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USGS2016

Soil mercury distribution in adjacent coniferous and deciduous stands highly impacted by acid rain in the Ore Mountains, Czech Republic

Forests play a primary role in the cycling and storage of mercury (Hg) in terrestrial ecosystems. This study aimed to assess differences in Hg cycling and storage resulting from different vegetation at two adjacent forest stands - beech and spruce. The study site Načetín in the Czech Republic's Black Triangle received high atmospheric loadings of Hg from coal combustion in the second half of the 20th century as documented by peat accumulation rates reaching 100 μg m −2 y −1 . In 2004, the annual litterfall Hg flux was 22.5 μg m −2 y −1 in the beech stand and 14.5 μg m −2 y −1 in the spruce stand. Soil concentrations and pools of Hg had a strong positive relation to soil organic matter and concentrations of soil sulfur (S) and nitrogen (N). O-horizon Hg concentrations ranged from 245 to 495 μg kg −1 and were greater in the spruce stand soil, probably as a result of greater dry Hg deposition. Mineral soil Hg concentrations ranged from 51 to 163 μg kg −1 and were greater in the beech stand soil due to its greater capacity to store organic carbon (C). The Hg/C ratio increased with depth from 0.3 in the O-horizon to 3.8 μg g −1 in the C horizon of spruce soil and from 0.7 to 2.7 μg g −1 in beech soil. The Hg/C ratio was greater at all mineral soil depths in the spruce stand. The organic soil Hg pools in beech and spruce stands (6.4 and 5.7 mg m −2 , respectively) were considerably lower than corresponding mineral soil Hg pools (39.1 and 25.8 mg m −2 ). Despite the important role of S in Hg cycling, differences in soil Hg distribution at both stands could not be attributed to differences in soil sulfur speciation.

Ore Mountains↗

USGS2018

Four-dimensional isotopic approach to identify perchlorate sources in groundwater: Application to the Rialto-Colton and Chino subbasins, southern California (USA)

Perchlorate (ClO 4 − ) in groundwater can be from synthetic or natural sources. Natural sources include ClO 4 − associated with historical application of imported natural nitrate fertilizer from the Atacama Desert of Chile, and indigenous ClO 4 − that accumulates locally in arid regions from atmospheric deposition. The Rialto-Colton groundwater subbasin, 80 km east of Los Angeles, California, includes two mapped ClO 4 − plumes from known military/industrial sources. Larger areas downgradient from those plumes, and in the Chino subbasin to the southwest, also contain ClO 4 − . Perchlorate from wells was analyzed for chlorine and oxygen stable isotope ratios (δ 37 Cl, δ 18 O, Δ 17 O) and radioactive chlorine-36( 36 Cl) isotopic abundance, along with other geochemical, isotopic, and hydrogeologic data. Isotopic data show that synthetic ClO 4 − was the dominant source within the mapped plumes. Downgradient from the mapped plumes, and in the Chino subbasin, the dominant source of ClO 4 − was related to past agricultural use of Chilean (Atacama) nitrate fertilizer. The 36 Cl and δ 18 O data indicate that wells having predominantly synthetic or Atacama ClO 4 − also contained small fractions of indigenous ClO 4 − . Little or no differences were observed in isotopic composition or ClO 4 − source with depth in depth-dependent data from selected wells. Indigenous ClO 4 − was most evident in upgradient wells having ClO 4 − concentrations <1 μg/L, consistent with its occurrence as a background constituent throughout the region. Stable isotope ratios of chlorine and oxygen and 36 Cl isotopic abundance data provided relatively unambiguous discrimination of synthetic and Atacama sources in most wells having ClO 4 − concentrations greater than 1 μg/L.

California↗

USGS2020

Batch extraction method to estimate total dissolved solids (TDS) release from coal refuse and overburden

A rapid batch extraction method was evaluated to estimate potential for total dissolved solids (TDS) release by 65 samples of rock from coal and gas-bearing strata of the Appalachian Basin in eastern USA. Three different extractant solutions were considered: deionized water (DI), DI equilibrated with 10% CO 2 atmosphere (DI + CO 2 ), or 30% H 2 O 2 under 10% CO 2 (H 2 O 2 +CO 2 ). In all extractions, 10 g of pulverized rock (<0.5-mm) were mixed with 20 mL of extractant solution and shaken for 4 h at 50 rpm and 20–22 °C. The 65 rock samples were classified as coal (n=3), overburden (n = 17), coal refuse that had weathered in the field (n = 14), unleached coal refuse that had oxidized during indoor storage (n = 20), gas-bearing shale (n = 10), and pyrite (n = 1). Extracts were analyzed for specific conductance (SC), TDS, pH, and major and trace elements, and subsequently speciated to determine ionic contributions to SC. The pH of extractant blanks decreased in the order DI (6.0), DI + CO 2 (5.1), and H 2 O 2 +CO 2 (2.6). The DI extractant was effective for mobilizing soluble SO 4 and Cl salts. The DI + CO 2 extractant increased weathering of carbonates and resulted in equivalent or greater TDS than the DI leach of the same material. The H 2 O 2 +CO 2 extractant increased weathering of sulfides (and carbonates) and resulted in the greatest TDS production and lowest pH values. Of the 65 samples, 19 had leachate chemistry data from previous column experiments and 35 were paired to 10 field sites with leachate chemistry data. When accounting for the water-to-rock ratio, TDS from DI and DI + CO 2 extractions were correlated to TDS from column experiments while TDS from H 2 O 2 +CO 2 extractions was not. In contrast to column experiments, field SC was better correlated to SC measured from H 2 O 2 +CO 2 extractions than DI extractions. The field SC and SC from H 2 O 2 +CO 2 extractions were statistically indistinguishable for 7 of 9 paired data sets while SC from DI extractions underestimated field SC in 5 of 9 cases. Upscaling comparisons suggest that (1) weathering reactions in the field are more aggressive than DI water or synthetic rainwater extractants used in batch or column tests, and (2) a batch extraction method utilizing 30% H 2 O 2 (which is mildly acidic without CO 2 enrichment) could be effective for identifying rocks that will release high amounts of TDS.

Applied Geochemistry↗

USGS2022

Isotopic discrimination of natural and anthropogenic perchlorate sources in groundwater in a semi-arid region of northeastern Oregon (USA)

Perchlorate (ClO4−) has synthetic and natural sources. Synthetic ClO4− is released to the environment from its use as an oxidant in military and aerospace applications, and from its presence in a variety of common commercial products, such as safety flares, chlorate herbicides, and fireworks. Natural sources of ClO4− in the environment include imported nitrate fertilizers derived from salt deposits in the Atacama Desert of Chile and indigenous natural ClO4− that accumulates in unsaturated soils and groundwaters in other arid and semi-arid environments, largely from atmospheric deposition. The stable isotope ratios of chlorine (37Cl/35Cl) and oxygen (18O/16O, 17O/16O) and the isotopic abundance of radioactive 36Cl in ClO4− can be used to discriminate these different sources. Perchlorate was previously detected at relatively high concentrations (3.8–34.7 μg/L) in groundwater from many wells in the Boardman-Umatilla area near the Columbia River in northeastern Oregon, which is a semi-arid, highly agricultural, heavily irrigated area that includes several past and current military installations. Eight representative groundwater wells were sampled throughout this region and isotopic characteristics of ClO4− collected from each well were measured along with other chemical and isotopic parameters including tritium and other groundwater age indicators. Isotopic data indicate that indigenous natural ClO4− was present in groundwater from all sampled wells and was the predominant source in five of the wells. Synthetic ClO4− was present in the three remaining wells with natural ClO4−, and a minor fraction of Atacama-fertilizer-derived ClO4− was indicated in one of the wells. Data from this study expand the geographic area of the USA in which indigenous natural ClO4− has been detected to include the semi-arid northwest. This study also illustrates the role of irrigation recharge as a mechanism for producing relatively high concentrations of indigenous natural ClO4− in groundwater by flushing accumulated salts from the unsaturated zone.

Oregon↗

USGS2014

Aquatic CAM photosynthesis: a brief history of its discovery

Aquatic CAM (Crassulacean Acid Metabolism) photosynthesis was discovered while investigating an unrelated biochemical pathway concerned with anaerobic metabolism. George Bowes was a significant contributor to this project early in its infancy. Not only did he provide me with some valuable perspectives on peer review rejections, but by working with his gas exchange system I was able to take our initial observations of diel fluctuations in malic acid to the next level, showing this aquatic plant exhibited dark CO2 uptake. CAM is universal in all aquatic species of the worldwide Lycophyta genus Isoetes and non-existent in terrestrial Isoetes. Outside of this genus aquatic CAM has a limited occurrence in three other families, including the Crassulaceae. This discovery led to fascinating adventures in the highlands of the Peruvian Andes in search of Stylites, a terrestrial relative of Isoetes. Stylites is a plant that is hermetically sealed from the atmosphere and obtains all of its carbon from terrestrial sources and recycles carbon through CAM. Considering the Mesozoic origin of Isoetes in shallow pools, coupled with the fact that aquatic Isoetes universally possess CAM, suggests the earliest evolution of CAM photosynthesis was most likely not in terrestrial plants.

Aquatic Botany↗

USGS2004

Modification of pure oxygen absorption equipment for concurrent stripping of carbon dioxide

The high solubility of carbon dioxide precludes significant desorption within commercial oxygen absorption equipment. This operating characteristic of the equipment limits its application in recirculating water culture systems despite its ability to significantly increase allowable fish loading rates (kg/(L min)). Carbon dioxide (DC) is typically removed by air stripping. This process requires a significant energy input for forced air movement, air heating in cold climates and water pumping. We developed a modification for a spray tower that provides for carbon dioxide desorption as well as oxygen absorption. Elimination of the air-stripping step reduces pumping costs while allowing dissolved nitrogen to drop below saturation concentrations. This latter response provides for an improvement in oxygen absorption efficiency within the spray tower. DC desorption is achieved by directing head-space gases from the spray tower (O2, N2, CO2) through a sealed packed tower scrubber receiving a 2 N NaOH solution. Carbon dioxide is selectively removed from the gas stream, by chemical reaction, forming the product Na 2CO3. Scrubber off-gas, lean with regard to carbon dioxide but still rich with oxygen, is redirected through the spray tower for further stripping of DC and absorption of oxygen. Make-up NaOH is metered into the scrubbing solution sump on an as needed basis as directed by a feedback control loop programmed to maintain a scrubbing solution pH of 11.4-11.8. The spent NaOH solution is collected, then regenerated for reuse, in a batch process that requires relatively inexpensive hydrated lime (Ca(OH)2). A by-product of the regeneration step is an alkaline filter cake, which may have use in bio-solids stabilization. Given the enhanced gas transfer rates possible with chemical reaction, the required NaOH solution flow rate through the scrubber represents a fraction of the spray tower water flow rate. Further, isolation of the water being treated from the atmosphere (1), allows for an improvement in oxygen absorption efficiency by maintaining DN well below local saturation concentrations (2), minimizes building energy requirements related to heating and ventilation and (3), reduces the potential for pathogen transmittance. We report on the performance of a test scrubber evaluated over a range of NaOH solution temperatures, pH, packing irrigation rates, and gas stream compositions. We also describe our experience with the process in a pilot scale recirculating water (trout) production system.

Conference Paper↗

USGS2006

Limestone fluidized bed treatment of acid-impacted water at the Craig Brook National Fish Hatchery, Maine, USA

Decades of atmospheric acid deposition have resulted in widespread lake and river acidification in the northeastern U.S. Biological effects of acidification include increased mortality of sensitive aquatic species such as the endangered Atlantic salmon (Salmo salar). The purpose of this paper is to describe the development of a limestone-based fluidized bed system for the treatment of acid-impacted waters. The treatment system was tested at the Craig Brook National Fish Hatchery in East Orland, Maine over a period of 3 years. The product water from the treatment system was diluted with hatchery water to prepare water supplies with three different levels of alkalinity for testing of fish health and survival. Based on positive results from a prototype system used in the first year of the study, a larger demonstration system was used in the second and third years with the objective of decreasing operating costs. Carbon dioxide was used to accelerate limestone dissolution, and was the major factor in system performance, as evidenced by the model result: Alk = 72.84 ?? P(CO2)1/2; R2 = 0.975. No significant acidic incursions were noted for the control water over the course of the study. Had these incursions occurred, survivability in the untreated water would likely have been much more severely impacted. Treated water consistently provided elevated alkalinity and pH above that of the hatchery source water. ?? 2005 Elsevier B.V. All rights reserved.

Aquacultural Engineering↗

USGS2012

Carbon dioxide stripping in aquaculture -- part II: development of gas transfer models

The basic mass transfer equation for gases such as oxygen and carbon dioxide can be derived from integration of the driving force equation. Because of the physical characteristics of the gas transfer processes, slightly different models are used for aerators tested under the non steady-state procedures, than for packed columns, or weirs. It is suggested that the standard condition for carbon dioxide should be 20 °C, 1 atm, CCO 2 =20 mg/kg, and XCO 2 =0.000285. The selection of the standard condition for carbon dioxide based on a fixed mole fraction ensures that standardized carbon dioxide transfer rates will be comparable even though the value of C* CO 2 in the atmosphere is increasing with time. The computation of mass transfer for carbon dioxide is complicated by the impact of water depth and gas phase enrichment on the saturation concentration within the unit, although the importance of either factor depends strongly on the specific type of aerator. For some types of aerators, the most accurate gas phase model remains to be determined for carbon dioxide. The assumption that carbon dioxide can be treated as a non-reactive gas in packed columns may apply for cold acidic waters but not for warm alkaline waters.

Aquacultural Engineering↗

USGS2005

The carbon dioxide cycle

The seasonal CO2 cycle on Mars refers to the exchange of carbon dioxide between dry ice in the seasonal polar caps and gaseous carbon dioxide in the atmosphere. This review focuses on breakthroughs in understanding the process involving seasonal carbon dioxide phase changes that have occurred as a result of observations by Mars Global Surveyor.

Advances in Space Research↗

USGS2008

Satellite remotely-sensed land surface parameters and their climatic effects for three metropolitan regions

By using both high-resolution orthoimagery and medium-resolution Landsat satellite imagery with other geospatial information, several land surface parameters including impervious surfaces and land surface temperatures for three geographically distinct urban areas in the United States – Seattle, Washington, Tampa Bay, Florida, and Las Vegas, Nevada, are obtained. Percent impervious surface is used to quantitatively define the spatial extent and development density of urban land use. Land surface temperatures were retrieved by using a single band algorithm that processes both thermal infrared satellite data and total atmospheric water vapor content. Land surface temperatures were analyzed for different land use and land cover categories in the three regions. The heterogeneity of urban land surface and associated spatial extents were shown to influence surface thermal conditions because of the removal of vegetative cover, the introduction of non-transpiring surfaces, and the reduction in evaporation over urban impervious surfaces. Fifty years of in situ climate data were integrated to assess regional climatic conditions. The spatial structure of surface heating influenced by landscape characteristics has a profound influence on regional climate conditions, especially through urban heat island effects.

Advances in Space Research↗

USGS2011

Design of ecoregional monitoring in conservation areas of high-latitude ecosystems under contemporary climate change

Land ownership in Alaska includes a mosaic of federally managed units. Within its agency’s context, each unit has its own management strategy, authority, and resources of conservation concern, many of which are migratory animals. Though some units are geographically isolated, many are nevertheless linked by paths of abiotic and biotic flows, such as rivers, air masses, flyways, and terrestrial and aquatic migration routes. Furthermore, individual land units exist within the context of a larger landscape pattern of shifting conditions, requiring managers to understand at larger spatial scales the status and trends in the synchrony and spatial concurrence of species and associated suitable habitats. Results of these changes will determine the ability of Alaska lands to continue to: provide habitat for local and migratory species; absorb species whose ranges are shifting northward; and experience mitigation or exacerbation of climate change through positive and negative atmospheric feedbacks. We discuss the geographic and statutory contexts that influence development of ecological monitoring; argue for the inclusion of significant amounts of broad-scale monitoring; discuss the importance of defining clear programmatic and monitoring objectives; and draw from lessons learned from existing long-term, broad-scale monitoring programs to apply to the specific contexts relevant to high-latitude protected areas such as those in Alaska. Such areas are distinguished by their: marked seasonality; relatively large magnitudes of contemporary change in climatic parameters; and relative inaccessibility due to broad spatial extent, very low (or zero) road density, and steep and glaciated areas. For ecological monitoring to effectively support management decisions in high-latitude areas such as Alaska, a monitoring program ideally would be structured to address the actual spatial and temporal scales of relevant processes, rather than the artificial boundaries of individual land-management units. Heuristic models provide a means by which to integrate understanding of ecosystem structure, composition, and function, in the midst of numerous ecosystem drivers.

Alaska↗

USGS2010

Computer algorithm for analyzing and processing borehole strainmeter data

The newly installed Plate Boundary Observatory (PBO) strainmeters record signals from tectonic activity, Earth tides, and atmospheric pressure. Important information about tectonic processes may occur at amplitudes at and below tidal strains and pressure loading. If incorrect assumptions are made regarding the background noise in the strain data, then the estimates of tectonic signal amplitudes may be incorrect. Furthermore, the use of simplifying assumptions that data are uncorrelated can lead to incorrect results and pressure loading and tides may not be completely removed from the raw data. Instead, any algorithm used to process strainmeter data must incorporate the strong temporal correlations that are inherent with these data. The technique described here uses least squares but employs data covariance that describes the temporal correlation of strainmeter data. There are several advantages to this method since many parameters are estimated simultaneously. These parameters include: (1) functional terms that describe the underlying error model, (2) the tidal terms, (3) the pressure loading term(s), (4) amplitudes of offsets, either those from earthquakes or from the instrument, (5) rate and changes in rate, and (6) the amplitudes and time constants of either logarithmic or exponential curves that can characterize postseismic deformation or diffusion of fluids near the strainmeter. With the proper error model, realistic estimates of the standard errors of the various parameters are obtained; this is especially critical in determining the statistical significance of a suspected, tectonic strain signal. The program also provides a method of tracking the various adjustments required to process strainmeter data. In addition, the program provides several plots to assist with identifying either tectonic signals or other signals that may need to be removed before any geophysical signal can be identified.

Computers & Geosciences↗

USGS2006

Late Quaternary eolian dust in surficial deposits of a Colorado Plateau grassland: Controls on distribution and ecologic effects

In a semi-arid, upland setting on the Colorado Plateau that is underlain by nutrient-poor Paleozoic eolian sandstone, alternating episodes of dune activity and soil formation during the late Pleistocene and Holocene have produced dominantly sandy deposits that support grass and shrub communities. These deposits also contain eolian dust, especially in paleosols. Eolian dust in these deposits is indicated by several mineralogic and chemical disparities with local bedrock, but it is most readily shown by the abundance of titaniferous magnetite in the sandy deposits that is absent in local bedrock. Magnetite and some potential plant nutrients (especially, P, K, Na, Mn, and Zn) covary positively with depth (3-4 m) in dune-crest and dune-swale settings. Magnetite abundance also correlates strongly and positively with abundances of other elements (e.g., Ti, Li, As, Th, La, and Sc) that are geochemically stable in these environments. Soil-property variations with depth can be ascribed to three primary factors: (1) shifts in local geomorphic setting; (2) accumulation of relatively high amounts of atmospheric mineral dust inputs during periods of land-surface stability; and (3) variations in dust flux and composition that are likely related to changes in dust-source regions. Shifts in geomorphic setting are revealed by large variations in soil texture and are also expressed by changes in soil chemical and magnetic properties. Variable dust inputs are indicated by both changes in dust flux and changes in relations among magnetic, chemical, and textural properties. The largest of these changes is found in sediment that spans late Pleistocene to early Holocene time. Increased dust inputs to the central Colorado Plateau during this period may have been related to desiccation and shrinkage of large lakes from about 12 to 8 ka in western North America that exposed vast surfaces capable of emitting dust. Soil properties that result from variable dust accumulation and redistribution in these surficial deposits during the late Quaternary are important to modern ecosystem dynamics because some plants today utilize nutrients deposited as long ago as about 12-15 ky and because variations in fine-grained (silt) sediment, including eolian dust, influence soil-moisture capacity.

Catena↗

USGS2013

Sediment accretion and organic carbon burial relative to sea-level rise and storm events in two mangrove forests in Everglades National Park

The goal of this investigation was to examine how sediment accretion and organic carbon (OC) burial rates in mangrove forests respond to climate change. Specifically, will the accretion rates keep pace with sea-level rise, and what is the source and fate of OC in the system? Mass accumulation, accretion and OC burial rates were determined via 210 Pb dating (i.e. 100 year time scale) on sediment cores collected from two mangrove forest sites within Everglades National Park, Florida (USA). Enhanced mass accumulation, accretion and OC burial rates were found in an upper layer that corresponded to a well-documented storm surge deposit. Accretion rates were 5.9 and 6.5 mm yr −1 within the storm deposit compared to overall rates of 2.5 and 3.6 mm yr −1 . These rates were found to be matching or exceeding average sea-level rise reported for Key West, Florida. Organic carbon burial rates were 260 and 393 g m −2 yr −1 within the storm deposit compared to 151 and 168 g m −2 yr −1 overall burial rates. The overall rates are similar to global estimates for OC burial in marine wetlands. With tropical storms being a frequent occurrence in this region the resulting storm surge deposits are an important mechanism for maintaining both overall accretion and OC burial rates. Enhanced OC burial rates within the storm deposit could be due to an increase in productivity created from higher concentrations of phosphorus within storm-delivered sediments and/or from the deposition of allochthonous OC. Climate change-amplified storms and sea-level rise could damage mangrove forests, exposing previously buried OC to oxidation and contribute to increasing atmospheric CO 2 concentrations. However, the processes described here provide a mechanism whereby oxidation of OC would be limited and the overall OC reservoir maintained within the mangrove forest sediments.

Florida↗

USGS2005

Mineralogical and geochemical consequences of the long-term presence of CO2 in natural reservoirs: An example from the Springerville-St. Johns Field, Arizona, and New Mexico, U.S.A

The Springerville-St. Johns CO2 field in eastern Arizona and western New Mexico is one of more than a dozen gas fields developed within the Colorado Plateau and Southern Rocky Mountain region. Extensive travertine (CaCO3) deposits record a long history of CO2 migration and leakage to the atmosphere. The oldest travertine deposits may have formed during the initial filling of the CO2 reservoir when groundwaters exsolved CO2 upon reaching the surface. The youngest travertine deposits are associated with springs on the floor of the Little Colorado River valley, but travertine deposition appears to be insignificant today. Older deposits occur up to 325 m above the valley floor. Geologic relationships suggest travertine deposition began in the late Pleistocene after volcanic activity ended at ???0.3 Ma. Most of the CaCO3 could have been derived from dissolution of the underlying limestones and dolomites. Interactions between the reservoir fluids and rocks were observed in core samples from one of the intervals that produced dry gas. These reactions resulted in the dissolution of carbonate cements and detrital feldspars and the formation of dawsonite and kaolinite. Geochemical simulations suggest that the dawsonite could have been deposited when the CO2 fugacity reached 20 bars and that the kaolinite formed as the CO2 fugacity decreased. Corrosion of drill pipe by acidic waters and a pronounced HCO3 anomaly above the CO2 reservoir provide evidence of a continuing flux of CO2 from depth. CO2 storage occurs primarily as dissolved carbonate species and as gas accumulations. Only a small percentage of the CO2 was sequestered in secondary minerals. ?? 2005 Elsevier B.V. All rights reserved.

Chemical Geology↗

USGS2008

The effect of acid rain and altitude on concentration, δ34S, and δ18O of sulfate in the water from Sudety Mountains, Poland

The analyses of sulfate content, δ 34 S and δ 18 O of dissolved sulfate, and δ 18 O of water were carried out in a 14 km 2 crystalline massif located in the Sudety Mountains (SW Poland) to 1) assess the amount of the sulfate delivered to the surface and groundwater systems by modern atmospheric precipitation, 2) determine the effect of altitude on these parameters, and 3) investigate their seasonal variations. In April and November of 2002, August 2003, and March and September of 2005, samples of water were collected from springs and streams of the massif. During these seasons, sulfate contents and δ 18 O(SO 4 2− ) values varied from 5.80 to 18.00 mg/l and from 3.96 to 8.23&permil;, respectively, showing distinctively higher values of δ 18 O(SO 4 2− ) in wet seasons. The δ 34 S(SO 4 2− ) values had a relatively narrow range from 4.09 to 5.28&permil; and were similar to those reported for organic matter in soil and the canopy throughfall in the Sudety Mountains. Sulfate content, δ 34 S(SO 4 2− ), δ 18 O(SO 4 2− ), and δ 18 O(H 2 O) values revealed a remarkable dependence on the altitude. The calculated altitude effects for five season averages of these parameters were − 1.00 mg/l/100 m, − 0.18&permil;/100 m, − 0.27&permil;/100 m, and − 0.17&permil;/100 m, respectively. This dependence on the altitude resulted mainly from the mixing of sulfates of different origins such as anthropogenic sulfate, sulfate produced in the soil within the weathered zone of the massif, and that one from the tree canopy. The oxygen isotope mass balance indicates that, in the study area, about one third of the sulfate delivered to the surface and groundwater by modern precipitation comes from anthropogenic pollution. Further interaction of meteoric water within the weathered rocks causes a continuous decrease of δ 18 O(SO 4 2− ) values resulting from biological transformation of the sulfate due to plant vegetation and decomposition of organic matter.

Sudety Mountains↗

USGS2009

Halogen degassing during ascent and eruption of water-poor basaltic magma

A study of volcanic gas composition and matrix glass volatile concentrations has allowed a model for halogen degassing to be formulated for K??lauea Volcano, Hawai'i. Volcanic gases emitted during 2004-2005 were characterised by a molar SO 2 /HCl of 10-64, with a mean of 33; and a molar HF/HCl of 0-5, with a mean of 1.0 (from approximately 2500 measurements). The HF/HCl ratio was more variable than the SO 2 /HCl ratio, and the two correlate weakly. Variations in ratio took place over rapid timescales (seconds). Matrix glasses of Pele's tears erupted in 2006 have a mean S, Cl and F content of 67, 85 and 173??ppm respectively, but are associated with a large range in S/F. A model is developed that describes the open system degassing of halogens from parental magmas, using the glass data from this study, previously published results and parameterisation of sulphur degassing from previous work. The results illustrate that halogen degassing takes place at pressures of < 1??MPa, equivalent to < ~ 35??m in the conduit. Fluid-melt partition coefficients for Cl and F are low (< 1.5); F only degasses appreciably at < 0.1??MPa above atmospheric pressure, virtually at the top of the magma column. This model reproduces the volcanic gas data and other observations of volcanic activity well and is consistent with other studies of halogen degassing from basaltic magmas. The model suggests that variation in volcanic gas halogen ratios is caused by exsolution and gas-melt separation at low pressures in the conduit. There is no evidence that either diffusive fractionation or near-vent chemical reactions involving halogens is important in the system, although these processes cannot be ruled out. The fluxes of HCl and HF from K??lauea during 2004-5 were ~ 25 and 12??t/d respectively. ?? 2008 Elsevier B.V.

Chemical Geology↗

USGS2009

The δ 15 N and δ 18 O values of N 2 O produced during the co-oxidation of ammonia by methanotrophic bacteria

In order to determine if the δ 15 N and δ 18 O values of N 2 O produced during co-oxidation of NH 4 + by methanotrophic (methane oxidizing) bacteria can be isotopically distinguished from N 2 O produced either by autotrophic nitrifying or denitrifying bacteria, we conducted laboratory incubation experiments with pure cultures of methanotrophic bacteria that were provided NH 4 Cl as an oxidation substrate. The N 2 O produced during NH 4 + oxidation by methanotrophic bacteria showed nitrogen isotope fractionation between NH 4 + and N 2 O ( ε N 2 O–NH 4 + ) of − 48 and − 55&permil; for Methylomonas methanica and Methylosinus trichosporium , OB3b respectively. These large fractionations are similar to those previously measured for autotrophic nitrifying bacteria and consistent with N 2 O formation by multiple rate limiting steps that include NH 4 + oxidation by the methane monooxygenase enzyme and reduction of NO 2 − to N 2 O. Consequently, N 2 O formed by NH 4 + oxidation via methanotrophic or autotrophic nitrifying bacteria might generally be characterized by lower δ 15 N N 2 O values than that formed by denitrificaiton, although this also depends on the variability of δ 15 N of available nitrogen sources (e.g., NH 4 + , NO 3 − , NO 2 − ). Additional incubations with M. trichosporium OB3b at high and low CH 4 conditions in waters of different δ 18 O values revealed that 19–27% of the oxygen in N 2 O was derived from O 2 with the remainder from water. The biochemical mechanisms that could explain this amount of O 2 incorporation are discussed. The δ 18 O of N 2 O formed under high CH 4 conditions was ~ + 15&permil; more positive than that formed under lower CH 4 conditions. This enrichment resulted in part from the incorporation of O 2 into N 2 O that was enriched in 18 O due to an isotope fractionation effect of − 16.1 ± 2.0&permil; and − 17.5 ± 5.4&permil; associated with O 2 consumption during the high and low methane concentration incubations, respectively. Therefore, N 2 O formed by NH 4 + oxidation via methanotrophic or autotrophic nitrifying bacteria can have very positive δ 18 O N 2 O values if the O 2 incorporated is previously enriched in 18 O from high rates of respiration. Nitrous oxide was collected from various depths in soils overlying a coal-bed methane seep where methanotrophic bacteria are naturally enriched. In one sampling when soil methane concentrations were very high, the δ 18 O VSMOW values of the N 2 O were highly enriched (+ 50&permil;), consistent with our laboratory experiments. Thus, soils overlying methane seeps could provide an 18 O-enriched source of atmospheric N 2 O.

Chemical Geology↗