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USGS2011

Sources of mercury to San Francisco Bay surface sediment as revealed by mercury stable isotopes

Mercury (Hg) concentrations and isotopic compositions were examined in shallow-water surface sediment (0–2 cm) from San Francisco (SF) Bay to determine the extent to which historic Hg mining contributes to current Hg contamination in SF Bay, and to assess the use of Hg isotopes to trace sources of contamination in estuaries. Inter-tidal and wetland sediment had total Hg (Hg T ) concentrations ranging from 161 to 1529 ng/g with no simple gradients of spatial variation. In contrast, inter-tidal and wetland sediment displayed a geographic gradient of δ 202 Hg values, ranging from -0.30% in the southern-most part of SF Bay (draining the New Almaden Hg District) to -0.99% in the northern-most part of SF Bay near the Sacramento–San Joaquin River Delta. Similar to SF Bay inter-tidal sediment, surface sediment from the Alviso Slough channel draining into South SF Bay had a δ 202 Hg value of -0.29%, while surface sediment from the Cosumnes River and Sacramento–San Joaquin River Delta draining into north SF Bay had lower average δ 202 Hg values of -0.90% and -0.75%, respectively. This isotopic trend suggests that Hg-contaminated sediment from the New Almaden Hg District mixes with Hg-contaminated sediment from a low δ 202 Hg source north of SF Bay. Tailings and thermally decomposed ore (calcine) from the New Idria Hg mine in the California Coast Range had average δ 202 Hg values of -0.37 and +0.03%, respectively, showing that Hg calcination fractionates Hg isotopes resulting in Hg contamination from Hg(II) mine waste products with higher δ 202 Hg values than metallic Hg(0) produced from Hg mines. Thus, there is evidence for at least two distinct isotopic signals for Hg contamination in SF Bay: Hg associated with calcine waste materials at Hg mines in the Coast Range, such as New Almaden and New Idria; and Hg(0) produced from these mines and used in placer gold mines and/or in other industrial processes in the Sierra Nevada region and SF Bay area.

California↗

USGS2011

Fundamental studies on kinetic isotope effect (KIE) of hydrogen isotope fractionation in natural gas systems

Based on quantum chemistry calculations for normal octane homolytic cracking, a kinetic hydrogen isotope fractionation model for methane, ethane, and propane formation is proposed. The activation energy differences between D-substitute and non-substituted methane, ethane, and propane are 318.6, 281.7, and 280.2 cal/mol, respectively. In order to determine the effect of the entropy contribution for hydrogen isotopic substitution, a transition state for ethane bond rupture was determined based on density function theory (DFT) calculations. The kinetic isotope effect (KIE) associated with bond rupture in D and H substituted ethane results in a frequency factor ratio of 1.07. Based on the proposed mathematical model of hydrogen isotope fractionation, one can potentially quantify natural gas thermal maturity from measured hydrogen isotope values. Calculated gas maturity values determined by the proposed mathematical model using δD values in ethane from several basins in the world are in close agreement with similar predictions based on the δ 13 C composition of ethane. However, gas maturity values calculated from field data of methane and propane using both hydrogen and carbon kinetic isotopic models do not agree as closely. It is possible that δD values in methane may be affected by microbial mixing and that propane values might be more susceptible to hydrogen exchange with water or to analytical errors. Although the model used in this study is quite preliminary, the results demonstrate that kinetic isotope fractionation effects in hydrogen may be useful in quantitative models of natural gas generation, and that δD values in ethane might be more suitable for modeling than comparable values in methane and propane.

Geochimica et Cosmochimica Acta↗

USGS2011

Paleoenvironmental implications of taxonomic variation among δ 15 N values of chloropigments

Natural variations in the ratios of nitrogen isotopes in biomass reflect variations in nutrient sources utilized for growth. In order to use δ 15 N values of chloropigments of photosynthetic organisms to determine the corresponding δ 15 N values of biomass – and by extension, surface waters – the isotopic offset between chlorophyll and biomass must be constrained. Here we examine this offset in various geologically-relevant taxa, grown using nutrient sources that may approximate ocean conditions at different times in Earth’s history. Phytoplankton in this study include cyanobacteria (diazotrophic and non-diazotrophic), eukaryotic algae (red and green), and anoxygenic photosynthetic bacteria (Proteobacteria), as well as environmental samples from sulfidic lake water. Cultures were grown using N 2 , NO 3 − , and NH 4 + as nitrogen sources, and were examined under different light regimes and growth conditions. We find surprisingly high variability in the isotopic difference (δ 15 N biomass − δ 15 N chloropigment ) for prokaryotes, with average values for species ranging from −12.2&permil; to +11.7&permil;. We define this difference as ε por , a term that encompasses diagenetic porphyrins and chlorins, as well as chlorophyll. Negative values of ε por reflect chloropigments that are 15 N-enriched relative to biomass. Notably, this enrichment appears to occur only in cyanobacteria. The average value of ε por for freshwater cyanobacterial species is −9.8 ± 1.8&permil;, while for marine cyanobacteria it is −0.9 ± 1.3&permil;. These isotopic effects group environmentally but not phylogenetically, e.g., ε por values for freshwater Chroococcales resemble those of freshwater Nostocales but differ from those of marine Chroococcales. Our measured values of ε por for eukaryotic algae (range = 4.7–8.7&permil;) are similar to previous reports for pure cultures. For all taxa studied, values of ε por do not depend on the type of nitrogen substrate used for growth. The observed environmental control of ε por suggests that values of ε por could be useful for determining the fractional burial of eukaryotic vs. cyanobacterial organic matter in the sedimentary record.

Geochimica et Cosmochimica Acta↗

USGS2011

Fluoride geochemistry of thermal waters in Yellowstone National Park: I. Aqueous fluoride speciation

Thermal water samples from Yellowstone National Park (YNP) have a wide range of pH (1–10), temperature, and high concentrations of fluoride (up to 50 mg/l). High fluoride concentrations are found in waters with field pH higher than 6 (except those in Crater Hills) and temperatures higher than 50 °C based on data from more than 750 water samples covering most thermal areas in YNP from 1975 to 2008. In this study, more than 140 water samples from YNP collected in 2006–2009 were analyzed for free-fluoride activity by ion-selective electrode (ISE) method as an independent check on the reliability of fluoride speciation calculations. The free to total fluoride concentration ratio ranged from <1% at low pH values to >99% at high pH. The wide range in fluoride activity can be explained by strong complexing with H + and Al 3+ under acidic conditions and lack of complexing under basic conditions. Differences between the free-fluoride activities calculated with the WATEQ4F code and those measured by ISE were within 0.3–30% for more than 90% of samples at or above 10 −6 molar, providing corroboration for chemical speciation models for a wide range of pH and chemistry of YNP thermal waters. Calculated speciation results show that free fluoride, F − , and major complexes ( HF ( aq ) 0 "> HF(aq)0 , AlF 2+ , AlF 2 + "> AlF2+ and AlF 3 0 "> AlF30 ) account for more than 95% of total fluoride. Occasionally, some complex species like AlF 4 - "> AlF4- , FeF 2+ , FeF 2 + "> FeF2+ , MgF + and BF 2 ( OH ) 2 - "> BF2(OH)2- may comprise 1–10% when the concentrations of the appropriate components are high. According to the simulation results by PHREEQC and calculated results, the ratio of main fluoride species to total fluoride varies as a function of pH and the concentrations and ratios of F and Al.

Yellowstone National Park↗

USGS2011

Ammonium in thermal waters of Yellowstone National Park: Processes affecting speciation and isotope fractionation

Dissolved inorganic nitrogen, largely in reduced form (NH 4 (T)≈NH 4(aq) + +NH 3(aq) o ), has been documented in thermal waters throughout Yellowstone National Park, with concentrations ranging from a few micromolar along the Firehole River to millimolar concentrations at Washburn Hot Springs. Indirect evidence from rock nitrogen analyses and previous work on organic compounds associated with Washburn Hot Springs and the Mirror Plateau indicate multiple sources for thermal water NH 4 (T), including Mesozoic marine sedimentary rocks, Eocene lacustrine deposits, and glacial deposits. A positive correlation between NH 4 (T) concentration and δ 18 O of thermal water indicates that boiling is an important mechanism for increasing concentrations of NH 4 (T) and other solutes in some areas. The isotopic composition of dissolved NH 4 (T) is highly variable (δ 15 N = −6‰ to +30‰) and is positively correlated with pH values. In comparison to likely δ 15 N values of nitrogen source materials (+1‰ to +7‰), high δ 15 N values in hot springs with pH >5 are attributed to isotope fractionation associated with NH 3(aq) o loss by volatilization. NH 4 (T) in springs with low pH typically is relatively unfractionated, except for some acid springs with negative δ 15 N values that are attributed to NH 3(g) o condensation. NH 4 (T) concentration and isotopic variations were evident spatially (between springs) and temporally (in individual springs). These variations are likely to be reflected in biomass and sediments associated with the hot springs and outflows. Elevated NH 4 (T) concentrations can persist for 10s to 1000s of meters in surface waters draining hot spring areas before being completely assimilated or oxidized.

Yellowstone National Park↗

USGS2011

Holocene and late glacial palaeoceanography and palaeolimnology of the Black Sea: Changing sediment provenance and basin hydrography over the past 20,000 years

The elemental geochemistry of Late Pleistocene and Holocene sediments of the Black Sea, recovered in box cores from the basin margins and a 5-m gravity core from the central abyssal region of the basin, identifies two terrigenous sediment sources over the last 20 kyrs. One source region includes Anatolia and the southern Caucasus; the second region is the area drained by rivers entering the Black Sea from Eastern Europe. Alkali metal:Al and heavy:light rare-earth element ratios reveal that the relative contribution of the two sources shifted abruptly every few thousand years during the late glacial and early Holocene lacustrine phase of the basin. The shifts in source were coeval with changes in the lake level as determined from the distribution of quartz and the heavy mineral-hosted trace elements Ti and Zr. The geochemistry of the abyssal sediments further recorded a sequence of changes to the geochemistry of the water column following the lacustrine phase, when high salinity Mediterranean water entered the basin beginning 9.3 kyrs BP. Bottom water that had been oxic throughout the lake phase became anoxic at approximately 8.4 kyrs BP, as recorded by the accumulation from the water column of several redox-sensitive trace metals (Mo, Re, U). The accumulation of organic carbon and several trace nutrients (Cd, Cu, Ni, Zn) increased sharply ca. 0.4 kyrs later, at 8.0 kyrs BP, reflecting an increase of primary productivity. Its increase was coeval with a shift in the dinoflagellate ecology from stenohaline to euryhaline assemblages. During this profound environmental change from the lacustrine to the marine phase, the accumulation rate of the lithogenous sediment fraction decreased as much as 10-fold in response to the rise of the water level in the basin from a low stand ca. 9.3 ka to its current level.

Geochimica et Cosmochimica Acta↗

USGS2012

A new method of calculating electrical conductivity with applications to natural waters

A new method is presented for calculating the electrical conductivity of natural waters that is accurate over a large range of effective ionic strength (0.0004–0.7 mol kg −1 ), temperature (0–95 °C), pH (1–10), and conductivity (30–70,000 μS cm −1 ). The method incorporates a reliable set of equations to calculate the ionic molal conductivities of cations and anions (H + , Li + , Na + , K + , Cs + , NH 4 + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , F − , Cl − , Br − , SO 4 2- , HCO 3 - , CO 3 2- , NO 3 - , and OH − ), environmentally important trace metals (Al 3+ , Cu 2+ , Fe 2+ , Fe 3+ , Mn 2+ , and Zn 2+ ), and ion pairs (HSO 4 - , NaSO 4 - , NaCO 3 - , and ). These equations are based on new electrical conductivity measurements for electrolytes found in a wide range of natural waters. In addition, the method is coupled to a geochemical speciation model that is used to calculate the speciated concentrations required for accurate conductivity calculations. The method was thoroughly tested by calculating the conductivities of 1593 natural water samples and the mean difference between the calculated and measured conductivities was −0.7 ± 5%. Many of the samples tested were selected to determine the limits of the method and include acid mine waters, geothermal waters, seawater, dilute mountain waters, and river water impacted by municipal waste water. Transport numbers were calculated and H + , Na + , Ca 2+ , Mg 2+ , NH 4 + , K + , Cl − , SO 4 2- , HCO 3 - , CP 3 2- , F − , Al 3+ , Fe 2+ , NO 3 - , and substantially contributed (>10%) to the conductivity of at least one of the samples. Conductivity imbalance in conjunction with charge imbalance can be used to identify whether a cation or an anion measurement is likely in error, thereby providing an additional quality assurance/quality control constraint on water analyses.

Geochimica et Cosmochimica Acta↗

USGS2012

Evaluating Re-Os systematics in organic-rich sedimentary rocks in response to petroleum generation using hydrous pyrolysis experiments

Successful application of the 187 Re– 187 Os geochronometer has enabled the determination of accurate and precise depositional ages for organic-rich sedimentary rocks (ORS) as well as establishing timing constraints of petroleum generation. However, we do not fully understand the systematics and transfer behaviour of Re and Os between ORS and petroleum products (e.g., bitumen and oil). To more fully understand the behaviour of Re–Os systematics in both source rocks and petroleum products we apply hydrous pyrolysis to two immature hydrocarbon source rocks: the Permian Phosphoria Formation (TOC = 17.4%; Type II-S kerogen) and the Jurassic Staffin Formation (TOC = 2.5%; Type III kerogen). The laboratory-based hydrous pyrolysis experiments were carried out for 72 h at 250, 300, 325 and 350 °C. These experiments provided us with whole rock, extracted rock and bitumen and in some cases expelled oil and asphaltene for evaluation of Re–Os isotopic and elemental abundance. The data from these experiments demonstrate that the majority (>95%) of Re and Os are housed within extracted rock and that thermal maturation does not result in significant transfer of Re or Os from the extracted rock into organic phases. Based on existing thermodynamic data our findings suggest that organic chelating sites have a greater affinity for the quadravalent states of Re and Os than sulphides. Across the temperature range of the hydrous pyrolysis experiments both whole rock and extracted rock 187 Re/ 188 Os ratios show small variations (3.3% and 4.7%, for Staffin, respectively and 6.3% and 4.9% for Phosphoria, respectively). Similarly, the 187 Os/ 188 Os ratios show only minor variations for the Staffin and Phosphoria whole rock and extracted rock samples (0.6% and 1.4% and 1.3% and 2.2%). These isotopic data strongly suggest that crude oil generation through hydrous pyrolysis experiments does not disturb the Re–Os systematics in ORS as supported by various studies on natural systems. The elemental abundance data reveal limited transfer of Re and Os into the bitumen from a Type III kerogen in comparison to Type II-S kerogen (0.02% vs. 3.7%), suggesting that these metals are very tightly bound in Type III kerogen structure. The 187 Os/ 188 Os data from the pyrolysis generated Phosphoria bitumens display minor variation (4%) across the experimental temperatures, with values similar to that of the source rock. This indicates that the isotopic composition of the bitumen reflects the isotopic composition of the source rock at the time of petroleum generation. These data further support the premise that the Os isotopic composition of oils and bitumens can be used to fingerprint petroleum deposits to specific source rocks. Oil generated through the hydrous pyrolysis experiments does not contain appreciable quantities of Re or Os (~120 and ~3 ppt, respectively), in contrast to natural oils (2–50 ppb and 34–288 ppt for Re and Os, respectively), which may suggest that kinetic parameters are fundamental to the transfer of Re and Os from source rocks to oils. From this we hypothesise that, at the temperatures employed in hydrous pyrolysis, Re and Os are assimilated into the extracted rock as a result of cross-linking reactions.

Geochimica et Cosmochimica Acta↗

USGS2012

An initial investigation into the organic matter biogeochemistry of the Congo River

The Congo River, which drains pristine tropical forest and savannah and is the second largest exporter of terrestrial carbon to the ocean, was sampled in early 2008 to investigate organic matter (OM) dynamics in this historically understudied river basin. We examined the elemental (%OC, %N, C:N), isotopic (δ 13 C, Δ 14 C, δ 15 N) and biochemical composition (lignin phenols) of coarse particulate (>63 μm; CPOM) and fine particulate (0.7–63 μm; FPOM) OM and DOC, δ 13 C, Δ 14 C and lignin phenol composition with respect to dissolved OM (<0.7 μm; DOM) from five sites in the Congo River Basin. At all sample locations the organic carbon load was dominated by the dissolved phase (~82–89% of total organic carbon) and the total suspended sediment load was principally fine particulate material (~81–91% fine suspended sediment). Distinct compositional and isotopic differences were observed between all fractions. Congo CPOM, FPOM and DOM all originated from vegetation and soil inputs as evidenced by elemental, isotopic and lignin phenol data, however FPOM was derived from much older carbon pools (mean Δ 14 C = -62.2 ± -13.2&permil;, n = 5) compared to CPOM and DOM (mean Δ 14 C = 55.7 ± 30.6&permil;, n = 4 and 73.4 ± 16.1&permil;, n = 5 respectively). The modern radiocarbon ages for DOM belie a degraded lignin compositional signature (i.e. elevated acid:aldehyde ratios (Ad:Al) relative to CPOM and FPOM), and indicate that the application of OM degradation patterns derived from particulate phase studies to dissolved samples needs to be reassessed: these elevated ratios are likely attributable to fractionation processes during solubilization of plant material. The relatively low DOM carbon-normalized lignin yields (Λ8; 0.67–1.12 (mg(100 mg OC) -1 )) could also reflect fractionation processes, however, they have also been interpreted as an indication of significant microbial or algal sources of DOM. CPOM appears to be well preserved higher vascular plant material as evidenced by its modern radiocarbon age, elevated C:N (17.2–27.1) and Λ8 values (4.56–7.59 (mg(100 mg OC) -1 )). In relation to CPOM, the aged FPOM fraction (320–580 ybp 14 C ages) was comparatively degraded, as demonstrated by its nitrogen enrichment (C:N 11.4–14.3), lower Λ8 (2.80–4.31 (mg(100 mg OC) -1 )) and elevated lignin Ad:Al values similar to soil derived OM. In this study we observed little modification of the OM signature from sample sites near the cities of Brazzaville and Kinshasa to the head of the estuary (~350 km) highlighting the potential for future studies to assess seasonal and long-term OM dynamics from this logistically feasible location and derive relevant information with respect to OM exported to the Atlantic Ocean. The relative lack of OM data for the Congo River Basin highlights the importance of studies such as this for establishing baselines upon which to gauge future change.

Congo River↗

USGS2012

Modeling radium distribution in coastal aquifers during sea level changes: The Dead Sea case

We present a new approach to studying the behavior of radium isotopes in a coastal aquifer. In order to simulate radium isotope distributions in the dynamic flow field of the Dead Sea aquifer, a multi-species density dependent flow model (SUTRA-MS) was used. Field data show that the activity of 226 Ra decreases from 140 to 60 dpm/L upon entering the aquifer from the Dead Sea, and then further decreases linearly due to mixing with Ra-poor fresh water. On the other hand, an increase is observed in the activity of the shorter-lived isotopes (up to 52 dpm/L 224 Ra and 31 dpm/L 223 Ra), which are relatively low in Dead Sea water (up to 2.5 dpm/L 224 Ra and 0.5 dpm/L 223 Ra). The activities of the short lived radium isotopes also decrease with decreasing salinity, which is due to the effect of salinity on the adsorption of radium. The relationship between 224 Ra and salinity suggests that the adsorption partition coefficient ( K ) is linearly related to salinity. Simulations of the steady-state conditions, show that the distance where equilibrium activity is attained for each radium isotope is affected by the isotope half-life, K and the groundwater velocity, resulting in a longer distance for the long-lived radium isotopes. K affects the radium distribution in transient conditions, especially that of the long-lived radium isotopes. The transient conditions in the Dead Sea system, with a 1 m/yr lake level drop, together with the radium field data, constrains K to be relatively low (<10). Thus, the sharp decrease in 226 Ra cannot be explained by adsorption, and it is better explained by removal via coprecipitation, probably with barite or celestine.

Dead Sea↗

USGS2012

Carbon sequestration via reaction with basaltic rocks: geochemical modeling and experimental results

Basaltic rocks are potential repositories for sequestering carbon dioxide (CO 2 ) because of their capacity for trapping CO 2 in carbonate minerals. We carried out a series of thermodynamic equilibrium models and high pressure experiments, reacting basalt with CO 2 -charged fluids over a range of conditions from 50 to 200 °C at 300 bar. Results indicate basalt has a high reactivity to CO 2 acidified brine. Carbon dioxide is taken up from solution at all temperatures from 50 to 200 °C, 300 bar, but the maximum extent and rate of reaction occurs at 100 °C, 300 bar. Reaction path simulations utilizing the geochemical modeling program CHILLER predicted an equilibrium carbonate alteration assemblage of calcite, magnesite, and siderite, but the only secondary carbonate identified in the experiments was a ferroan magnesite. The amount of uptake at 100 °C, 300 bar ranged from 8% by weight for a typical tholeite to 26% for a picrite. The actual amount of CO2 uptake and extent of rock alteration coincides directly with the magnesium content of the rock suggesting that overall reaction extent is controlled by bulk basalt Mg content. In terms of sequestering CO 2 , an average basaltic MgO content of 8% is equivalent to 2.6 × 10 8 metric ton CO 2 /km 3 basalt.

Geochimica et Cosmochimica Acta↗

USGS2012

Insights from fumarole gas geochemistry on the origin of hydrothermal fluids on the Yellowstone Plateau

The chemistry of Yellowstone fumarole gases shows the existence of two component waters, type MC, influenced by the addition of deep mantle fluid, and type CC, influenced by crustal interactions (CC). MC is high in 3 He/ 4 He (22 Ra) and low in 4 He/ 40 Ar (∼1), reflecting input of deep mantle components. The other water is characterized by 4 He concentrations 3–4 orders of magnitude higher than air-saturated meteoric water (ASW). These high He concentrations originate through circulation in Pleistocene volcanic rocks, as well as outgassing of Tertiary and older (including Archean) basement, some of which could be particularly rich in uranium, a major 4 He source. Consideration of CO 2 –CH 4 –CO–H 2 O–H 2 gas equilibrium reactions indicates equilibration temperatures from 170 °C to 310 °C. The estimated temperatures highly correlate with noble-gas variations, suggesting that the two waters differ in temperature. Type CC is ∼170 °C whereas the MC is hotter, at 340 °C. This result is similar to models proposed by previous studies of thermal water chemistry. However, instead of mixing the deep hot component simply with cold, meteoric waters we argue that addition of a 4 He-rich component, equilibrated at temperatures around 170 °C, is necessary to explain the range in fumarole gas chemistry.

Wyoming↗

USGS2013

Variations of iron flux and organic carbon remineralization in a subterranean estuary caused by interannual variations in recharge

We determine the inter-annual variations in diagenetic reaction rates of sedimentary iron (Fe ) in an east Florida subterranean estuary and evaluate the connection between metal fluxes and recharge to the coastal aquifer. Over the three-year study period (from 2004 to 2007), the amount of Fe-oxides reduced at the study site decreased from 192 g/yr to 153 g/yr and associated organic carbon (OC) remineralization decreased from 48 g/yr to 38 g/yr. These reductions occurred although the Fe-oxide reduction rates remained constant around 1 mg/cm 2 /yr. These results suggest that changes in flow rates of submarine groundwater discharge (SGD) related to changes in precipitation may be important to fluxes of the diagenetic reaction products. Rainfall at a weather station approximately 5 km from the field area decreased from 12.6 cm/month to 8.4 cm/month from 2004 to 2007. Monthly potential evapotranspiration (PET) calculated from Thornthwaite’s method indicated potential evapotranspiration cycled from about 3 cm/month in the winter to about 15 cm/month in the summer so that net annual recharge to the aquifer decreased from 40 cm in 2004 to -10 cm in 2007. Simultaneously, with the decrease in recharge of groundwater, freshwater SGD decreased by around 20% and caused the originally 25 m wide freshwater seepage face to decrease in width by about 5 m. The smaller seepage face reduced the area under which Fe-oxides were undergoing reductive dissolution. Consequently, the observed decrease in Fe flux is controlled by hydrology of the subterranean estuary. These results point out the need to better understand linkages between temporal variations in diagenetic reactions and changes in flow within subterranean estuaries in order to accurately constrain their contribution to oceanic fluxes of solutes from subterranean estuaries.

Florida↗

USGS2013

Abundance, size distributions and trace-element binding of organic and iron-rich nanocolloids in Alaskan rivers, as revealed by field-flow fractionation and ICP-MS

Water samples were collected from six small rivers in the Yukon River basin in central Alaska to examine the role of colloids and organic matter in the transport of trace elements in Northern high latitude watersheds influenced by permafrost. Concentrations of dissolved organic carbon (DOC), selected elements (Al, Si, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr, Ba, Pb, U), and UV-absorbance spectra were measured in 0.45 μm filtered samples. ‘Nanocolloidal size distributions’ (0.5–40 nm, hydrodynamic diameter) of humic-type and chromophoric dissolved organic matter (CDOM), Cr, Mn, Fe, Co, Ni, Cu, Zn, and Pb were determined by on-line coupling of flow field-flow fractionation (FFF) to detectors including UV-absorbance, fluorescence, and ICP-MS. Total dissolved and nanocolloidal concentrations of the elements varied considerably between the rivers and between spring flood and late summer base flow. Data on specific UV-absorbance (SUVA), spectral slopes, and the nanocolloidal fraction of the UV-absorbance indicated a decrease in aromaticity and size of CDOM from spring flood to late summer. The nanocolloidal size distributions indicated the presence of different ‘components’ of nanocolloids. ‘Fulvic-rich nanocolloids’ had a hydrodynamic diameter of 0.5–3 nm throughout the sampling season; ‘organic/iron-rich nanocolloids’ occurred in the <8 nm size range during the spring flood; whereas ‘iron-rich nanocolloids’ formed a discrete 4–40 nm components during summer base flow. Mn, Co, Ni, Cu and Zn were distributed between the nanocolloid components depending on the stability constant of the metal (+II)–organic complexes, while stronger association of Cr to the iron-rich nanocolloids was attributed to the higher oxidation states of Cr (+III or +IV). Changes in total dissolved element concentrations, size and composition of CDOM, and occurrence and size of organic/iron and iron-rich nanocolloids were related to variations in their sources from either the upper organic-rich soil or the deeper mineral layer, depending on seasonal variations in hydrological flow patterns and permafrost dynamics.

Alaska↗

USGS2013

Aeolian controls of soil geochemistry and weathering fluxes in high-elevation ecosystems of the Rocky Mountains, Colorado

When dust inputs are large or have persisted for long periods of time, the signature of dust additions are often apparent in soils. The of dust will be greatest where the geochemical composition of dust is distinct from local sources of soil parent material. In this study the influence of dust accretion on soil geochemistry is quantified for two different soils from the San Juan Mountains of southwestern Colorado, USA. At both study sites, dust is enriched in several trace elements relative to local rock, especially Cd, Cu, Pb, and Zn. Mass-balance calculations that do not explicitly account for dust inputs indicate the accumulation of some elements in soil beyond what can be explained by weathering of local rock. Most observed elemental enrichments are explained by accounting for the long-term accretion of dust, based on modern isotopic and geochemical estimates. One notable exception is Pb, which based on mass-balance calculations and isotopic measurements may have an additional source at one of the study sites. These results suggest that dust is a major factor influencing the development of soil in these settings and is also an important control of soil weathering fluxes. After accounting for dust inputs in mass-balance calculations, Si weathering fluxes from San Juan Mountain soils are within the range observed for other temperate systems. Comparing dust inputs with mass-balanced based flux estimates suggests dust could account for as much as 50–80% of total long-term chemical weathering fluxes. These results support the notion that dust inputs may sustain chemical weathering fluxes even in relatively young continental settings. Given the widespread input of far-traveled dust, the weathering of dust is likely and important and underappreciated aspect of the global weathering engine.

Colorado↗

USGS2013

Anaerobic methane oxidation in low-organic content methane seep sediments

Sulfate-dependent anaerobic oxidation of methane (AOM) is the key sedimentary microbial process limiting methane emissions from marine sediments and methane seeps. In this study, we investigate how the presence of low-organic content sediment influences the capacity and efficiency of AOM at Bullseye vent, a gas hydrate-bearing cold seep offshore of Vancouver Island, Canada. The upper 8 m of sediment contains < 0.4 wt% total organic carbon (OC) and primarily consists of glacially-derived material that was deposited 14,900 to 15,900 yrs BP during the retreat of the late Quaternary Cordilleran Ice Sheet. We hypothesize this aged and exceptionally low-OC content sedimentary OM is biologically refractory, thereby limiting degradation of non-methane OM by sulfate reduction and maximizing methane consumption by sulfate-dependent AOM. A radiocarbon-based dissolved inorganic carbon (DIC) isotope mass balance model demonstrates that respired DIC in sediment pore fluids is derived from a fossil carbon source that is devoid of 14 C. A fossil origin for the DIC precludes remineralization of non-fossil OM present within the sulfate zone as a significant contributor to pore water DIC, suggesting that nearly all sulfate is available for anaerobic oxidation of fossil seep methane. Methane flux from the SMT to the sediment water interface in a diffusion-dominated flux region of Bullseye vent was, on average, 96% less than at an OM-rich seep in the Gulf of Mexico with a similar methane flux regime. Evidence for enhanced methane oxidation capacity within OM-poor sediments has implications for assessing how climate-sensitive reservoirs of sedimentary methane (e.g., gas hydrate) will respond to ocean warming, particularly along glacially-influenced mid and high latitude continental margins.

Geochimica et Cosmochimica Acta↗

USGS2013

Determination of low-level mercury in coralline aragonite by calcination-isotope dilution-inductively coupled plasma-mass spectrometry and its application to Diploria specimens from Castle Harbour, Bermuda

We have developed a technique that combines a high temperature quartz furnace with inductively coupled plasma-mass spectrometry for the determination of Hg stored in the annual CaCO 3 bands found in coral skeletons. Substantial matrix effects, presumably due to the discontinuous introduction of CO 2 to the gas stream, were corrected for by simultaneously supplying a stream of argon containing highly enriched elemental 202 Hg o and observing peaks in the 200 Hg/ 202 Hg signal as the sample was decomposed. Primary signal calibration for Hg was achieved using gas injections from a saturated vapor standard. The absolute instrument detection limit was low (about 0.2 fmol), with a practical limit of detection (3 σ of blanks) of 2 fmol. Reproducibility of samples was (RSD) 15–27%. We applied this method to the determination of Hg concentrations in two colonies of Diploria labyrinthiformis collected from Castle Harbour, Bermuda, at a site about to be buried under the municipal waste landfill. The temporal reconstructions of Castle Harbour seawater Hg concentrations implied by the coral record show a decline throughout the period of record (1949–2008). The coral archived no apparent signal associated with waste disposal practices in the Harbour (bulk waste land-filling or, since 1994, disposal of waste incinerator ash), and mercury concentrations in the coral did not correlate to growth rate as assessed by linear extension. There was, however, a large and nearly exponential decrease in apparent Hg concentration in the Harbour which circumstantially implicates the dredging and/or landfilling operations associated with the construction of the airport on St. David’s Island.

Geochimica et Cosmochimica Acta↗

USGS2013

Pathways of coupled arsenic and iron cycling in high arsenic groundwater of the Hetao basin, Inner Mongolia, China: an iron isotope approach

High As groundwater is widely distributed all over the world, which has posed a significant health impact on millions of people. Iron isotopes have recently been used to characterize Fe cycling in aqueous environments, but there is no information on Fe isotope characteristics in the groundwater. Since groundwater As behavior is closely associated with Fe cycling in the aquifers, Fe isotope signatures may help to characterize geochemical processes controlling As concentrations of shallow groundwaters. This study provides the first observation of Fe isotope fractionation in high As groundwater and evaluation of Fe cycling and As behaviors in shallow aquifers in terms of Fe isotope signatures. Thirty groundwater samples were taken for chemical and isotopic analysis in the Hetao basin, Inner Mongolia. Thirty-two sediments were sampled as well from shallow aquifers for Fe isotope analysis. Results showed that groundwater was normally enriched in isotopically light Fe with δ 56 Fe values between −3.40&permil; and 0.58&permil; and median of −1.14&permil;, while heavier δ 56 Fe values were observed in the sediments (between −1.10&permil; and 0.75&permil;, median +0.36&permil;). In reducing conditions, groundwaters generally had higher δ 56 Fe values, in comparison with oxic conditions. High As groundwaters, generally occurring in reducing conditions, had high δ 56 Fe values, while low As groundwaters normally had low δ 56 Fe values. Although sediment δ 56 Fe values were generally independent of lithological conditions, a large variation in sediment δ 56 Fe values was observed in the oxidation–reduction transition zone. Three pathways were identified for Fe cycling in shallow groundwater, including dissimilatory reduction of Fe(III) oxides, re-adsorption of Fe(II), and precipitation of pyrite and siderite. Dissimilatory reduction of Fe(III) oxides resulted in light δ 56 Fe values (around −1.0&permil;) and high As concentration (>50 μg/L) in groundwater in anoxic conditions. Re-adsorption of isotopically heavy Fe(II) produced by microbially mediated reduction of Fe(III) oxides led to further enrichment of isotopically light Fe in groundwater (up to −3.4&permil; of δ 56 Fe) in anoxic–suboxic conditions. Arsenic re-adsorption was expected to occur along with Fe(II) re-adsorption, decreasing groundwater As concentrations. In strongly reducing conditions, precipitation of isotopically light Fe-pyrite and/or siderite increased groundwater δ 56 Fe values, reaching +0.58&permil; δ 56 Fe, with a subsequent decrease in As concentrations via co-precipitation. The mixed effect of those pathways would regulate As and Fe cycling in most groundwaters.

Inner Mongolia↗