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Interpretation of geochemical reactions and isotopic composition of groundwater provides a method to determine hydrological parameters such as porosity, hydraulic conductivity, and groundwater flow rates. This geochemical method is largely independent of the more conventional approach of determining these parameters by an evaluation of physical properties of aquifer systems. -from Authors
The Heath, Great Cranberry Island, Maine, offers a unique locality for studying lateral and vertical relationships between radically different peat types within 1 km 2 . The majority of The Heath is a Sphagnum moss-dominated raised bog. Surrounding the raised bog is a swamp/marsh complex containing grass, sedge, Sphagnum moss, alder, tamarack, and skunk cabbage. Swamp/ marsh-deposited peat occurs both around the margins of The Heath and under Sphagnum -dominated peat, which was deposited within the raised bog. A third peat type, dominated by herbaceous aquatics, is present underlying the swamp/marsh-dominated peat but is not present as a dominant botanical community of The Heath. The three peat types have major differences in petrographic characteristics, ash contents, and associated minerals. Sulfur contents range from a low of 0.19 wt.% (dry) within the raised bog to a high of 4.44 wt% (dry) near the west end of The Heath, where swamp/marsh peat occurring directly behind a storm beach berm has been influenced by marine waters. The presence of major geochemical variations within a 1-km 2 peat deposit suggests the need for in-depth characterization of potential peat resources prior to use.
Organic petrography via incident light microscopy has broad application to shale petroleum systems, including delineation of thermal maturity windows and determination of organo-facies. Incident light microscopy allows practitioners the ability to identify various types of organic components and demonstrates that solid bitumen is the dominant organic matter occurring in shale plays of peak oil and gas window thermal maturity, whereas oil-prone Type I/II kerogens have converted to hydrocarbons and are not present. High magnification SEM observation of an interconnected organic porosity occurring in the solid bitumen of thermally mature shale reservoirs has enabled major advances in our understanding of hydrocarbon migration and storage in shale, but suffers from inability to confirm the type of organic matter present. Herein we review organic petrography applications in the North American shale plays through discussion of incident light photographic examples. In the first part of the manuscript we provide basic practical information on the measurement of organic reflectance and outline fluorescence microscopy and other petrographic approaches to the determination of thermal maturity. In the second half of the paper we discuss applications of organic petrography and SEM in all of the major shale petroleum systems in North America including tight oil plays such as the Bakken, Eagle Ford and Niobrara, and shale gas and condensate plays including the Barnett, Duvernay, Haynesville-Bossier, Marcellus, Utica, and Woodford, among others. Our review suggests systematic research employing correlative high resolution imaging techniques and in situ geochemical probing is needed to better document hydrocarbon storage, migration and wettability properties of solid bitumen at the pressure and temperature conditions of shale reservoirs.
Results from the Färoe-Iceland Ridge Experiment (FIRE) constrain the crustal thickness as 19 km under the Northern Volcanic Zone of Iceland and 35 km under older Tertiary areas of northeastern Iceland. The Moho is defined by strong P wave and S wave reflections. Synthetic seismogram modeling of the Moho reflection indicates mantle velocities of at least 8.0 km/s beneath the Tertiary areas of northeastern Iceland and at least 7.9 km/s beneath the neovolcanic zone. Crustal diving rays resolve the structure of the upper and lower crust. Surface P wave velocities are 1.1–4.0 km/s in Quaternary rocks and are rather higher, 4.4–4.7 km/s, in the Tertiary basalts that outcrop elsewhere. The highest crustal P wave velocities observed directly from diving rays are 7.1 km/s, from rays that turn at 24 km depth. Velocities of 7.35 km/s at the base of the crust are inferred from extrapolation of the lower crustal velocity gradient (0.024 s −1 ). A Poisson's ratio of approximately 0.27, equivalent to an S wave to P wave travel time ratio of 1.78, is measured throughout the crust east of the neovolcanic zone. The Poisson's ratio and the steep Moho topography (in places up to 30° from the horizontal) indicate that the entire crust outside the neovolcanic zone is cool (<800°C). Gravity data are well matched by a velocity/density conversion of our seismic crustal model and indicate a region of low mantle density beneath the neovolcanic zone, believed to be due to elevated mantle temperatures. The crustal thickness in the neovolcanic zone is consistent with geochemical estimates of the melt generation, placing constraints on the flow within the Iceland mantle plume.
Study Region This study region encompasses the Transboundary San Pedro and Santa Cruz aquifers which are shared between the states of Sonora (Mexico) and Arizona (US). Special regional considerations include a semi-arid climate, basin-fill aquifers with predominantly montane recharge areas, economic drivers in the mining, trade, and military sectors, groundwater-dependent cities with expanding cones of depression, interbasin groundwater transfers, ground- and surface-water contamination, and protected aquatic and riparian habitats that act as significant migration corridors for hundreds of species, including some that are threatened and endangered. Study Focus We focus on lessons learned from the hydrologic assessment of the Transboundary San Pedro and Santa Cruz aquifers. We conducted the work, in two phases: (1) laying the groundwork and (2) implementation. The “laying the groundwork” phase consisted of binational meetings with stakeholders and key actors (agencies and individuals), and the development of an understanding of the physical, institutional, historical, and socio-political context. This led to signing of the binational Transboundary Aquifer Assessment Program (TAAP) agreement in 2009 and detailed the process for cooperation and coordination in the assessment of shared aquifers. The implementation phase began with an agreement to proceed with the study of four “focus” aquifers (Santa Cruz, San Pedro, Mesilla (Conejos-Médanos in Mexico), and Hueco Bolson (Bolsón del Hueco in Mexico)) and development of associated technical teams. Though we do include a brief discussion of the lessons learned from the physical science portion of the study, the results have been described and published elsewhere. The bulk of the paper instead focuses on the findings and lessons learned from the integration of social-science perspectives into a largely physical-science based program, since there is a growing recognition of the need for this type of approach especially in the management and assessment of transboundary aquifers. New Hydrological Insights for the Region The Sonora-Arizona effort succeeded because both countries were adequately represented, and because of flexibility of skills and ability of teams comprising both university and government scientists. Teams included social and earth scientists. Including the social sciences was critical to research design and implementation, and to addressing the cultural, institutional, and socio-political contexts of transboundary aquifer assessment. Significant components of the continuing implementation phase include strategic planning, data compilation and analysis, cross-border integration of datasets, geophysical and geochemical surveys, and internal, peer, and stakeholder engagement.
The Center Pond pluton is a calc-alkaline post-tectonic Acadian body intruding chlorite grade Silurian metasediments of E-central Maine. Mapping and petrographic work reveal that the pluton contains 5 igneous rock types; quartz diorite, hornblende-biotite granodiorite, biotite granite, porphyritic granite, and aplitic granite. The linearity of major and trace element trends and Rb-Sr isotope systematics indicate that partial melting and unmixing of a single mafic or intermediate metaigneous rock to restite (residual phases in equilibrium with the melting event at depth) and near-eutectic minimum melt may account for much of the observed geochemical variation within the Center Pond pluton. Major and trace element trends rule out fractional crystallization as a model for Center Pond. -from Authors
Currently, little is known about the impact of climate change on groundwater recharge in the Sierra Nevada and southern Cascade Range of California or other mountainous regions of the world. The purpose of this study was to determine whether small alpine peat lands called fens can be used as whole-ecosystem gauges of groundwater recharge through time. Fens are sustained by groundwater discharge and are highly sensitive to changes in groundwater flow due to hydrologic disturbance including climate change. Seven fens in the Sierra Nevada and southern Cascade Range were studied over a 50-80 year period using historic aerial photography. In each aerial photograph, fen areas were identified as open lawn and partially treed areas that exhibited (1) dark brownish-green coloring or various shades of gray and black in black and white imagery and (2) mottling of colors and clustering of vegetation, which signified a distinct moss canopy with overlying clumped sedge vegetation. In addition to the aerial photography study, a climate analysis for the study sites was carried out using both measured data (U.S. Department of Agriculture Natural Resources Conservation Service SNOwpack TELemetry system) and modeled data (a downscaled version of the Parameter-elevation Regressions on Independent Slopes Model) for the period from 1951 to 2010. Over the study period, the five fens in the Sierra Nevada were found to be decreasing between 10% and 16% in delineated area. The climate analysis revealed significant increases through time in annual mean minimum temperature (T min ) between 1951-1980 and 1981-2010. In addition, April 1 snow water equivalent and snowpack longevity also decreased between 1951-1980 and 1981-2010. For the fens in the Cascade Range, there were no discernible changes in delineated area. At these sites, increases in T min occurred only within the past 20-25 years and decreases in snowpack longevity were more subtle. A conceptual model is presented, which illustrates that basic differences in hydrogeology of the Sierra Nevada vs. the Cascade Range may control the threshold at which changes in delineated fen areas are discernible. Overall, the results from this study show that fens in the Sierra Nevada have strong potential as whole ecosystem gauges for determining long-term changes in groundwater recharge under climate change. Due to either more moderate climate change and/or hydrogeological differences, fens in the southern Cascade Range currently do not appear to have the same utility. A greater sample size of fens in the Sierra Nevada is needed to confirm the general applicability of this method. In addition, future work needs to focus on integrating fen monitoring with geochemical and/or isotopic process-level studies in order to quantify changes in groundwater recharge identified using this new approach.
Established chemometric and geochemical techniques were applied to water quality data from 23 National Irrigation Water Quality Program (NIWQP) study areas in the Western United States. These techniques were applied to the NIWQP data set to identify common geochemical processes responsible for mobilization of selenium and to develop a classification model that uses major-ion concentrations to identify areas that contain elevated selenium concentrations in water that could pose a hazard to water fowl. Pattern recognition modeling of the simple-salt data computed with the SNORM geochemical program indicate three principal components that explain 95% of the total variance. A three-dimensional plot of PC 1, 2 and 3 scores shows three distinct clusters that correspond to distinct hydrochemical facies denoted as facies 1, 2 and 3. Facies 1 samples are distinguished by water samples without the CaCO 3 simple salt and elevated concentrations of NaCl, CaSO 4 , MgSO 4 and Na 2 SO 4 simple salts relative to water samples in facies 2 and 3. Water samples in facies 2 are distinguished from facies 1 by the absence of the MgSO 4 simple salt and the presence of the CaCO 3 simple salt. Water samples in facies 3 are similar to samples in facies 2, with the absence of both MgSO 4 and CaSO 4 simple salts. Water samples in facies 1 have the largest selenium concentration (10 μg l −1 ), compared to a median concentration of 2·0 μg l −1 and less than 1·0 μg l −1 for samples in facies 2 and 3. A classification model using the soft independent modeling by class analogy (SIMCA) algorithm was constructed with data from the NIWQP study areas. The classification model was successful in identifying water samples with a selenium concentration that is hazardous to some species of water-fowl from a test data set comprised of 2,060 water samples from throughout Utah and Wyoming. Application of chemometric and geochemical techniques during data synthesis analysis of multivariate environmental databases from other national-scale environmental programs such as the NIWQP could also provide useful insights for addressing ‘real world’ environmental problems.
Chemical hydrogeology, including organic and inorganic aspects, has contributed to an increased understanding of groundwater flow systems, geologic processes, and stressed environments. Most of the basic principles of inorganic-chemical hydrogeology were first established by investigations of organic-free, regional-scale systems for which simplifying assumptions could be made. The problems of groundwater contamination are causing a shift of emphasis to microscale systems that are dominated by organic-chemical reactions and that are providing an impetus for the study of naturally occurring and manmade organic material. Along with the decrease in scale, physical and chemical heterogeneity become major controls. Current investigations and those selected from the literature demonstrate that heterogeneity increases in importance as the study site decreases from regional-scale to macroscale to microscale. Increased understanding of regional-scale flow systems is demonstrated by selection of investigations of carbonate and volcanic aquifers to show how applications of present-day concepts and techniques can identify controlling chemical reactions and determine their rates; identify groundwater flow paths and determine flow velocity; and determine aquifer characteristics. The role of chemical hydrogeology in understanding geologic processes of macroscale systems is exemplified by selection of investigations in coastal aquifers. Phenomena associated with the mixing zone generated by encroaching sea water include an increase in heterogeneity of permeability, diagenesis of minerals, and formation of geomorphic features, such as caves, lagoons, and bays. Ore deposits of manganese and uranium, along with a simulation model of ore-forming fluids, demonstrate the influence of heterogeneity and of organic compounds on geochemical reactions associated with genesis of mineral deposits. In microscale environments, importance of heterogeneity and consequences of organic reactions in determining the distribution and concentrations cf. constituents are provided by several studies, including infiltration of sewage effluent and migration of creosote in coastal plain aquifers. These studies show that heterogeneity and the dominance of organically controlled reactions greatly increase the complexity of investigations.Current investigations and those selected from the literature demonstrate that heterogeneity increases in importance as the study site decreases from regional-scale to macroscale to microscale. Increased understanding of regional-scale flow systems is demonstrated by selection of investigations of carbonate and volcanic aquifers to show how application of present-day concepts and techniques can identify controlling chemical reactions and determine their rates; identify groundwater flow paths and determine flow velocity; and determine aquifer characteristics. The role of chemical hydrogeology in understanding geologic processes of macroscale systems is exemplified by selection of investigations in coastal aquifers. Ore deposits of manganese and uranium, along with a simulation model of ore-forming fluids, demonstrate the influence of heterogeneity and of organic compounds on geochemical reactions associated with genesis of mineral deposits. In microscale environments, importance of heterogeneity is illustrated by studies of infiltration of sewage effluent and migration of creosote in coastal plain aquifers.
Effects of extremely high carbon dioxide (CO 2 ) concentrations on soil microbial communities and associated processes are largely unknown. We studied a wetland area affected by spots of subcrustal CO 2 degassing (mofettes) with focus on anaerobic autotrophic methanogenesis and acetogenesis because the pore gas phase was largely hypoxic. Compared with a reference soil, the mofette was more acidic (ΔpH ~0.8), strongly enriched in organic carbon (up to 10 times), and exhibited lower prokaryotic diversity. It was dominated by methanogens and subdivision 1Acidobacteria, which likely thrived under stable hypoxia and acidic pH. Anoxic incubations revealed enhanced formation of acetate and methane (CH 4 ) from hydrogen (H 2 ) and CO 2 consistent with elevated CH 4 and acetate levels in the mofette soil. 13 CO 2 mofette soil incubations showed high label incorporations with ~512   ng 13 C   g   (dry weight (dw)) soil −1   d −1 into the bulk soil and up to 10.7   ng 13 C   g   (dw) soil −1   d −1 into almost all analyzed bacterial lipids. Incorporation of CO 2 -derived carbon into archaeal lipids was much lower and restricted to the first 10   cm of the soil. DNA-SIP analysis revealed that acidophilic methanogens affiliated withMethanoregulaceae and hitherto unknown acetogens appeared to be involved in the chemolithoautotrophic utilization of 13 CO 2 . Subdivision 1 Acidobacteriaceae assimilated 13 CO 2 likely via anaplerotic reactions because Acidobacteriaceae are not known to harbor enzymatic pathways for autotrophic CO 2 assimilation. We conclude that CO 2 -induced geochemical changes promoted anaerobic and acidophilic organisms and altered carbon turnover in affected soils.
Multichannel electrical resistivity (ER) measurements were conducted at two contrasting coastal sites in Hawaii to obtain new information on the spatial scales and dynamics of the fresh water–seawater interface and rates of coastal groundwater exchange. At Kiholo Bay (located on the dry, Kona side of the Big Island) and at a site in Maunalua Bay (Oahu), there is an evidence for abundant submarine groundwater discharge (SGD). However, the hydrologic and geologic controls on coastal groundwater discharge are likely to be different at these two sites. While at Kiholo Bay SGD is predominantly through lava tubes, at the Maunalua Bay site exchange occurs mostly through nearshore submarine springs. In order to calculate SGD fluxes, it is important to understand the spatial and temporal scales of coastal groundwater exchange. From ER time series data, subsurface salinity distributions were calculated using site-specific formation factors. A salinity mass balance box model was then used to calculate rates of point source (i.e., spatially discreet) and total fresh water discharge. From these data, mean SGD rates were calculated for Kiholo Bay (∼9,200 m 3 /d) and for the Maunalua Bay site (∼5,900 m 3 /d). While such results are on the same order of magnitude to geochemical tracer-derived SGD rates, the ER SGD rates provide enhanced details of coastal groundwater exchange that can enable a more cohesive whole watershed perspective.
Better characterization of the geochemical evolution of groundwater south of Grand Canyon, Arizona (USA), is needed to understand natural conditions and assess potential effects from breccia-pipe uranium mining in the region. Geochemical signatures of groundwater at 28 sampling locations were evaluated; baseline concentrations for select trace elements (As, B, Ba, Cr, Li, Mo, Rb, Se, Sr, Th, Tl, U, V) were established, and anomalous chemistry characteristics were identified. Concentrations at some groundwater sites exceeded the USEPA drinking water standard for As of 10 μg/L (Red Canyon, Miners, JT, Havasu, and Warm Springs) and U of 30 μg/L (Salt Creek Spring). Four springs from the study area (Blue, Havasu, Fern, and Warm Springs) had unique chemistry, which may indicate a deep flow path or potential contribution of fluids from lower in the crust. Other springs in the study area were distinguished by major anion water type: sulfate, bicarbonate, and a mixture of the two. Water type distinctions were somewhat spatially segregated, with sulfate type present on the western side of the study area, bicarbonate type on the eastern side, and a mixture of the two interspersed between the endmember sites. Sulfate-type water from this study area had low strontium isotopic ratio (87Sr/86Sr) values. The location of spring discharge within single drainages of the Grand Canyon may influence chemistry, as groundwater discharging from bedrock was altered after flowing through alluvial material. Geochemical analysis of groundwater in Grand Canyon indicates the importance of continued monitoring and better understanding of short-term chemical fluctuations.
We have used visible and near‐infrared Panoramic Camera (Pancam) spectral data acquired by the Opportunity rover to analyze 15 rock fragments at the Meridiani Planum landing site. These spectral results were then compared to geochemistry measurements made by the in situ instruments Mössbauer (MB) and Alpha Particle X‐ray Spectrometer (APXS) to determine the feasibility of mineralogic characterization from Pancam data. Our results suggest that dust and alteration rinds coat many rock fragments, which limits our ability to adequately measure the mineralogy of some rocks from Pancam spectra relative to the different field of view and penetration depths of MB and APXS. Viewing and lighting geometry, along with sampling size, also complicate the spectral characterization of the rocks. Rock fragments with the same geochemistry of sulfate‐rich outcrops have similar spectra, although the sulfate‐rich composition cannot be ascertained based upon Pancam spectra alone. FeNi meteorites have spectral characteristics, particularly ferric oxide coatings, that generally differentiate them from other rocks at the landing site. Stony meteorites and impact fragments with unknown compositions have a diverse range of spectral properties and are not well constrained nor diagnostic in Pancam data. Bounce Rock, with its unique basalt composition, is easily differentiated in the Pancam data from all other rock types at Meridiani Planum. Our Pancam analyses of small pebbles adjacent to these 15 rock fragments suggests that other rock types may exist at the landing site but have not yet been geochemically measured.
Marked changes in sediment types deposited in Cabin Lake, near Cordova, Alaska, represent environmental shifts during the early and late Holocene, including fluctuations in the terminal position of Sheridan Glacier. Cabin Lake is situated to receive meltwater during periods when the outwash plain of the advancing Sheridan Glacier had aggraded. A brief early Holocene advance from 11.2 to 11.0 cal ka is represented by glacial rock flour near the base of the sediment core. Non-glacial lake conditions were restored for about 1000 years before the water level in Cabin Lake lowered and the core site became a fen. The fen indicates drier-than-present conditions leading up to the Holocene thermal maximum. An unconformity spanning 5400 years during the mid-Holocene is overlain by peat until 1110 CE when meltwater from Sheridan Glacier returned to the basin. Three intervals of an advanced Sheridan Glacier are recorded in the Cabin Lake sediments during the late Holocene: 1110–1180, 1260–1540 and 1610–1780 CE. The sedimentary sequence also contains the first five reported tephra deposits from the Copper River delta region, and their geochemical signatures suggest that the sources are the Cook Inlet volcanoes Redoubt, Augustine and Crater Peak, and possibly Mt Churchill in the Wrangell Volcanic field.
Nineteen tephra layers within the Wilson Creek formation near Mono Lake provide a record of late Pleistocene to early Holocene volcanic activity from the nearby Mono Craters and are important chronostratigraphic markers for paleomagnetic, paleoclimatic, and paleoecologic studies. These stratigraphically important tephra deposits can be geochemically identified using compositions of their titanomagnetite phenocrysts. Titanomagnetite compositions display a broad range (X Usp 0.26–0.39), which allow the tephra layers to be distinguished despite the indistinguishable major-element glass compositions (76–77 wt% SiO 2 ) of their hosts. The concentrations of Ti and Fe in titanomagnetite display geochemical and stratigraphic groupings that allow clear discrimination between older (> 57 ka) and younger (< 41 ka) tephras. Some individual tephra layers can be uniquely identified on the basis of titanomagnetite MgO, MnO, and Al 2 O 3 contents. In addition, a few tephra layers can be correlated to their source vents by their titanomagnetite compositions. The unique geochemical fingerprint of the Mono Craters-sourced titanomagnetites also allows the discrimination of two tephra layers apparently sourced from nearby Mammoth Mountain volcano in Long Valley.
Understanding nutrient pathways to streams will improve nutrient management strategies and estimates of the time lag between when changes in land use practices occur and when water quality effects that result from these changes are observed. Nitrate and orthophosphate (OP) concentrations in several environmental compartments were examined in watersheds having a range of base flow index (BFI) values across the continental United States to determine the dominant pathways for water and nutrient inputs to streams. Estimates of the proportion of stream nitrate that was derived from groundwater increased as BFI increased. Nitrate concentration gradients between groundwater and surface water further supported the groundwater source of nitrate in these high BFI streams. However, nitrate concentrations in stream-bed pore water in all settings were typically lower than stream or upland groundwater concentrations, suggesting that nitrate discharge to streams was not uniform through the bed. Rather, preferential pathways (e.g., springs, seeps) may allow high nitrate groundwater to bypass sites of high biogeochemical transformation. Rapid pathway compartments (e.g., overland flow, tile drains) had OP concentrations that were typically higher than in streams and were important OP conveyers in most of these watersheds. In contrast to nitrate, the proportion of stream OP that is derived from ground water did not systematically increase as BFI increased. While typically not the dominant source of OP, groundwater discharge was an important pathway of OP transport to streams when BFI values were very high and when geochemical conditions favored OP mobility in groundwater. Copyright ?? 2009 by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America. All rights reserved.
Efficient biodegradation of subsurface contaminants requires two elements: (1) microbial populations with the necessary degradative capabilities, and (2) favorable subsurface geochemical and hydrological conditions. Practical constraints on experimental design and interpretation in both the hydrogeological and microbiological sciences have resulted in limited knowledge of the interaction between hydrogeological and microbiological features of subsurface environments. These practical constraints include: (1) inconsistencies between the scales of investigation in the hydrogeological and microbiological sciences, and (2) practical limitations on the ability to accurately define microbial populations in environmental samples. However, advances in application of small-scale sampling methods and interdisciplinary approaches to site investigations are beginning to significantly improve understanding of hydrogeological and microbiological interactions. Likewise, culture-based and molecular analyses of microbial populations in subsurface contaminant plumes have revealed significant adaptation of microbial populations to plume environmental conditions. Results of recent studies suggest that variability in subsurface geochemical and hydrological conditions significantly influences subsurface microbial-community structure. Combined investigations of site conditions and microbial-community structure provide the knowledge needed to understand interactions between subsurface microbial populations, plume geochemistry, and contaminant biodegradation.
A reconnaissance study of 28 trace metals in samples of surface soil (0-2.5 cm deep), subsurface soil (15-20 cm deep), and big sagebrush ( Artemisia tridentata ) that were collected from the Powder River Basin in Wyoming and Montana indicates that little variation occurs in nature at scales greater than about 35 km. This general lack of broadscale variation suggests that simple summary statistics for these materials could provide basinwide geochemical baselines for use in monitoring secular changes in the local geochemical environment. Samples of big sagebrush near the Dave Johnston Power Plant at the southern edge of the basin exhibit statistically significant reductions of strontium, vanadium, uranium, and selenium eastward from the plant.