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Seasonal/yearly salinity variations in San Francisco Bay

The ability of resource agencies to manage fish, wildlife and freshwater supplies of San Francisco Bay estuary requires an integrated knowledge of the relations between the biota and their physical environment. A key factor in these relations is the role of salinity in determining both the physical and the biological character of the estuary. The saltiness of the water, and particularly its seasonal and interannual patterns of variability, affects which aquatic species live where within the estuary. Salinity also determines where water can and cannot be diverted for human consumption and irrigated agriculture, and plays a role in determining the capacity of the estuary to cleanse itself of wastes. In short, salinity is a fundamental property of estuarine physics and chemistry that, in turn, determines the biological characteristics of each estuary. Freshwater is a major control on estuarine salinity. Most freshwater supplied to the Bay is from river flow through the Delta, which is primarily runoff from the Sierra Nevada. Most contaminants in San Francisco Bay are from the Sacramento/San Joaquin Valley and the local watershed around the Bay rather than the sea or atmosphere. Land is the primary source of freshwater and freshwater serves as a tracer of land-derived substances such as the trace metals (copper, lead and selenium), pesticides and plant nutrients (nitrate and phosphate). The U.S. Geological Survey is collaborating with other agencies and institutions in studying San Francisco Bay salinity using field observations and numerical simulations to define the physical processes that control salinity. The issues that arise from salinity fluctuations, however, differ in the northern and southern parts of the bay. In North Bay we need to know how salinity responds to freshwater flow through the Sacramento/San Joaquin Delta; this knowledge will benefit water managers who determine how much delta flow is needed a) to protect freshwater supplies for municipal water use and b) modulate salinity for a healthy estuary. In South Bay we need to know where the freshwater comes from (the distant Delta or local streams) to sort out the sources of a) contamination or b) dilution.

California

Determination of the components of stormflow using water chemistry and environmental isotopes, Mattole River basin, California

The chemical and isotopic composition of rainfall and stream water was monitored during a storm in the Mattole River basin of northwestern California. About 250 mm of rain fell during 6 days (∼80% within a 42 h period) in late January, 1972, following 24 days of little or no precipitation. River discharge near Petrolia increased from 22 m 3 s −1 to a maximum of 1300 m 3 s −1 while chloride and silica concentrations decreased only from 3.2 to 2.1 and 11.5 to 8.6 mgl −1 , respectively. Meanwhile, the isotopic composition of the river changed from δD = -42%, δ 18 O = -6.8% and 40 tritium units (T.U.) to extreme values at highest flow of δD = -35%, δ 18 O = -5.9% and 25 T.U. in response to volume-weighted rainfall averaging δD = -19.5%, δ 18 O = -3.1% and 18 T.U. Despite much rainfall of a composition quite different from that of the prestorm river water, “buffering” processes in the watershed greatly restricted changes in the chemical and isotopic content of the river during storm runoff. Because of the physical and hydrologic characteristics of the watershed, major contributions of groundwater to stormflow are very unlikely. The large increase in dissolved chemical load observed at maximum river discharge required that extensive interaction with, and presumably penetration of, soils occurred within a few hours time. Such a large increase in chemical load also required subsurface stormflow throughout a high proportion of the watershed. Chemical and isotopic stabilization of stormflow is believed to be due mainly to displacement of prestorm soil water, with some effects on river chemistry due to rapid rain-soil interactions. The isotopic and chemical composition of prestorm soil moisture cannot readily be predicted a priori because of possible variability in rainfall composition, evaporation, and exchange with atmospheric moisture, nor can it be assumed that baseflow has a predictable relation to the chemical or isotopic composition of water displaced from soils during storms. Therefore, it seems inappropriate to draw conclusions as to the relative proportions of groundwater and rainfall in runoff from a particular storm based only on the average compositions of rainfall, stormflow, and prestorm river water, as has been done in most previous isotope hydrograph studies. Given the great variation in hydrology, topography, soil characteristics, rainfall intensity and quantity, etc. from place to place, the relative amount of overland flow, subsurface flow from the unsaturated zone and of groundwater in stormflow can vary greatly in time and space.

California

Chemistry of unsaturated zone gases sampled in open boreholes at the crest of Yucca Mountain, Nevada: Data and basic concepts of chemical and physical processes in the mountain

Boreholes open to the unsaturated zone at the crest of Yucca Mountain, Nevada, were variously sampled for CO 2 (including 13 C and 14 C), CH 4 , N 2 , O 2 , Ar, CFC-11, CFC-12, and CFC-113 from 1986 to 1993. Air enters the mountain in outcrops, principally on the eastern slope, is enriched in CO 2 by mixing with soil gas, and is advected to the mountain crest, where it returns to the atmosphere. The CFC data indicate that travel times of the advecting gas in the shallow Tiva Canyon hydrogeologic unit are ≤5 years. The 14 C activities are postbomb to depths of 100 m, indicating little retardation of 14 CO 2 in the shallow flow systems. The 14 C activities from 168 to 404 m in the Topopah Spring hydrogeologic unit are 85–90 pMC at borehole USW-UZ6. The CFC data show that the drilling of USW-UZ6 in 1984 has altered the natural system by providing a conduit through the Paintbrush Nonwelded unit, allowing flow from Topopah Spring outcrops in Solitario Canyon on the west to USW-UZ6, upward in the borehole through the Paintbrush, to the shallow Tiva Canyon flow systems, and out of the mountain.

Nevada

Tampa Bay Ocean and Coastal Acidification Monitoring Quality Assurance Project Plan

Coastal acidification caused by eutrophication, freshwater inflow, and upwelling is already affecting many estuaries worldwide and can be exacerbated by ocean acidification that is caused by increasing carbon dioxide in the atmosphere. Effective management, mitigation, and (or) adaptation to the effects of coastal and ocean acidification require careful monitoring of the resulting changes in seawater chemistry. Local, regional, and national agencies and institutions organizing acidification-monitoring and research efforts work toward standardizing data collection and reporting protocols so that data can be shared and compared across regions and synthesized into national assessments. This document describes a Quality Assurance Project Plan for the collection and reporting of seawater chemical and physical data using standardized methods and published best practices relevant for monitoring coastal and ocean acidification. The plan specifically addresses procedures for a joint partnership, the Tampa Bay Ocean and Coastal Acidification Monitoring project, conducted by the U.S. Geological Survey, the U.S. Environmental Protection Agency, and the Tampa Bay Estuary Program in the Tampa Bay estuary, Florida. The plan describes recommended procedures for project organization, sampling process design and methods, data-quality objectives and criteria, data validation and management procedures, and project deliverables.

Florida

Timescales and processes of methane hydrate formation and breakdown, with application to geologic systems

Gas hydrate is an ice-like form of water and low molecular weight gas stable at temperatures of roughly -10ºC to 25ºC and pressures of ~3 to 30 MPa in geologic systems. Natural gas hydrates sequester an estimated one-sixth of Earth’s methane and are found primarily in deepwater marine sediments on continental margins, but also in permafrost areas and under continental ice sheets. When gas hydrate is removed from its stability field, its breakdown has implications for the global carbon cycle, ocean chemistry, marine geohazards, and interactions between the geosphere and the ocean-atmosphere system. Gas hydrate breakdown can also be artificially driven as a component of studies assessing the resource potential of these deposits. Furthermore, geologic processes and perturbations to the ocean-atmosphere system (e.g., warming temperatures) can cause not only dissociation, but also more widespread dissolution of hydrate or even formation of new hydrate in reservoirs. Linkages between gas hydrate and disparate aspects of Earth’s near-surface physical, chemical, and biological systems render an assessment of the rates and processes affecting the persistence of gas hydrate an appropriate Centennial Grand Challenge. This paper reviews the thermodynamic controls on methane hydrate stability and then describes the relative importance of kinetic, mass transfer, and heat transfer processes in the formation and breakdown (dissociation and dissolution) of gas hydrate. Results from numerical modeling, laboratory, and some fields studies are used to summarize the rates of hydrate formation and breakdown, followed by an extensive treatment of hydrate dynamics in marine and cryospheric gas hydrate systems.

Journal of Geophysical Research-Solid Earth

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

Soils and paleosols

Soils are naturally occurring bodies that form in the interface between the geosphere, biosphere, hydrosphere , and atmosphere. They are the medium for much of the Earth's plant and animal growth. Soil morphology and how it evolves are functions of the soil-forming factors of climate, organisms, relief, parent material, and time. The expression of soil morphology takes the form of layers, called horizons, that differ in their color, particle size distribution, structure, chemistry, and organic matter content from the parent material. A fundamental soil mapping unit in the USA is the soil order and 12 soil orders have been defined on the basis of soil morphology, physical and chemical properties, and climate. Soil geography in the USA is explained by an examination of how these 12 soil orders are found in particular climates, under specific vegetation communities, how they develop from compositionally distinct parent materials, or how they are a result of the age of soil parent material. Paleosols are ancient soils, those that formed in the past. Three types of paleosols are recognized, buried soils (those covered by a younger sediment or rock), exhumed paleosols (formerly buried soils that are now exposed at the surface due to erosion of overlying materials), and relict paleosols (soils that occur at the land surface, but which formed in an environment, such as a climate or biome, very different from that at the present time). Paleosols can help define geologic contacts and can aid in elucidating past climates or vegetation regimes. Although there are rich geologic records of paleosols in the Quaternary, there is an increasing recognition of the importance of all these features in the longer, pre-Quaternary geologic record.

Book chapter

Iron mineralogy and bioaccessibility of dust generated from soils as determined by reflectance spectroscopy and magnetic and chemical properties--Nellis Dunes recreational area, Nevada

Atmospheric mineral dust exerts many important effects on the Earth system, such as atmospheric temperatures, marine productivity, and melting of snow and ice. Mineral dust also can have detrimental effects on human health through respiration of very small particles and the leaching of metals in various organs. These effects can be better understood through characterization of the physical and chemical properties of dust, including certain iron oxide minerals, for their extraordinary radiative properties and possible effects on lung inflammation. Studies of dust from the Nellis Dunes recreation area near Las Vegas, Nevada, focus on characteristics of radiative properties (capacity of dust to absorb solar radiation), iron oxide mineral type and size, chemistry, and bioaccessibility of metals in fluids that simulate human gastric, lung, and phagolysosomal fluids. In samples of dust from the Nellis Dunes recreation area with median grain sizes of 2.4, 3.1, and 4.3 micrometers, the ferric oxide minerals goethite and hematite, at least some of it nanosized, were identified. In one sample, in vitro bioaccessibility experiments revealed high bioaccessibility of arsenic in all three biofluids and higher leachate concentration and bioaccessibility for copper, uranium, and vanadium in the simulated lung fluid than in the phagolysosomal fluid. The combination of methods used here to characterize mineral dust at the Nellis Dunes recreation area can be applied to global dust and broad issues of public health.

Nevada

Controls of stream chemistry and fish populations in the Neversink watershed, Catskill Mountains, New York

The Neversink Watershed Study was initiated in 1991 to develop an understanding of the key natural processes that control water quality within the forested, 166 km 2 (64 mi 2 ), Neversink River watershed; part of the New York City drinking water supply system, in the Catskill Mountain region of New York. The study entailed (1) hydrological investigations of water movement from the atmosphere to streams, (2) biogeochemical investigations of nitrogen and calcium, important nutrients in forest and aquatic ecosystems whose availability has been altered by acidic deposition, (3) an investigation of elevational patterns in atmospheric deposition, and (4) fisheries investigations to determine the relative importance of physical habitat and acidic deposition in controlling the abundance and diversity of fish species in the watershed. This report summarizes the results of these investigations, which have also been presented, in detail, in peer-reviewed technical articles and reports that are cited throughout the text.

New York

Characterization of major-ion chemistry and nutrients in headwater streams along the Appalachian National Scenic Trail and within adjacent watersheds, Maine to Georgia

An inventory of water-quality data on field parameters, major ions, and nutrients provided a summary of water quality in headwater (first- and second-order) streams within watersheds along the Appalachian National Scenic Trail (Appalachian Trail). Data from 1,817 sampling sites in 831 catchments were used for the water-quality summary. Catchment delineations from NHDPlus were used as the fundamental geographic units for this project. Criteria used to evaluate sampling sites for inclusion were based on selected physical attributes of the catchments adjacent to the Appalachian Trail, including stream elevation, percentage of developed land cover, and percentage of agricultural land cover. The headwater streams of the Appalachian Trail are generally dilute waters, with low pH, low acid neutralizing capacity (ANC), and low concentrations of nutrients. The median pH value was slightly acidic at 6.7; the median specific conductance value was 23.6 microsiemens per centimeter, and the median ANC value was 98.7 milliequivalents per liter (μeq/L). Median concentrations of cations (calcium, magnesium, sodium, and potassium) were each less than 1.5 milligrams per liter (mg/L), and median concentrations of anions (bicarbonate, chloride, fluoride, sulfate, and nitrate) were less than 10 mg/L. Differences in water-quality constituent levels along the Appalachian Trail may be related to elevation, atmospheric deposition, geology, and land cover. Spatial variations were summarized by ecological sections (ecosections) developed by the U.S. Forest Service. Specific conductance, pH, ANC, and concentrations of major ions (calcium, chloride, magnesium, sodium, and sulfate) were all negatively correlated with elevation. The highest elevation ecosections (White Mountains, Blue Ridge Mountains, and Allegheny Mountains) had the lowest pH, ANC, and concentrations of major ions. The lowest elevation ecosections (Lower New England and Hudson Valley) generally had the highest pH, ANC, and concentrations of major ions. The geology in discrete portions of these two ecosections was classified as containing carbonate minerals which has likely influenced the chemical character of the streamwater. Specific conductance, pH, ANC, and concentrations of major ions (calcium, chloride, magnesium, sodium, and sulfate) were all positively correlated with percentages of developed and agricultural land uses at the lower elevations of the central region of the Appalachian Trail (including the Green-Taconic-Berkshire Mountains, Lower New England, Hudson Valley, and Northern Ridge and Valley ecosections). The distinctly different chemical character of the streams in the central sections of the Appalachian Trail is likely related to the lower elevations, the presence of carbonate minerals in the geology, higher percentages of developed and agricultural land uses, and possibly the higher inputs of sulfate and nitrate from atmospheric deposition. Acid deposition of sulfate and nitrate are important influences on the acid-base chemistry of the surface waters of the Appalachian Trail. Atmospheric deposition estimates are consistently high (more than 18 kilograms per hectare (kg/ha) for sulfate, and more than 16 kg/ha for nitrate) at both the highest and lowest elevations. However, the lowest elevation (Green-Taconic-Berkshire Mountains, Lower New England, Hudson Valley, Northern Glaciated Allegheny Plateau, and Northern Ridge and Valley ecosections) included the largest spatial area of sustained high estimates of atmospheric deposition. Calcium-bicarbonate was the most frequently calculated water type in the Lower New England and Hudson Valley ecosections. In the northern and southern sections of the Appalachian Trail mix-cation water types were most prevalent and sulfate was the predominate anion. The predominance of the sulfate anion in the surface waters of the northern and southern ecosections likely reflects the influence of sulfate deposition. Although the central portion of the Appalachian Trail has the largest spatial area of high atmospheric acid deposition, the lower ionic strength waters in the northern and southern ecosections of the Appalachian Trail may have been more adversely affected by acid deposition. The low ionic strength of the streams in the White Mountains, Blue Ridge Mountains, and Allegheny Mountains ecosections makes parts of these regions susceptible to seasonal or event-driven episodic acidification, which can be detrimental to health of aquatic and terrestrial ecosystems. Median catchment ANC values were classified into three groups - acidic, sensitive, and insensitive. The White Mountains, Blue Ridge Mountains, and Allegheny Mountains ecosections included the highest frequency of catchments classified as acidic or sensitive. More than 56 percent of the catchments from the White Mountains ecosection were classified as sensitive to acidic inputs. In the Blue Ridge ecosection, 1.6 percent of the catchments were classified as acidic, and 38.2 percent of the catchments were classified as sensitive to acidic inputs. In the Allegheny Mountains ecosection, 17.6 percent of the catchments were classified as acidic, and 29.4 percent of the catchments were classified as sensitive to acidic inputs. Median concentrations of nitrogen species were less than 0.4 mg/L, and median concentrations of total phosphorus were less than 0.02 mg/L along the Appalachian Trail. A comparison of median catchment concentrations of nutrients to estimated national background concentrations demonstrated that concentrations along the Appalachian Trail are generally lower. A comparison of median concentrations of total nitrogen and total phosphorus to the U.S. Environmental Protection Agency's (USEPA) nutrient criteria for the Eastern U.S. ecoregions showed that the concentrations of total nitrogen in the northern section of the Appalachian Trail were generally higher than the USEPA criterion. Similarly, median concentrations of total phosphorus in the southern regions of the Appalachian Trail were approximately twice as high as USEPA criteria. Sections of the Appalachian Trail are adjacent to modest amounts of agricultural and developed land areas. These nonforested land areas may be contributing to the percentage of catchments in which concentrations of total nitrogen and total phosphorus are higher than USEPA nutrient ecoregion criteria.

Connecticut, Georgia, Maine, Massachusetts, Maryla

USGS Field Activities 12BHM01, 12BHM02, 12BHM03, 12BHM04, and 12BHM05 on the West Florida Shelf, in February, April, May, June, and August 2012

Atmospheric carbon dioxide (CO 2 ) is absorbed by the ocean’s surface where it combines with seawater to form a weak, naturally occurring acid called carbonic acid (H 2 CO 3 ). Increasing carbon dioxide in the atmosphere results in the absorption of more CO 2 by the ocean and, therefore, increases in the acidity of seawater. This process, known as ocean acidification, has the potential to elicit change in ecosystems and organisms by disrupting biological processes. For example, ocean acidification is a problem for marine organisms such as corals, foraminifera, and algae that precipitate calcium carbonate to form their skeletons and shells (Kleypas and others, 2006). The effects are related to corresponding changes in the carbonate saturation state (Ω), where Ω is the ratio of the ion concentration product (Ca 2+ x CO 3 2- ) to the stoichiometric aragonite solubility product (K*sp) (Langdon and Atkinson, 2005). Because pH and CO 3 2- are strongly interdependent through the inorganic carbon system, the decrease in pH will cause a proportionally greater decrease in CO 3 2- . Globally, ocean acidification is occurring faster than at any time in the last 300 million years (Broeker and others, 1979). Recent evidence indicates that individual oceans are responding at different rates, depending on physical and biological processes. For example in the Arctic Ocean, the rate of saturation state decrease was 2.1 percent per year between 1997 and 2010 (Robbins and others., 2013) in an area as large as Montana, largely because of increases in melt of ice, versus the average rate observed for the Pacific Ocean (0.36 percent per year) (Feely and others, 2012). Unfortunately, comparative data sets over multiyear time frames are often not available because time series baseline carbon information has not been collected in many oceans. Data are needed in subtropical latitudes where carbonate saturation states are already naturally low and fluctuate seasonally. These data will help construct a baseline for the assessment of future changes. As part of the U.S. Geological Survey (USGS) Coastal and Marine Geology Program project "R esponse of Florida Shelf Ecosystems to Climate Change " and in partnership with Kendra Daly, University of South Florida ( USF ), data on surface ocean carbonate chemistry were collected on five cruises along transects on the shallow inner west Florida shelf and northern Gulf of Mexico in 2012. Data from the 2011 cruises were also published (Robbins and others., 2013). The data collected allows the USGS, National Oceanic and Atmospheric Administration ( NOAA ), and USF scientists to map variations in ocean chemistry including carbonate saturation states along designated tracks. The USGS also partners with NOAA and the National Aeronautics and Space Administration ( NASA ) to model air-sea flux as part of a Gulf of Mexico Carbon Synthesis project led by NASA.

Florida

Simulations of Groundwater Flow and Particle Tracking Analysis in the Area Contributing Recharge to a Public-Supply Well near Tampa, Florida, 2002-05

Shallow ground water in the north-central Tampa Bay region, Florida, is affected by elevated nitrate concentrations, the presence of volatile organic compounds, and pesticides as a result of groundwater development and intensive urban land use. The region relies primarily on groundwater for drinking-water supplies. Sustainability of groundwater quality for public supply requires monitoring and understanding of the mechanisms controlling the vulnerability of public-supply wells to contamination. A single public-supply well was selected for intensive study based on the need to evaluate the dominant processes affecting the vulnerability of public-supply wells in the Upper Floridan aquifer in the City of Temple Terrace near Tampa, Florida, and the presence of a variety of chemical constituents in water from the well. A network of 29 monitoring wells was installed, and water and sediment samples were collected within the area contributing recharge to the selected public-supply well to support a detailed analysis of physical and chemical conditions and processes affecting the water chemistry in the well. A three-dimensional, steady-state groundwater flow model was developed to evaluate the age of groundwater reaching the well and to test hypotheses on the vulnerability of the well to nonpoint source input of nitrate. Particle tracking data were used to calculate environmental tracer concentrations of tritium and sulfur hexafluoride and to calibrate traveltimes and compute flow paths and advective travel times in the model area. The traveltime of particles reaching the selected public-supply well ranged from less than 1 day to 127.0 years, with a median of 13.1 years; nearly 45 percent of the simulated particle ages were less than about 10 years. Nitrate concentrations, derived primarily from residential/commercial fertilizer use and atmospheric deposition, were highest (2.4 and 6.11 milligrams per liter as nitrogen, median and maximum, respectively) in shallow groundwater from the surficial aquifer system and lowest (less than the detection level of 0.06 milligram per liter) in the deeper Upper Floridan aquifer. Denitrification occurred near the interface of the surficial aquifer system and the underlying intermediate confining unit, within the intermediate confining unit, and within the Upper Floridan aquifer because of reducing conditions in this part of the flow system. However, simulations indicate that the rapid movement of water from the surficial aquifer system to the selected public-supply well through karst features (sinkholes) and conduit layers that bypass the denitrifying zones (short-circuits), coupled with high pumping rates, allow nitrate to reach the selected public-supply well in concentrations that resemble those of the overlying surficial aquifer system. Water from the surficial aquifer system with elevated concentrations of nitrate and low concentrations of some volatile organic compounds and pesticides is expected to continue moving into the selected public-supply well, because calculated flux-weighted concentrations indicate the proportion of young affected water contributing to the well is likely to remain relatively stable over time. The calculated nitrate concentration in the selected public-supply well indicates a lag of 1 to 10 years between peak concentrations of nonpoint source contaminants in recharge and appearance in the well.

Scientific Investigations Report

From pools to flow: The PROMISE framework for new insights on soil carbon cycling in a changing world

Soils represent the largest terrestrial reservoir of organic carbon, and the balance between soil organic carbon (SOC) formation and loss will drive powerful carbon‐climate feedbacks over the coming century. To date, efforts to predict SOC dynamics have rested on pool‐based models, which assume classes of SOC with internally homogenous physicochemical properties. However, emerging evidence suggests that soil carbon turnover is not dominantly controlled by the chemistry of carbon inputs, but rather by restrictions on microbial access to organic matter in the spatially heterogeneous soil environment. The dynamic processes that control the physicochemical protection of carbon translate poorly to pool‐based SOC models; as a result, we are challenged to mechanistically predict how environmental change will impact movement of carbon between soils and the atmosphere. Here, we propose a novel conceptual framework to explore controls on belowground carbon cycling: P robabilistic R epresentation of O rganic M atter I nteractions within the S oil E nvironment (PROMISE). In contrast to traditional model frameworks, PROMISE does not attempt to define carbon pools united by common thermodynamic or functional attributes. Rather, the PROMISE concept considers how SOC cycling rates are governed by the stochastic processes that influence the proximity between microbial decomposers and organic matter, with emphasis on their physical location in the soil matrix. We illustrate the applications of this framework with a new biogeochemical simulation model that traces the fate of individual carbon atoms as they interact with their environment, undergoing biochemical transformations and moving through the soil pore space. We also discuss how the PROMISE framework reshapes dialogue around issues related to SOC management in a changing world. We intend the PROMISE framework to spur the development of new hypotheses, analytical tools, and model structures across disciplines that will illuminate mechanistic controls on the flow of carbon between plant, soil, and atmospheric pools.

Global Change Biology

The solusphere - its inferences and study

Water is a fundamental geologic agent active in rock decomposition, erosion, and synthesis. Solutes in water are of particular interest to geochemists as sources of raw material for synthesis or as products of decomposition. When geochemical studies move from the laboratory into natural environment many variables relating to solute hydrology must be considered. As a focal point there has been designed a graphical representation of solute hydrology, the solusphere, which embodies the concepts of land-water occurrence and movement on which are superimposed geologic, biologic, physical, chemical, and cultural processes affecting solutes. The solusphere is demonstrated by passing an imaginary plane through the centre of the earth. This plane intercepts concentric zones designated as rock flowage, saturation, aeration, surface activity, and atmosphere. Transport processes carry solutes within and between zones without alteration or conversion. However, whether stationary or in motion, the water's solute character is constantly subject to (1) alteration processes that change concentration by addition or subtraction of solutes or solvent without loss of solute identities, and (2) conversion processes that change the chemical state and form of solutes. The geochemist is concerned with specific conversion processes, but he also must consider transport, alteration, and other conversion processes that are continually modifying the materials with which he is dealing in nature. The solusphere is an attempt to organize processes affecting the chemical quality of land waters into a unified field of science much like the field of marine chemistry.

Geochimica et Cosmochimica Acta

Chemical and physical controls on mercury source signatures in stream fish from the northeastern United States

Streams in the northeastern U.S. receive mercury (Hg) in varying proportions from atmospheric deposition and legacy point sources, making it difficult to attribute shifts in fish concentrations directly back to changes in Hg source management. Mercury stable isotope tracers were utilized to relate sources of Hg to co-located fish and bed sediments from 23 streams across a forested to urban-industrial land-use gradient within this region. Mass-dependent isotopes (δ202Hg) in prey and game fish at forested sites were depleted (medians -0.95 and -0.83 ‰, respectively) in comparison to fish from urban-industrial settings (medians -0.26 and -0.38 ‰, respectively); the forested site group also had higher prey fish Hg concentrations. The separation of Hg isotope signatures in fish was strongly related to in-stream and watershed land-use indicator variables. Fish isotopes were strongly correlated with bed sediment isotopes, but the comparison of isotopic composition between fish and sediment was variable due to differing ecosystem-specific drivers controlling the extent of MeHg formation. The multivariable approach of analyzing watershed characteristics and stream chemistry reveals that the Hg isotope composition in fish is linked to current and historic Hg sources in the northeastern U.S. and can be used to trace bioaccumulated Hg.

Environmental Science & Technology

Variation in the terrestrial isotopic composition and atomic weight of argon

The isotopic composition and atomic weight of argon (Ar) are variable in terrestrial materials. Those variations are a source of uncertainty in the assignment of standard properties for Ar, but they provide useful information in many areas of science. Variations in the stable isotopic composition and atomic weight of Ar are caused by several different processes, including (1) isotope production from other elements by radioactive decay (radiogenic isotopes) or other nuclear transformations (e.g., nucleogenic isotopes), and (2) isotopic fractionation by physical-chemical processes such as diffusion or phase equilibria. Physical-chemical processes cause correlated mass-dependent variations in the Ar isotope-amount ratios ( 40 Ar/ 36 Ar, 38 Ar/ 36 Ar), whereas nuclear transformation processes cause non-mass-dependent variations. While atmospheric Ar can serve as an abundant and homogeneous isotopic reference, deviations from the atmospheric isotopic ratios in other Ar occurrences limit the precision with which a standard atomic weight can be given for Ar. Published data indicate variation of Ar atomic weights in normal terrestrial materials between about 39.7931 and 39.9624. The upper bound of this interval is given by the atomic mass of 40 Ar, as some samples contain almost pure radiogenic 40 Ar. The lower bound is derived from analyses of pitchblende (uranium mineral) containing large amounts of nucleogenic 36 Ar and 38 Ar. Within this interval, measurements of different isotope ratios ( 40 Ar/ 36 Ar or 38 Ar/ 36 Ar) at various levels of precision are widely used for studies in geochronology, water–rock interaction, atmospheric evolution, and other fields.

Pure and Applied Chemistry

West Florida Shelf: A natural laboratory for the study of ocean acidificiation

Declining oceanic pH and carbonate-ion concentrations are well-known consequences of increased atmospheric and surface-ocean partial pressure of carbon dioxide (pCO2). The possible subject of shifts in seawater carbonate chemistry on biocalcification and survival rates of marine organisms provides questions amenable to both experimental and field study (Kleypas and Langdon, 2006). To date, limited quantitative data exist with which to formalize and test hypotheses regarding such impacts, particularly in continental-shelf settings. The continental shelves of Florida provide an ideal natural laboratory in which to test latitudinal (and temperature and depth) shifts in habitat ranges of calcifying organisms. Both the east and west Florida shelves extend from warm temperate to subtropical latitudes; additionally, the west Florida shelf has very little siliciclastic influx to mask the carbonate production. This study utilizes the natural laboratory of the west and southwest Florida shelf (fig 1.1) to examine the transition from foramol (predominately foraminifera and molluscan) carbonate sediments, characteristic of the west-central Florida shelf, to chlorozoan (algal and coral) sediments characteristic of the southwest Florida shelf. The west Florida shelf is a mixed siliciclastic carbonate ramp that to the south transitions to the carbonate-dominated southwest Florida shelf (Enos, 1977; Brooks and others, 2003). The west Florida shelf is a distally steepened carbonate ramp that is ~250 kilometers (km) wide (Read, 1985). It is covered by a veneer of unconsolidated sediment consisting of mainly biogenic carbonate and quartz in the near shore, with subordinate amounts of phosphate. The sediment-distribution pattern is largely a function of proximity to source, with physical processes playing a minor role in distribution. The carbonate sand-and-gravel fraction is produced by organisms within the depositional basin of the west Florida shelf (Brooks and others, 2003). The southwest Florida shelf is a rimmed carbonate margin where organisms produce virtually all of the substrate; it also exhibits a greater sediment thickness as compared to the west Florida shelf (Enos, 1977). Temperature, which is usually associated with latitude, plays a major role in locations of foramol versus chlorozoan assemblages, but other factors beyond latitude influence temperature on the west and southwest Florida shelves. The potential of cooler, deep-water upwelling and transport over the bottom waters of the shelf may have a significant role in the species assemblage at the sediment/water interface and ultimately on location of foramol versus chlorozoan production. Deep water transported onto and over the shelf may also have environmental ramifications beyond temperature by bringing in water of different chemistry.

Open-File Report

Ground water to surface water: Chemistry of thermal outflows in Yellowstone National Park

Geothermal waters in the earth’s subsurface boil with steam separation and may mix with dilute ground waters (that may or may not contain sulfuric acid from sulfur oxidation), resulting in a wide range of compositions when they discharge and emerge at the surface. As they discharge onto the ground surface they undergo evaporative cooling, degassing, oxidation, and mineral precipitation. Within this aquatic environment of rapidly changing physical and chemical parameters, numerous microbial communities develop—some of which affect oxidation and mineral precipitation. Microbes are responsible for rapid oxidation of iron and arsenic in thermal outflows, and for catalyzing the production of sulfuric acid from the oxidation of elemental sulfur. The attractive visual display of colors observed in Yellowstone’s geothermal waters reflects this interplay of physical, chemical, and biological phenomena. Oxidation of dissolved sulfide to thiosulfate occurs abiotically, and thiosulfate can be found in many of Yellowstone’s thermal waters—at any pH, temperature, and composition. Polythionates, on the other hand, are rarely found in Yellowstone waters but are associated with sulfur hydrolysis in Cinder Pool. Oxidation rates of iron and arsenic in overflows have been estimated at 1-3 mM/h and 0.04-0.1 mM/h, respectively—orders of magnitude faster than the abiotic rate. The abiotic production of thiosulfate from oxidation of dissolved sulfi de at Angel Terrace and Ojo Caliente is about 3-30 µM/min, faster by 2-3 orders of magnitude than the laboratory rate at 25°C. The partitioning of dissolved sulfide between that volatilized to the air and that oxidized to thiosulfate has been estimated at Angel Terrace and at Ojo Caliente. For the pH range of 6-8 and the temperature range of 50-93°C, 67-86% of the dissolved sulfide is lost to the atmosphere and 10-33% is oxidized to thiosulfate. Only a very small percentage, if any, forms elemental sulfur under these conditions.

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