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At least 1,711 records · Page 95Linked to original sources
USGS2026

Metalloporphyrins in the Eagle Ford Shale

Using Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), Zheng et al. (2018, Energy & Fuels 32, 10382) reported abundant iron and vanadyl porphyrins and minor amounts of gallium and nickel porphyrins in asphaltenes extracted from a single lower Eagle Ford Shale sample. This finding is most unusual as iron and gallium porphyrins have been previously found only in coal. In this study, petroporphyrins in samples of the Eagle Ford Shale previously studied by French et al. (2020, Marine Petrol. Geol. 118, 104459), were examined using atmospheric pressure photoionization (APPI) FT-ICR-MS. Vanadyl porphyrins (N4VO) dominated the asphaltenes in thermally immature (VRo < 0.56%) samples decreasing in relative abundance with increasing maturity. Only minor amounts of nickel porphyrins were detected in the immature and early oil samples. The distribution of the vanadyl porphyrins is comparable to those reported for marine oils at varying levels of maturity. Immature samples contained porphyrins that were predominantly deoxophylloerythroetio- (DPEP: DBE = 18) and di- deoxophylloerythroetio (di-DPEP: DBE = 19) porphyrins, while ETIO- (DBE = 17), rhodo- (DBE = 20, 21, and 22) and higher condensed (DBE ≥ 23) porphyrins increased with increasing maturity. The vanadyl porphyrins included species with additional one to three oxygen atoms (N4VOx, x= 1 to 4) and one sulfur atom with one to two oxygen atoms (S1N4VOx, x=1 to 3). The degree of additional oxygen and sulfur atoms is consistent with O/C and Sorg/C of associated kerogen. No iron or gallium porphyrins were detected, showing that they are not a ubiquitous feature of the Eagle Ford. We hypothesize that the previously reported iron and gallium porphyrins (Zheng et al., 2018) were present because the specific sample that was analyzed in detail was from the early onset of the Cenomanian–Turonian oceanic anoxic event (OAE-2) in contrast to the samples investigated in this study that are primarily from the lower part of the Eagle Ford pre-dating OAE-2. Submarine volcanism, associated with eruption of large igneous provinces, occurred pre-OAE-2, injecting iron and other inorganic nutrients, giving rise to algal blooms and the acidification of the seawater. At the onset of OAE-2, boreal water masses flowed into the southern Western Interior Seaway, shifting the water column to more oxygenated conditions. Low pH-high Eh (oxic) conditions enhance the availability of iron and gallium such that these events abruptly changed the seawater chemistry, specifically enriching iron and gallium relative to vanadium and nickel. These pH-Eh conditions are similar to the depositional conditions associated with coals, which are known to contain iron and gallium porphyrins, suggesting similar conditions resulted in iron and gallium metalation of porphyrins in the marine setting of the Western Interior Seaway.

Texas↗
USGS2009

Endogenic carbonate sedimentation in Bear Lake, Utah and Idaho, over the last two glacial-interglacial cycles

Sediments deposited over the past 220,000 years in Bear Lake, Utah and Idaho, are predominantly calcareous silty clay, with calcite as the dominant carbonate mineral. The abundance of siliciclastic sediment indicates that the Bear River usually was connected to Bear Lake. However, three marl intervals containing more than 50% CaCO 3 were deposited during the Holocene and the last two interglacial intervals, equivalent to marine oxygen isotope stages (MIS) 5 and 7, indicating times when the Bear River was not connected to the lake. Aragonite is the dominant mineral in two of these three high-carbonate intervals. The high-carbonate, aragonitic intervals coincide with warm interglacial continental climates and warm Pacific sea-surface temperatures. Aragonite also is the dominant mineral in a carbonate-cemented microbialite mound that formed in the southwestern part of the lake over the last several thousand years. The history of carbonate sedimentation in Bear Lake is documented through the study of isotopic ratios of oxygen, carbon, and strontium, organic carbon content, CaCO 3 content, X-ray diffraction mineralogy, and HCl-leach chemistry on samples from sediment traps, gravity cores, piston cores, drill cores, and microbialites. Sediment-trap studies show that the carbonate mineral that precipitates in the surface waters of the lake today is high-Mg calcite. The lake began to precipitate high-Mg calcite sometime in the mid-twentieth century after the artificial diversion of Bear River into Bear Lake that began in 1911. This diversion drastically reduced the salinity and Mg 2+ :Ca 2+ of the lake water and changed the primary carbonate precipitate from aragonite to high-Mg calcite. However, sediment-trap and core studies show that aragonite is the dominant mineral accumulating on the lake floor today, even though it is not precipitating in surface waters. The isotopic studies show that this aragonite is derived from reworking and redistribution of shallow-water sediment that is at least 50 yr old, and probably older. Apparently, the microbialite mound also stopped forming aragonite cement sometime after Bear River diversion. Because of reworking of old aragonite, the bulk mineralogy of carbonate in bottom sediments has not changed very much since the diversion. However, the diversion is marked by very distinct changes in the chemical and isotopic composition of the bulk carbonate. After the last glacial interval (LGI), a large amount of endogenic carbonate began to precipitate in Bear Lake when the Pacific moisture that filled the large pluvial lakes of the Great Basin during the LGI diminished, and Bear River apparently abandoned Bear Lake. At first, the carbonate that formed was low-Mg calcite, but ???11,000 years ago, salinity and Mg 2+ :Ca 2+ thresholds must have been crossed because the amount of aragonite gradually increased. Aragonite is the dominant carbonate mineral that has accumulated in the lake for the past 7000 years, with the addition of high-Mg calcite after the diversion of Bear River into the lake at the beginning of the twentieth century. Copyright ?? 2009 The Geological Society of America.

Special Paper of the Geological Society of America↗
USGS1974

Some morphometric properties of experimentally cratered surfaces

The temperature and chemical conditions (pH, gas pressure, and ion activities) in a geothermal aquifer supplying a producing bore can be calculated from the enthalpy of the total fluid (liquid + vapor) produced and chemical analyses of water and steam separated and collected at known pressures. Alternatively, if a single water phase exists in the aquifer, the complete analysis (including gases) of a sample collected from the aquifer by a downhole sampler is sufficient to determine the aquifer chemistry without a measured value of the enthalpy. The assumptions made are that the fluid is produced from a single aquifer and is homogeneous in enthalpy and chemical composition. These calculations of aquifer chemistry involving large amounts of ancillary information and many iterations require computer methods. A computer program in PL-1 to perform these calculations is available from the National Technical Information Service as document PB-219 376.

Journal of Research of the U.S. Geological Survey↗
USGS1995

Soil-solution chemistry in a low-elevation spruce-fir ecosystem, Howland, Maine

Soil solutions were collected monthly by tension and zero-tension lysimeters in a low-elevation red spruce stand in east-central Maine from May 1987 through December 1992. Soil solutions collected by Oa tension lysimeters had higher concentrations of most constituents than the Oa zero-tension lysimeters. In Oa horizon soil solutions growing season concentrations for SO 4 , Ca, and Mg averaged 57, 43, and 30 μmol L −1 in tension lysimeters, and 43, 28, and 19 μmol L −1 in zero-tension lysimeters, respectively. Because tension lysimeters remove water held by the soil at tensions up to 10 kPa, solutions are assumed to have more time to react with the soil compared to freely draining solutions collected by zero-tension lysimeters. Solutions collected in the Bs horizon by both types of collectors were similar which was attributed to the frequency of time periods when the water table was above the Bs lysimeters. Concentrations of SO 4 and NO 3 at this site were lower than concentrations reported for most other eastern U.S. spruce-fir sites, but base cation concentrations fell in the same range. Aluminum concentrations in this study were also lower than reported for other sites in the eastern U.S. and Ca/Al ratios did not suggest inhibition of Ca uptake by roots. Concentrations of SO 4 , Ca, K, and Cl decreased significantly in both the Oa and Bs horizons over the 56-month sampling period, which could reflect decreasing deposition rates for sulfur and base cations, climatic influences, or natural variation. A longer record of measured fluxes will be needed to adequately define temporal trends in solution chemistry and their causes.

Maine↗
USGS2006

Application of municipal biosolids to dry-land wheat fields - A monitoring program near Deer Trail, Colorado (USA). A presentation for an international conference: "The Future of Agriculture: Science, Stewardship, and Sustainability", August 7-9, 2006, Sacramento, CA

Since late 1993, Metro Wastewater Reclamation District of Denver (Metro District), a large wastewater treatment plant in Denver, Colorado, has applied Grade I, Class B biosolids to about 52,000 acres of non-irrigated farmland and rangeland near Deer Trail, Colorado. In cooperation with the Metro District in 1993, the U.S. Geological Survey (USGS) began monitoring ground water at part of this site. In 1999, the USGS began a more comprehensive study of the entire site to address stakeholder concerns about the chemical effects of biosolids applications. This more comprehensive monitoring program has recently been extended through 2010. Monitoring components of the more comprehensive study included biosolids collected at the wastewater treatment plant, soil, crops, dust, alluvial and bedrock ground water, and stream bed sediment. Streams at the site are dry most of the year, so samples of stream bed sediment deposited after rain were used to indicate surface-water effects. This presentation will only address biosolids, soil, and crops. More information about these and the other monitoring components are presented in the literature (e.g., Yager and others, 2004a, b, c, d) and at the USGS Web site for the Deer Trail area studies at http://co.water.usgs.gov/projects/CO406/CO406.html. Priority parameters identified by the stakeholders for all monitoring components, included the total concentrations of nine trace elements (arsenic, cadmium, copper, lead, mercury, molybdenum, nickel, selenium, and zinc), plutonium isotopes, and gross alpha and beta activity, regulated by Colorado for biosolids to be used as an agricultural soil amendment. Nitrogen and chromium also were priority parameters for ground water and sediment components. In general, the objective of each component of the study was to determine whether concentrations of priority parameters (1) were higher than regulatory limits, (2) were increasing with time, or (3) were significantly higher in biosolids-applied areas than in a similar farmed area where biosolids were not applied. Where sufficient samples could be collected, statistical methods were used to evaluate effects. Rigorous quality assurance was included in all aspects of the study. The roles of hydrology and geology also were considered in the design, data collection, and interpretation phases of the study. Study results indicate that the chemistry of the biosolids from the Denver plant was consistent during 1999-2005, and total concentrations of regulated trace elements were consistently lower than the regulatory limits. Plutonium isotopes were not detected in the biosolids. Leach tests using deionized water to simulate natural precipitation indicate arsenic, molybdenum, and nickel were the most soluble priority parameters in the biosolids. Study results show no significant difference in concentrations of priority parameters between biosolids-applied soils and unamended soils where no biosolids were applied. However, biosolids were applied only twice during 1999-2003. The next soil sampling is not scheduled until 2010. To date concentrations of most of the priority parameters were not much greater in the biosolids than in natural soil from the sites. Therefore, many more biosolids applications would need to occur before biosolids effects on the soil priority constituents can be quantified. Leach tests using deionized water to simulate precipitation indicate that molybdenum and selenium were the priority parameters that were most soluble in both biosolids-applied soil and natural or unamended soil. Study results do not indicate significant differences in concentrations of priority parameters between crops grown in biosolids-applied areas and crops grown where no biosolids were applied. However, crops were grown only twice during 1999-2003, so only two crop samples could be collected. The wheat-grain elemental data collected during 1999-2003 for both biosolids-applied areas and unamended areas are similar

Open-File Report↗
USGS2006

Investigating the role of gas bubble formation and entrapment in contaminated aquifers: Reactive transport modelling

In many natural and contaminated aquifers, geochemical processes result in the production or consumption of dissolved gases. In cases where methanogenesis or denitrification occurs, the production of gases may result in the formation and growth of gas bubbles below the water table. Near the water table, entrapment of atmospheric gases during water table rise may provide a significant source of O 2 to waters otherwise depleted in O 2 . Furthermore, the presence of bubbles will affect the hydraulic conductivity of an aquifer, resulting in changes to the groundwater flow regime. The interactions between physical transport, biogeochemical processes, and gas bubble formation, entrapment and release is complex and requires suitable analysis tools. The objective of the present work is the development of a numerical model capable of quantitatively assessing these processes. The multicomponent reactive transport code MIN3P has been enhanced to simulate bubble growth and contraction due to in-situ gas production or consumption, bubble entrapment due to water table rise and subsequent re-equilibration of the bubble with ambient groundwater, and permeability changes due to trapped gas phase saturation. The resulting formulation allows for the investigation of complex geochemical systems where microbially mediated redox reactions both produce and consume gases as well as affect solution chemistry, alkalinity, and pH. The enhanced model has been used to simulate processes in a petroleum hydrocarbon contaminated aquifer where methanogenesis is an important redox process. The simulations are constrained by data from a crude oil spill site near Bemidji, MN. Our results suggest that permeability reduction in the methanogenic zone due to in-situ formation of gas bubbles, and dissolution of entrapped atmospheric bubbles near the water table, both work to attenuate the dissolved gas plume emanating from the source zone. Furthermore, the simulations demonstrate that under the given conditions more than 50% of all produced CH 4 partitions to the gas phase or is aerobically oxidised near the water table, suggesting that these processes should be accounted for when assessing the rate and extent of methanogenic degradation of hydrocarbons.

Journal of Contaminant Hydrology↗
USGS2014

In situ and laboratory toxicity of coalbed natural gas produced waters with elevated sodium bicarbonate

Some tributaries in the Powder River Structural Basin, USA, were historically ephemeral, but now contain water year round as a result of discharge of coalbed natural gas (CBNG)-produced waters. This presented the opportunity to study field sites with 100% effluent water with elevated concentrations of sodium bicarbonate. In situ experiments, static renewal experiments performed simultaneously with in situ experiments, and static renewal experiments performed with site water in the laboratory demonstrated that CBNG-produced water reduces survival of fathead minnow ( Pimephales promelas ) and pallid sturgeon ( Scaphirhynchus albus ). Age affected survival of fathead minnow, where fish 2 d posthatch (dph) were more sensitive than 6 dph fish, but pallid sturgeon survival was adversely affected at both 4 and 6 dph. This may have implications for acute assays that allow for the use of fish up to 14 dph. The survival of early lifestage fish is reduced significantly in the field when concentrations of NaHCO 3 rise to more than 1500 mg/L (also expressed as >1245 mg HCO 3 (-) /L). Treatment with the Higgin's Loop technology and dilution of untreated water increased survival in the laboratory. The mixing zones of the 3 outfalls studied ranged from approximately 800 m to 1200 m below the confluence. These experiments addressed the acute toxicity of effluent waters but did not address issues related to the volumes of water that may be added to the watershed.

Environmental Toxicology and Chemistry↗
USGS1998

Development and application of a marine sediment pore-water toxicity test using Ulva fasciata zoospores

An acute (96 h) pore-water toxicity test protocol using germination and growth of Ulva fasciata zoospores as endpoints was developed to test the toxicity of marine and estuarine sediment pore-water samples. Tests with an organic toxicant (sodium dodecyl sulfate; SDS), three metals (Cd, Cu, and Zn), and ammonia (NH 3 ) were conducted to determine zoospore sensitivity. Zoospore germination and gametophyte growth were as sensitive to SDS as sea urchin ( Arbacia punctulata ) fertilization and embryological development. Zoospore sensitivity to metals was greater than or comparable to that of adult macroalgae. Zoospores were less sensitive to NH 3 than were other commonly used toxicity test organisms. Test results using this algal assay with sediment pore-water samples with high NH 3 concentrations were compared with results from sea urchin fertilization and embryological development tests for the same samples. Ulva fasciata zoospore germination was not affected by samples with high NH 3 concentrations that were toxic in both sea urchin tests. Zoospore tolerance of NH 3 and sensitivity to other contaminants indicate that their response may be useful in toxicity identification evaluation studies with pore-water samples that contain high concentrations of unionized NH 3 .

Environmental Toxicology and Chemistry↗
USGS1989

Shape-selective adsorption of aromatic molecules from water by tetramethylammonium-smectite

The adsorption of aromatic compounds by smectite exchanged with tetramethylammonium (TMA) has been studied. Aromatic compounds adsorbed by TMA-smectite are assumed to adopt a tilted orientation in a face-to-face arrangment with the TMA tetrahedra. The sorptive characteristics of TMA-smectite were influenced strongly by the presence of water. The dry TMA-smectite showed little selectivity in the uptake of benzen, toluene and xylene. In the presence of water, TMA-smectite showed a high degree of selectivity based on molecular size/shape, resulting in high uptake of benzene and progressively lower uptake of larger aromatic molecules. This selectivity appeared to result from the shrinkage of interlamellar cavities by water.

Journal of the Chemical Society, Faraday Transacti↗
USGS2010

Formation of the Wiesloch Mississippi Valley-type Zn-Pb-Ag deposit in the extensional setting of the Upper Rhinegraben, SW Germany

The Mississippi Valley-type (MVT) Zn–Pb–Ag deposit in the Wiesloch area, Southwest Germany, is controlled by graben-related faults of the Upper Rhinegraben. Mineralization occurs as vein fillings and irregular replacement ore bodies consisting of sphalerite, banded sphalerite, galena, pyrite, sulfosalts (jordanite and geocronite), barite, and calcite in the Middle Triassic carbonate host rock. Combining paragenetic information, fluid inclusion investigations, stable isotope and mineral chemistry with thermodynamic modeling, we have derived a model for the formation of the Wiesloch deposit. This model involves fluid mixing between ascending hot brines (originating in the crystalline basement) with sedimentary formation waters. The ascending brines originally had a near-neutral pH (around 6) and intermediate oxidation state, reflecting equilibrium with granites and gneisses in the basement. During fluid ascent and cooling, the pH of the brine shifted towards more acidic (around 4) and the oxidation state increased to conditions above the hematite-magnetite buffer. These chemical characteristics contrast strongly with those of the pore and fracture fluid residing in the limestone aquifer, which had a pH between 8 and 9 in equilibrium with calcite and was rather reduced due to the presence of organic matter in the limestone. Mixing between these two fluids resulted in a strong decrease in the solubility of silver-bearing sphalerite and galena, and calcite. Besides Wiesloch, several Pb–Zn deposits are known along the Upper Rhinegraben, including hydrothermal vein-type deposits like Badenweiler and the Michael mine near Lahr. They all share the same fluid origin and formation process and only differ in details of their host rock and fluid cooling paths. The mechanism of fluid mixing also seems to be responsible for the formation of other MVT deposits in Europe (e.g., Réocin, Northern Spain; Trèves, Southern France; and Cracow-Silesia, Poland), which show notable similarities in terms of their age, mineralogy. and mineral chemistry to the MVT deposit near Wiesloch.

Mineralium Deposita↗
USGS2008

Trends in snowpack chemistry and comparison to National Atmospheric Deposition Program results for the Rocky Mountains, US, 1993-2004

Seasonal snowpack chemistry data from the Rocky Mountain region of the US was examined to identify long-term trends in concentration and chemical deposition in snow and in snow-water equivalent. For the period 1993-2004, comparisons of trends were made between 54 Rocky Mountain Snowpack sites and 16 National Atmospheric Deposition Program wetfall sites located nearby in the region. The region was divided into three subregions: Northern, Central, and Southern. A non-parametric correlation method known as the Regional Kendall Test was used. This technique collectively computed the slope, direction, and probability of trend for several sites at once in each of the Northern, Central, and Southern Rockies subregions. Seasonal Kendall tests were used to evaluate trends at individual sites. Significant trends occurred during the period in wetfall and snowpack concentrations and deposition, and in precipitation. For the comparison, trends in concentrations of ammonium, nitrate, and sulfate for the two networks were in fair agreement. In several cases, increases in ammonium and nitrate concentrations, and decreases in sulfate concentrations for both wetfall and snowpack were consistent in the three subregions. However, deposition patterns between wetfall and snowpack more often were opposite, particularly for ammonium and nitrate. Decreases in ammonium and nitrate deposition in wetfall in the central and southern rockies subregions mostly were moderately significant (p<0.11) in constrast to highly significant increases in snowpack (p<0.02). These opposite trends likely are explained by different rates of declining precipitation during the recent drought (1999-2004) and increasing concentration. Furthermore, dry deposition was an important factor in total deposition of nitrogen in the region. Sulfate deposition decreased with moderate to high significance in all three subregions in both wetfall and snowpack. Precipitation trends consistently were downward and significant for wetfall, snowpack, and snow-telemetry data for the central and southern rockies subregions (p<0.03), while no trends were noted for the Northern Rockies subregion.

Atmospheric Environment↗
USGS2011

The Alaska Geochemical Database: v. 1.0 - Geologic Materials

What is the AGDB?: The Alaska Geochemical Database (AGDB) is a new, comprehensive compilation of geologic, spatial, descriptive, mineralogical, and analytical geochemical data for samples collected in Alaska and surrounding waters by the U.S. Geological Survey (USGS) from 1962 to 2009. Data for geologic materials (rocks, minerals and mineral separates, soils, lake sediments, bulk stream sediments, and a variety of heavy-mineral concentrates) will be released as a two-sided DVD (USGS Digital Data Series DS 637 v. 1.0) in October of 2011. Future data releases will include water, organic and leachate samples. The AGDB contains all Alaskan data from USGS legacy databases (for example, the RASS and PLUTO systems), and all results produced by USGS in-house and contract chemistry laboratories through December 2009. The database includes geochemical data resulting from the reanalysis of archived materials, such as those from the Alaska Mineral Resource Assessment (AMRAP) and National Uranium Resource Evaluation (NURE) programs, for additional elements and by newer methods. Reanalyses include samples collected statewide as part of the National Geochemical Survey, and samples from a project across the Alaska Range (data released in 2010). The AGDB also contains data for geologic materials from Alaska submitted by USGS researchers to non-USGS and non-contract labs, and a variety of other Alaskan geologic materials samples. Quality Control: Data in the AGDB have undergone extensive quality control screening including searching field notes and maps for accurate location information, verifying media and sample type, linking analytical data to geologic parameters recorded by the submitter, and documenting sample preparation and analytical methods. Data Files The AGDB v. 1.0 two-sided DVD includes: * a 4.3 GB Microsoft Access&reg; 2007 relational database (as two linked .mdb files); * the same database in Microsoft Access&reg; 2003; * Microsoft Excel&reg; spreadsheet tables (.xls files) and ASCII text files that display the results of common queries to the database (for example, Ag-Cr values for concentrate samples; rock samples by quadrangle); * references for analytical methods; * references to published data; and * metadata in three file formats. Data Availability: * The Alaska Geochemical Database will be available in a searchable, spatially referenced, online format at http://mrdata.usgs.gov/; estimated availability early 2012. * A 2012 update (AGDB v. 2.0) will include water, organic, leachate, and miscellaneous sample media. For More Information: On sample media or analytical methods: http://minerals.cr.usgs.gov/projects/analytical_chem/references.html Text prepared by Jeanine M. Schmidt and Matt Granitto Figure prepared by Nora Shew; Layout by Jeanine Schmidt Artwork on page 1 by Daniel Granitto (used by permission) The USGS Mineral Resources Program is the sole Federal provider of research and information on nonfuel mineral resources.

Fact Sheet↗
USGS1991

Rare earth elements in Japan Sea sediments and diagenetic behavior of Ce/Ce∗: results from ODP Leg 127

The relative effects of paleoceanographic and paleogeographic variations, sediment lithology, and diagenetic processes on the recorded rare earth element (REE) chemistry of Japan Sea sediments are evaluated by investigating REE total abundances and relative fractionations in 59 samples from Ocean Drilling Program Leg 127. REE total abundances (&Sigma;REE) in the Japan Sea are strongly dependent upon the paleoceanographic position of a given site with respect to terrigenous and biogenic sources. REE concentrations at Site 794 (Yamato Basin) overall correspond well to aluminosilicate chemical indices and are strongly diluted by SiO 2 within the late Miocene-Pliocene diatomaceous sequence. Eu/Eu* values at Site 794 reach a maximum through the diatomaceous interval as well, most likely suggesting an association of Eu/Eu* with the siliceous component, or reflecting slight incorporation of a detrital feldspar phase. &Sigma;REE at Site 795 (Japan Basin) also is affiliated strongly with aluminosilicate phases, yet is diluted only slightly by siliceous input. At Site 797 (Yamato Basin), REE is not as clearly associated with the aluminosilicate fraction, is correlated moderately to siliceous input, and may be sporadically influenced by detrital heavy minerals originating from the nearby rifted continental fragment composing the Yamato Rise. The biogenic influence is largest at Site 794, moderately developed at Site 797, and of only minor importance at Site 795, reflecting basinal contrasts in productivity such that the Yamato Basin records greater biogenic input than the Japan Basin, while the most productive waters overlie the easternmost sequence of Site 794. Ce/Ce* profiles at all three sites increase monotonically with depth, and record progressive diagenetic LREE fractionation. The observed Ce/Ce* record does not respond to changes in oxygenation state of the overlying water, and Ce/Ce* correlated slightly better with depth than with age. The downhole increase in Ce/Ce* at Site 794 and Site 797 is a passive response to diagenetic transfer of LREE (except Ce) from sediment to interstitial water. At Site 795, the overall lack of correlation between Ce/Ce* and L (l n /Yb n suggests that other processes are occurring which mask the diagenetic behavior of all LREEs. First-order calculations of the Ce budget in Japan Sea waters and sediment indicate that ~20% of the excess Ce adsorbed by settling particles is recycled within the water column, and that an additional ~38% is recycled at or near the seafloor (data from Masuzawa and Koyama, 1989). Thus, because the remaining excess Ce is only ~10% of the total Ce, there is not a large source of Ce to the deeply buried sediment, further suggesting that the downhole increase in Ce/Ce* is a passive response to diagenetic behavior of the other LREEs. The REE chemistry of Japan Sea sediment therefore predicts successive downhole addition of LREEs to deeply-buried interstitial waters.

Geochimica et Cosmochimica Acta↗
USGS2022

Small anthropogenic landforms from past charcoal production control moisture dynamics and chemistry in northcentral Appalachian soils

Throughout the northeastern United States (U.S.) and Europe, relict charcoal hearths (RCHs) are regularly being discovered in proximity to furnaces once used for the extraction of metal from ore or quick-lime production; charcoal produced in hearths was used as a furnace fuel. Given previous research has shown that topographic and subsurface disturbance can be great when a hearth is constructed, we hypothesize that hearth construction alters surface hydrology and soil chemistry in environments in and near hearths. We used a landscape classification process to identify 6,758 hearths near furnaces at Greenwood and Pine Grove Furnace State Park, central and southcentral Pennsylvania, U.S. Two types of digital elevation model wetness indexes were used to quantify surface hydrology effects in and around hearths. Modeled wetness conditions were compared to field soil volumetric water content in RCHs near Greenwood Furnace State Park. Modeled wetness indexes indicate that RCH interiors are significantly wetter than RCH rim areas; RCHs are acting as a landscape moisture sink. Results also indicate that RCHs on slopes result in downslope drier conditions below RCHs. Field measured volumetric water content indicates that as distance from the center of the hearth increases, soil moisture significantly decreases. Geomorphic position was found to not be related to RCH wetness. Soil from RCHs, compared to nearby native soils, has significantly higher total C, a lower Mehlich 3 extractable acidity, higher Ca and P. No trend was evident with RCH soil chemistry and geomorphic position. The high frequency of RCH occurrence, in proximity to the furnace’s RCHs supported, suggests that RCHs today could locally be an important niche for understory flora and fauna. Further research could explore how RCHs might be affecting surrounding plant populations and how within RCH patterns, especially on hillslopes, might represent a distinctly different scale of physical and chemical variability.

Pennsylvania↗
USGS2011

Transient groundwater chemistry near a river: Effects on U(VI) transport in laboratory column experiments

In the 300 Area of a U(VI)-contaminated aquifer at Hanford, Washington, USA, inorganic carbon and major cations, which have large impacts on U(VI) transport, change on an hourly and seasonal basis near the Columbia River. Batch and column experiments were conducted to investigate the factors controlling U(VI) adsorption/desorption by changing chemical conditions over time. Low alkalinity and low Ca concentrations (Columbia River water) enhanced adsorption and reduced aqueous concentrations. Conversely, high alkalinity and high Ca concentrations (Hanford groundwater) reduced adsorption and increased aqueous concentrations of U(VI). An equilibrium surface complexation model calibrated using laboratory batch experiments accounted for the decrease in U(VI) adsorption observed with increasing (bi)carbonate concentrations and other aqueous chemical conditions. In the column experiment, alternating pulses of river and groundwater caused swings in aqueous U(VI) concentration. A multispecies multirate surface complexation reactive transport model simulated most of the major U(VI) changes in two column experiments. The modeling results also indicated that U(VI) transport in the studied sediment could be simulated by using a single kinetic rate without loss of accuracy in the simulations. Moreover, the capability of the model to predict U(VI) transport in Hanford groundwater under transient chemical conditions depends significantly on the knowledge of real-time change of local groundwater chemistry.

Washington↗
USGS2013

Wetlands serve as natural sources for improvement of stream ecosystem health in regions affected by acid deposition

For over 40 years, acid deposition has been recognized as a serious international environmental problem, but efforts to restore acidified streams and biota have had limited success. The need to better understand the effects of different sources of acidity on streams has become more pressing with the recent increases in surface water organic acids, or 'brownification' associated with climate change and decreased inorganic acid deposition. Here, we carried out a large scale multi-seasonal investigation in the Adirondacks, one of the most acid-impacted regions in the United States, to assess how acid stream producers respond to local and watershed influences and whether these influences can be used in acidification remediation. We explored the pathways of wetland control on aluminum chemistry and diatom taxonomic and functional composition. We demonstrate that streams with larger watershed wetlands have higher organic content, lower concentrations of acidic anions, and lower ratios of inorganic to organic monomeric aluminum, all beneficial for diatom biodiversity and guilds producing high biomass. Although brownification has been viewed as a form of pollution, our results indicate that it may be a stimulating force for biofilm producers with potentially positive consequences for higher trophic levels. Our research also reveals that the mechanism of watershed control of local stream diatom biodiversity through wetland export of organic matter is universal in running waters, operating not only in hard streams, as previously reported, but also in acid streams. Our findings that the negative impacts of acid deposition on Adirondack stream chemistry and biota can be mitigated by wetlands have important implications for biodiversity conservation and stream ecosystem management. Future acidification research should focus on the potential for wetlands to improve stream ecosystem health in acid-impacted regions and their direct use in stream restoration, for example, through stream rechanneling or wetland construction in appropriate hydrologic settings.

Global Change Biology↗
USGS2019

Aluminum mobility in mildly acidic mine drainage: Interactions between hydrobasaluminite, silica and trace metals from the nano to the meso-scale

Aluminum precipitates control the hydrochemistry and mineralogy of a broad variety of environments on Earth (e.g., acid mine drainage, AMD, coastal wetlands, boreal and alpine streams, tropical acid sulfate soils, laterites and bauxites, …). However, the geochemical and mineralogical processes controlling Al (and other associated metals and metalloids) transport and removal in those environments are not fully understood. The geochemical system of Paradise Portal (Colorado, USA) comprises sulfate-rich mildly acidic waters, the hydrochemistry of which is directly controlled by the massive precipitation of hydrobasaluminite Al 4 (SO 4 )(OH) 10 ·12-36H 2 O. Three connected but discernible aluminum precipitation stages were identified and described: 1) nanoparticle formation and size decrease along the creek, 2) hydrobasaluminite neoformation on the riverbed, and 3) precipitate accretion and accumulation on the riverbed leading to Al and Fe banded formations. The co-occurrence of Al and Si in the system was observed, recording significant amounts of Si accompanying the three different components of the system (i.e., nanoparticles and fresh and aged Al-precipitates). Also, abrupt and minor changes in the sedimentary record were described and proposed to be the response of the system to seasonal and interannual changes in AMD chemistry. Concerning the mobility of other metals and metalloids, P, Th, V, W, Ti and B showed a tendency to be preferentially incorporated into hydrobasaluminite, while others like Be, As, Se or Ba tend to remain dissolved in the water.

Chemical Geology↗