at near neutral pH. The inner-sphere adsorption mechanisms might be important in controlling dissolved arsenate and phosphate in amorphous aluminosilicate-rich low-temperature geochemical environments.

Environmental Science & Technology

Fractionation of fulvic acid by iron and aluminum oxides: influence on copper toxicity to Ceriodaphnia dubia

This study examines the effect on aquatic copper toxicity of the chemical fractionation of fulvic acid (FA) that results from its association with iron and aluminum oxyhydroxide precipitates. Fractionated and unfractionated FAs obtained from streamwater and suspended sediment were utilized in acute Cu toxicity tests on ,i>Ceriodaphnia dubia. Toxicity test results with equal FA concentrations (6 mg FA/L) show that the fractionated dissolved FA was 3 times less effective at reducing Cu toxicity (EC 50 13 ± 0.6 μg Cu/L) than were the unfractionated dissolved FAs (EC 50 39 ± 0.4 and 41 ± 1.2 μg Cu/L). The fractionation is a consequence of preferential sorption of molecules having strong metal-binding (more aromatic) moieties to precipitating Fe- and Al-rich oxyhydroxides, causing the remaining dissolved FA to be depleted in these functional groups. As a result, there is more bioavailable dissolved Cu in the water and hence greater potential for Cu toxicity to aquatic organisms. In predicting Cu toxicity, biotic ligand models (BLMs) take into account dissolved organic carbon (DOC) concentration; however, unless DOC characteristics are accounted for, model predictions can underestimate acute Cu toxicity for water containing fractionated dissolved FA. This may have implications for water-quality criteria in systems containing Fe- and Al-rich sediment, and in mined and mineralized areas in particular. Optical measurements, such as specific ultraviolet absorbance at 254 nm (SUVA 254 ), show promise for use as spectral indicators of DOC chemical fractionation and inferred increased Cu toxicity.

Environmental Science & Technology

Binding of pyrene to aquatic and commercial humic substances: The role of molecular weight and aromaticity

The binding of pyrene to a number of humic substances isolated from various aquatic sources and a commercial humic acid was measured using the solubility enhancement method. The humic materials used in this study were characterized by various spectroscopic and liquid chromatography methods. A strong correlation was observed between the pyrene binding coefficient, K(doc), and the molecular weights, molar absorptivities at 280 nm, and aromaticity of the aquatic humic substances. Binding of pyrene to the commercial humic acid, however, was significantly stronger and did not obey the relationships observed between K(doc) and the chemical properties of the aquatic humic substrates. These results suggest that the molecular weight and the aromatic content of the humic substrates exert influences on the binding of nonpolar and planar aromatic molecules and that the physicochemical properties of both humic materials and organic solutes are important in controlling the speciation of nonpolar organic contaminants in natural waters.

Environmental Science & Technology

Binding of polychlorinated biphenyls to aquatic humic substances: The role of substrate and sorbate properties on partitioning

Two ortho- (2,2‘,5 and 2,2‘,5,6‘) and a non-ortho- (3,3‘,4,4‘) substituted polychlorinated biphenyl (PCB) congeners were used to study the effects of sorbate structure in binding processes to two lacustrine fulvic acids. Binding constants were determined by solubility enhancement of the solutes by the fulvic acids. The binding of the ortho-trichlorobiphenyl was significantly less than the non-ortho-substituted tetrachlorobiphenyl to both fulvic acids. Surprisingly, the measured ortho-trichlorobiphenyl binding constant to both fulvic acids was approximately the same as the ortho-substituted tetrachlorobiphenyl. The effect of the chlorines in the ortho position inhibits free rotation around the 1,1‘ carbon bond, thereby making the molecule less able to interact effectively with the fulvic acid substrate relative to its non-ortho-substituted congeners. Finally, binding of all three PCBs to the Great Dismal Swamp fulvic acid was significantly higher than for the Pony Lake sample. This observation is attributable to the former substrate's higher degree of aromaticity and polarizability, which can potentially interact more favorably with the PCBs through an increase in van der Waals type interactions.

Environmental Science & Technology

Molecular dynamics simulation of nitric oxide in myoglobin

The infrared (IR) spectroscopy and ligand migration of photodissociated nitric oxide (NO) in and around the active sites in myoglobin (Mb) are investigated. A distributed multipolar model for open-shell systems is developed and used, which allows one to realistically describe the charge distribution around the diatomic probe molecule. The IR spectra were computed from the trajectories for two conformational substates at various temperatures. The lines are narrow (width of 3–7 cm –1 at 20–100 K), in agreement with the experimental observations where they have widths of 4–5 cm –1 at 4 K. It is found that within one conformational substate (B or C) the splitting of the spectrum can be correctly described compared with recent experiments. Similar to photodissociated CO in Mb, additional substates exist for NO in Mb, which are separated by barriers below 1 kcal/mol. Contrary to full quantum mechanical calculations, however, the force field and mixed QM/MM simulations do not correctly describe the relative shifts between the B- and C-states relative to gas-phase NO. Free energy simulations establish that NO preferably localizes in the distal site and the barrier for migration to the neighboring Xe4 pocket is Δ G B→C = 1.7–2.0 kcal/mol. The reverse barrier is Δ G B←C = 0.7 kcal/mol, which agrees well with the experimental value of 0.7 kcal/mol, estimated from kinetic data.

Journal of Physical Chemistry

Rapid fluid disruption: A source for self-potential anomalies on volcanoes

Self-potential (SP) anomalies observed above suspected magma reservoirs, dikes, etc., on various volcanoes (Kilauea, Hawaii; Mount Unzen, Japan; Piton de la Fournaise, Reunion Island, Miyake Jima, Japan) result from transient surface electric fields of tens of millivolts per kilometer and generally have a positive polarity. These SP anomalies are usually attributed to electrokinetic effects where properties controlling this process are poorly constrained. We propose an alternate explanation that contributions to electric fields of correct polarity should be expected from charge generation by fluid vaporization/disruption. As liquids are vaporized or removed as droplets by gas transport away from hot dike intrusions, both charge generation and local increase in electrical resistivity by removal of fluids should occur. We report laboratory observations of electric fields in hot rock samples generated by pulses of fluid (water) through the rock at atmospheric pressure. These indicate the relative amplitudes of rapid fluid disruption (RFD) potentials and electrokinetic potentials to be dramatically different and the signals are opposite in sign. Above vaporization temperatures, RFD effects of positive sign in the direction of gas flow dominate, whereas below these temperatures, effects of negative sign dominate. This suggests that the primary contribution to observed self-potential anomalies arises from gas-related charge transport processes at temperatures high enough to produce vigorous boiling and vapor transport. At lower temperatures, the primary contribution is from electrokinetic effects modulated perhaps by changing electrical resistivity and RFD effects from high-pressure but low-temperature CO2 and SO2 gas flow ripping water molecules from saturated crustal rocks. If charge generation is continuous, as could well occur above a newly emplaced dike, positive static potentials will be set up that could be sustained for many years, and the simplest method for identifying these hot, active regions would be to identify the SP anomalies they generate.

Hawai'i

Crystallographic controls on the frictional behavior of dry and water-saturated sheet structure minerals

We compare the frictional strengths of 17 sheet structure mineral powders, measured under dry and water-saturated conditions, to identify the factors that cause many of them to be relatively weak. The dry coefficient of friction μ ranges upward from 0.2 for graphite, leveling off at 0.8 for margarite, clintonite, gibbsite, kaolinite, and lizardite. The values of μ (dry) correlate directly with calculated (001) interlayer bond strengths of the minerals. This correlation occurs because shear becomes localized along boundary and Riedel shears and the platy minerals in them rotate into alignment with the shear planes. For those gouges with μ (dry) < 0.8, shear occurs by breaking the interlayer bonds to form new cleavage surfaces. Where μ (dry) = 0.8, consistent with Byerlee's law, the interlayer bonds are sufficiently strong that other frictional processes dominate. The transition in dry friction mechanisms corresponds to calculated surface energies of 2–3 J/m 2 . Adding water causes μ to decrease for every mineral tested except graphite. If the minerals are separated into groups with similar crystal structures, μ (wet) increases with increasing interlayer bond strength within each group. This relationship also holds for the swelling clay montmorillonite, whose water-saturated strength is consistent with the strengths of nonswelling clays of similar crystal structure. Water in the saturated gouges forms thin, structured films between the plate surfaces. The polar water molecules are bonded to the plate surfaces in proportion to the mineral's surface energy, and μ (wet) reflects the stresses required to shear through the water films.

Journal of Geophysical Research B: Solid Earth

Hydrated states of MgSO4 at equatorial latiudes on Mars

The stability of water ice, epsomite, and hexahydrite to loss of H 2O molecules to the atmosphere at equatorial latitudes of Mars was studied to determine their potential contributions to the measured abundance of water-equivalent hydrogen (WEH). Calculation of the relative humidity based on estimates of yearly averages of water-vapor pressures and temperatures at the Martian surface was used for this purpose. Water ice was found to be sufficiently unstable everywhere within 45?? of the equator that if the observed WEH is due to water ice, it requires a low-permeability cover layer near the surface to isolate the water ice below from the atmosphere above. In contrast, epsomite or hexahydrite may be stable in many near-equatorial locations where significant amounts of WEH are observed. Copyright 2004 by the American Geophysical Union.

Geophysical Research Letters

Measurement of soil carbon oxidation state and oxidative ratio by 13 C nuclear magnetic resonance

The oxidative ratio (OR) of the net ecosystem carbon balance is the ratio of net O 2 and CO 2 fluxes resulting from photosynthesis, respiration, decomposition, and other lateral and vertical carbon flows. The OR of the terrestrial biosphere must be well characterized to accurately estimate the terrestrial CO 2 sink using atmospheric measurements of changing O 2 and CO 2 levels. To estimate the OR of the terrestrial biosphere, measurements are needed of changes in the OR of aboveground and belowground carbon pools associated with decadal timescale disturbances (e.g., land use change and fire). The OR of aboveground pools can be measured using conventional approaches including elemental analysis. However, measuring the OR of soil carbon pools is technically challenging, and few soil OR data are available. In this paper we test three solid-state nuclear magnetic resonance (NMR) techniques for measuring soil OR, all based on measurements of the closely related parameter, organic carbon oxidation state (C ox ). Two of the three techniques make use of a molecular mixing model which converts NMR spectra into concentrations of a standard suite of biological molecules of known C ox . The third technique assigns C ox values to each peak in the NMR spectrum. We assess error associated with each technique using pure chemical compounds and plant biomass standards whose C ox and OR values can be directly measured by elemental analyses. The most accurate technique, direct polarization solid-state 13 C NMR with the molecular mixing model, agrees with elemental analyses to ??0.036 C ox units (??0.009 OR units). Using this technique, we show a large natural variability in soil C ox and OR values. Soil C ox values have a mean of -0.26 and a range from -0.45 to 0.30, corresponding to OR values of 1.08 ?? 0.06 and a range from 0.96 to 1.22. We also estimate the OR of the carbon flux from a boreal forest fire. Analysis of soils from nearby intact soil profiles imply that soil carbon losses associated with the fire had an OR of 1.09 1 (??0.00 3 ). Fire appears to be a major factor driving the soil C pool to higher oxidation states and lower OR values. Episodic fluxes caused by disturbances like fire may have substantially different ORs from ecosystem respiration fluxes and therefore should be better quantified to reduce uncertainties associated with our understanding of the global atmospheric carbon budget. Copyright 2009 by the American Geophysical Union.

Journal of Geophysical Research G: Biogeosciences

Assessing the seasonal dynamics of nitrate and sulfate aerosols at the South Pole utilizing stable isotopes

Atmospheric nitrate (NO 3 − = particulate NO 3 − + gas‐phase nitric acid [HNO 3 ]) and sulfate (SO 4 2− ) are key molecules that play important roles in numerous atmospheric processes. Here, the seasonal cycles of NO 3 − and total suspended particulate sulfate (SO 4 2− (TSP) ) were evaluated at the South Pole from aerosol samples collected weekly for approximately 10 months (26 January to 25 October) in 2002 and analyzed for their concentration and isotopic compositions. Aerosol NO 3 − was largely affected by snowpack emissions in which [NO 3 − ] and δ 15 N(NO 3 − ) were highest (49.3 ± 21.4 ng/m 3 , n = 8) and lowest (−47.0 ± 11.7‰, n = 5), respectively, during periods of sunlight in the interior of Antarctica. The seasonal cycle of Δ 17 O(NO 3 − ) reflected tropospheric chemistry year‐round with lower values observed during sunlight periods and higher values observed during dark periods, reflecting shifts from HO x ‐ to O 3 ‐dominated oxidation chemistry. SO 4 2− (TSP) concentrations were highest during austral summer and fall (86.7 ± 73.7 ng/m 3 , n = 18) and are indicated to be derived from dimethyl sulfide (DMS) emissions, as δ 34 S(SO 4 2− ) (TSP) values (18.5 ± 1.0‰, n = 10) were similar to literature δ 34 S(DMS) values. The seasonal cycle of Δ 17 O(SO 4 2− ) (TSP) exhibited minima during austral summer (0.9 ± 0.1‰, n = 5) and maxima during austral fall (1.3 ± 0.3‰, n = 6) and austral spring (1.6 ± 0.1‰, n = 5), indicating a shift from HO x ‐ to O 3 ‐dominated chemistry in the atmospheric derived SO 4 2− component. Overall, the budgets of NO 3 − and SO 4 2− (TSP) at the South Pole were complex functions of transport, localized chemistry, biological activity, and meteorological conditions, and these results will be important for interpretations of oxyanions in ice core records in the interior of Antarctica.

Journal of Geophysical Research D: Atmospheres

Anomalous noble gas solubility in liquid cloud water: Possible implications for noble gas temperatures and cloud physics

The noble gas temperature climate proxy is an established tool that has previously been applied to determine the source of groundwater recharge, however, unanswered questions remain. In fractured media (e.g., volcanic islands) recharge can be so rapid that groundwater is significantly depleted in heavy noble gases, indicating that the water has retained noble gas concentrations from higher elevations. Previous studies of rain samples have confirmed a match to patterns seen in fractured-rock groundwater for heavy noble gases along with a significant helium excess. Snow has been shown to be a credible source for both the helium excess and the observed heavy noble gas pattern. Here, liquid cloud water samples were collected at two mountainous sites and analyzed for noble gas concentrations. A pattern like that of rainwater was found. However, an analysis of diffusive uptake of noble gases into cloud water demonstrates that droplets of 1 mm diameter and smaller should be in constant solubility equilibrium with the atmosphere. To explain this, we present a novel hypothesis that relies on the assumption that liquid water consists of two types of water molecule clusters bounded by hydrogen bonds: a low-density ice-like structure and a high-density condensed structure. In this model, the pressure gradient near the surface of a droplet resulting from surface tension could allow for the formation of a surface layer that is rich in ice-like low density clusters. This can explain both the helium excess and the heavy noble gas depletion seen in the samples.

Puerto Rico

The Curiosity Rover’s exploration of Glen Torridon, Gale crater, Mars: An overview of the campaign and scientific results

The Mars Science Laboratory rover, Curiosity , explored the clay mineral-bearing Glen Torridon region for one martian year between January 2019 and January 2021, including a short campaign onto the Greenheugh pediment. The Glen Torridon campaign sought to characterize the geology of the area, seek evidence of habitable environments, and document the onset of a potentially global climatic transition during the Hesperian era. Curiosity roved 5 km in total throughout Glen Torridon, from the Vera Rubin ridge to the northern margin of the Greenheugh pediment. Curiosity acquired samples from 11 drill holes during this campaign and conducted the first martian thermochemolytic-based organics detection experiment with the Sample Analysis at Mars instrument suite. The lowest elevations within Glen Torridon represent a continuation of lacustrine Murray formation deposits, but overlying widespread cross bedded sandstones indicate an interval of more energetic fluvial environments and prompted the definition of a new stratigraphic formation in the Mount Sharp group called the Carolyn Shoemaker formation. Glen Torridon hosts abundant phyllosilicates yet remains compositionally and mineralogically comparable to the rest of the Mount Sharp group. Glen Torridon samples have a great diversity and abundance of sulfur-bearing organic molecules, which are consistent with the presence of ancient refractory organic matter. The Glen Torridon region experienced heterogeneous diagenesis, with the most striking alteration occurring just below the Siccar Point unconformity at the Greenheugh pediment. Results from the pediment campaign show that the capping sandstone formed within the Stimson Hesperian aeolian sand sea that experienced seasonal variations in wind direction.

JGR Planets

Organic matter availability and the production of methane-derived dissolved organic carbon at methane seeps

Methane seeps located along continental margins and slopes export sedimentary methane and dissolved organic carbon (DOC) into the ocean. The flux of these reduced carbon molecules from the seafloor into the ocean impacts ocean chemistry and supports deep-sea life. While significant effort has been made to understand how the anaerobic oxidation of methane (AOM) regulates the release of methane from the seafloor, little is known about the production of DOC in association with AOM or its flux and fate in the ocean. We hypothesize a mechanism for methane incorporation into DOC at seeps and investigate the relationship between sediment total organic carbon (TOC) availability and the incorporation of methane-derived carbon into DOC at four methane seep regions along the Cascadia margin, with a range of microbial and thermogenic methane sources. At sites with <2.0 wt.% TOC (Hydrate Ridge and Bullseye Vent), up to 60%–80% of carbon in DOC is methane-carbon, much more than sites with >2.0 wt.% TOC (Astoria Canyon and Barkley Canyon). We attribute the greater methane contribution at the more TOC-limited sites to a greater role of AOM in the carbon cycle, whereas at the organic matter-rich sites, microbial competition for sulfate as an electron acceptor for organic matter decomposition limits AOM and hence the transfer of carbon from methane to DOC. We estimate that the global diffusive flux of methane-derived DOC from the seafloor is 0.07–10.1 Tg C/yr, contributing to the stock of DOC present in the deep ocean and/or fueling the deep-sea microbial loop.

California, Oregon, Washington

Visible and near-infrared (0.4-2.5 μm) reflectance spectra of playa evaporite minerals

Visible and near-infrared (VNIR; 0.4&ndash;2.4 &mu;m) reflectance spectra were recorded for 35 saline minerals that represent the wide range of mineral and brine chemical compositions found in playa evaporite settings. The spectra show that many of the saline minerals exhibit diagnostic near-infrared absorption bands, chiefly attributable to vibrations of hydrogen-bonded structural water molecules. VNIR reflectance spectra can be used to detect minor hydrate phases present in mixtures dominated by anhydrous halite or thenardite, and therefore will be useful in combination with X ray diffraction data for characterizing natural saline mineral assemblages. In addition, VNIR reflectance spectra are sensitive to differences in sample hydration state and should facilitate in situ studies of minerals that occur as fragile, transitory dehydration products in natural salt crusts. The use of spectral reflectance measurements in playa studies should aid in mapping evaporite mineral distributions and may provide insight into the geochemical and hydrological controls on playa mineral and brine development.

Journal of Geophysical Research

Phytoplankton bloom dynamics in coastal ecosystems: A review with some general lessons from sustained investigation of San Francisco Bay, California

Phytoplankton blooms are prominent features of biological variability in shallow coastal ecosystems such as estuaries, lagoons, bays, and tidal rivers. Long-term observation and research in San Francisco Bay illustrates some patterns of phytoplankton spatial and temporal variability and the underlying mechanisms of this variability. Blooms are events of rapid production and accumulation of phytoplankton biomass that are usually responses to changing physical forcings originating in the coastal ocean (e.g., tides), the atmosphere (wind), or on the land surface (precipitation and river runoff). These physical forcings have different timescales of variability, so algal blooms can be short-term episodic events, recurrent seasonal phenomena, or rare events associated with exceptional climatic or hydrologic conditions. The biogeochemical role of phytoplankton primary production is to transform and incorporate reactive inorganic elements into organic forms, and these transformations are rapid and lead to measurable geochemical change during blooms. Examples include the depletion of inorganic nutrients (N, P, Si), supersaturation of oxygen and removal of carbon dioxide, shifts in the isotopic composition of reactive elements (C, N), production of climatically active trace gases (methyl bromide, dimethylsulfide), changes in the chemical form and toxicity of trace metals (As, Cd, Ni, Zn), changes in the biochemical composition and reactivity of the suspended particulate matter, and synthesis of organic matter required for the reproduction and growth of heterotrophs, including bacteria, zooplankton, and benthic consumer animals. Some classes of phytoplankton play special roles in the cycling of elements or synthesis of specific organic molecules, but we have only rudimentary understanding of the forces that select for and promote blooms of these species. Mounting evidence suggests that the natural cycles of bloom variability are being altered on a global scale by human activities including the input of toxic contaminants and nutrients, manipulation of river flows, and translocation of species. This hypothesis will be a key component of our effort to understand global change at the land-sea interface. Pursuit of this hypothesis will require creative approaches for distinguishing natural and anthropogenic sources of phytoplankton population variability, as well as recognition that the modes of human disturbance of coastal bloom cycles operate interactively and cannot be studied as isolated processes.

California

Contrasting evolutionary histories of MHC class I and class II loci in grouse—Effects of selection and gene conversion

Genes of the major histocompatibility complex (MHC) encode receptor molecules that are responsible for recognition of intracellular and extracellular pathogens (class I and class II genes, respectively) in vertebrates. Given the different roles of class I and II MHC genes, one might expect the strength of selection to differ between these two classes. Different selective pressures may also promote different rates of gene conversion at each class. Despite these predictions, surprisingly few studies have looked at differences between class I and II genes in terms of both selection and gene conversion. Here, we investigated the molecular evolution of MHC class I and II genes in five closely related species of prairie grouse ( Centrocercus and Tympanuchus ) that possess one class I and two class II loci. We found striking differences in the strength of balancing selection acting on MHC class I versus class II genes. More than half of the putative antigen-binding sites (ABS) of class II were under positive or episodic diversifying selection, compared with only 10 % at class I. We also found that gene conversion had a stronger role in shaping the evolution of MHC class II than class I. Overall, the combination of strong positive (balancing) selection and frequent gene conversion has maintained higher diversity of MHC class II than class I in prairie grouse. This is one of the first studies clearly demonstrating that macroevolutionary mechanisms can act differently on genes involved in the immune response against intracellular and extracellular pathogens.

Heredity

Improving eDNA yield and inhibitor reduction through increased water volumes and multi-filter isolation techniques

To inform management and conservation decisions, environmental DNA (eDNA) methods are used to detect genetic material shed into the water by imperiled and invasive species. Methodological enhancements are needed to reduce filter clogging, PCR inhibition, and false-negative detections when eDNA is at low concentrations. In the first of three simple experiments, we sought to ameliorate filter clogging from particulates and organic material through a scaled-up, multi-filter protocol. We combined four filters in a 5 mL Phenol-Chloroform-Isoamyl (PCI) procedure to allow for larger volumes of water (~1 L) to be filtered rapidly. Increasing the filtered water volume by four times resulted in 4.4X the yield of target DNA. Next, inhibition from organic material can reduce or block eDNA detections in PCR-based assays. To remove inhibitory compounds retained during eDNA isolation, we tested three methods to chemically strip inhibitors from eDNA molecules. The use of CTAB as a short-term (5–8 day) storage buffer, followed by a PCI isolation, resulted in the highest eDNA yields. Finally, as opposed to a linear relationship among increasing concentrations of filtered genomic eDNA, we observed a sharp change between the lower (70–280 ng) and higher (420–560 ng) amounts. This may be important for effectively precipitating eDNA during protocol testing.

Scientific Reports

Polyoxometalates from heteropoly "brown" precursors. A new structural class of mixed valence heteropolytungstates, [(XO4)W3IVW17VIO 62Hx]n-

Reduction of the α-Keggin anion [X n + O 4 W 12 O 36 ] [8 − n]− (X = H 2 2+ , B 3+ , Si 4+ ) by six electrons results in the known tungsten “brown” species [X n + O 4 (H 2 O) 3 W IV 3 W VI 9 O 33 ] [8 − n ]− in which three W atoms have been reduced from W VI to W IV , forming a metal–metal bonded triad. The W IV atoms have terminal water coordinated in place of terminal oxo groups. Additional tungstate can condense onto these water molecules in aqueous solution between pH = 4 and 6.5 to form the species reported here, [(XO 4 )W IV 3 W VI 17 O 62 H x ] y − . The boron derivative (X = B 3+ ) is more stable than the metatungstate (X = H 2 2+ ), both of which have been characterized by elemental analysis, 183 W NMR and X-ray crystal structure analysis. Eight additional tungstate groups condense in the form of a partial Keggin structure containing two triads and one dyad which is rotated 60° relative to a hypothetical α-isomer.

Journal of the Chemical Society, Dalton Transactio