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At least 1,585 records · Page 88Linked to original sources

Stratigraphy and correlation of the glacial deposits on the Montana Plains

Till units representing at least three pre-Illinoian continental glaciations, at least one Illinoian glaciation, and a late Wisconsin glaciation have been identified on the Montana Plains. Early Wisconsin or middle Wisconsin till units have not been identified. The southernmost limit of late Wisconsin glaciation is in Montana, more than 170 km south of the Lethbridge moraine in Alberta, Canada (Figs 1 and 2). An interpretation that the Lethbridge moraine is the limit of late Wisconsin glaciation (Stalker, 1977, 1980, 1983b; Stalker and Harrison, 1977; Rutter, 1980, 1981; Jackson, 1983) is incompatible with stratigraphic and morphologic evidence from Montana.

Montana, North Dakota↗

Palynological evidence for late miocene, pliocene and early pleistocene climate changes in the middle U.S. Atlantic Coastal Plain

Palynomorph assemblages from eight geologic formations in the Middle Atlantic Coastal Plain, ranging in age from latest Miocene to Early Pleistocene, have been interpreted in terms of terrestrial paleoclimates. The data suggest that a warm-temperate to subtropical climate, warmer than at present, prevailed at the close of the Miocene and the beginning of the Pliocene. At that time, there was little or no temperature gradient within the study area (36°30′ to 39°N). This warm period was followed by a warm-temperate interval in Virginia and North Carolina, with temperatures probably not very different from those of today, although a slight warming trend probably occurred during the deposition of the Colerain Beach Member of the Chowan River Formation. A definite cool interval is indicated by the presence of spruce pollen in the Bacons Castle Formation of Virginia. This interval is interpreted to have begun about 2.3–2.4 Ma, or possibly slightly later, simultaneous with the cooling that has been recorded in deep-sea cores of the North Atlantic Ocean, and in the pre-Tiglian of western Europe. This was followed by a warmer-than-present period that may be correlated with the Tiglian of the latest Pliocene. Finally, palynological data from the Cape May Formation of New Jersey suggest that a warm-temperate (warmer than at present) climate prevailed during the Early Pleistocene.

Delaware, Maryland, New Jersey, North Carolina, Vi↗

Sampling design for spatially distributed hydrogeologic and environmental processes

A methodology for the design of sampling networks over space is proposed. The methodology is based on spatial random field representations of nonhomogeneous natural processes, and on optimal spatial estimation techniques. One of the most important results of random field theory for physical sciences is its rationalization of correlations in spatial variability of natural processes. This correlation is extremely important both for interpreting spatially distributed observations and for predictive performance. The extent of site sampling and the types of data to be collected will depend on the relationship of subsurface variability to predictive uncertainty. While hypothesis formulation and initial identification of spatial variability characteristics are based on scientific understanding (such as knowledge of the physics of the underlying phenomena, geological interpretations, intuition and experience), the support offered by field data is statistically modelled. This model is not limited by the geometric nature of sampling and covers a wide range in subsurface uncertainties. A factorization scheme of the sampling error variance is derived, which possesses certain atttactive properties allowing significant savings in computations. By means of this scheme, a practical sampling design procedure providing suitable indices of the sampling error variance is established. These indices can be used by way of multiobjective decision criteria to obtain the best sampling strategy. Neither the actual implementation of the in-situ sampling nor the solution of the large spatial estimation systems of equations are necessary. The required values of the accuracy parameters involved in the network design are derived using reference charts (readily available for various combinations of data configurations and spatial variability parameters) and certain simple yet accurate analytical formulas. Insight is gained by applying the proposed sampling procedure to realistic examples related to sampling problems in two dimensions.

Advances in Water Resources↗

Aerial infrared surveys of Reykjanes and Torfajökull thermal areas, Iceland, with a section on cost of exploration surveys

In 1966 and 1968 aerial infrared surveys were conducted over 10 of 13 high-temperature thermal areas in Iceland. The surveys were made with an airborne scanner system, utilizing radiation in the 4.5–5.5 μm wavelength band. Supplementary ground geological studies were made in the Reykjanes and Torfajökull thermal areas to interpret features depicted on the infrared imagery and to relate zones of high heat flux to tectonic structure. In the Reykjanes area in southwestern Iceland a shallow ground temperature map was prepared for temperatures at a depth of 0.5 meters; comparison of this map with the infrared imagery reveals some striking similarities. It appears that aerial infrared surveys outline the surface thermal patterns of high-temperature areas and aid in relating these patterns to possible geological structures controlling the upflow of hot water. Amplitude-slicing techniques applied to the magnetically taped airborne scanner data permit an estimate to be made of the natural heat output on the basis of size of area and specific radiance. In addition to their value in preliminary studies of high-temperature areas, infrared surveys conducted at regular intervals over thermal area under exploitation can provide valuable data on changes that occur in surface manifestations with time. e.

Reykjanes, Torfajokull↗

Evaluation of Baltazor known geothermal resources area, Nevada

By virtue of the Geothermal Steam Act of 1970, the U.S. Geological Survey is required to appraise geothermal resources of the United States prior to competitive lease sales. This appraisal involves coordinated input from a variety of disciplines, starting with reconnaissance geology and geophysics. This paper describes how the results of several geophysical methods used in KGRA evaluation were interpreted by the authors, two geophysicists, involved with both the Evaluation Committee and the research program responsible for obtaining and interpreting the geophysical data to be used by the committee. ?? 1979.

Geothermics↗

Surface degassing and modifications to vesicle size distributions in active basalt flows

The character of the vesicle population in lava flows includes several measurable parameters that may provide important constraints on lava flow dynamics and rheology. Interpretation of vesicle size distributions (VSDs), however, requires an understanding of vesiculation processes in feeder conduits, and of post-eruption modifications to VSDs during transport and emplacement. To this end we collected samples from active basalt flows at Kilauea Volcano: (1) near the effusive Kupaianaha vent; (2) through skylights in the approximately isothermal Wahaula and Kamoamoa tube systems transporting lava to the coast; (3) from surface breakouts at different locations along the lava tubes; and (4) from different locations in a single breakout from a lava tube 1 km from the 51 vent at Pu'u ‘O’o. Near-vent samples are characterized by VSDs that show exponentially decreasing numbers of vesicles with increasing vesicle size. These size distributions suggest that nucleation and growth of bubbles were continuous during ascent in the conduit, with minor associated bubble coalescence resulting from differential bubble rise. The entire vesicle population can be attributed to shallow exsolution of H 2 O-dominated gases at rates consistent with those predicted by simple diffusion models. Measurements of H 2 O, CO 2 and S in the matrix glass show that the melt equilibrated rapidly at atmospheric pressure. Down-tube samples maintain similar VSD forms but show a progressive decrease in both overall vesicularity and mean vesicle size. We attribute this change to open system, “passive” rise and escape of larger bubbles to the surface. Such gas loss from the tube system results in the output of 1.2 × 10 6 g/day SO 2 , an output representing an addition of approximately 1% to overall volatile budget calculations. A steady increase in bubble number density with downstream distance is best explained by continued bubble nucleation at rates of 7–8/cm 3 s. Rates are ∼25% of those estimated from the vent samples, and thus represent volatile supersaturations considerably less than those of the conduit. We note also that the small total volume represented by this new bubble population does not: (1) measurably deplete the melt in volatiles; or (2) make up for the overall vesicularity decrease resulting from the loss of larger bubbles. Surface breakout samples have distinctive VSDs characterized by an extreme depletion in the small vesicle population. This results in samples with much lower number densities and larger mean vesicle sizes than corresponding tube samples. Similar VSD patterns have been observed in solidified lava flows and are interpreted to result from either static (wall rupture) or dynamic (bubble rise and capture) coalescence. Through comparison with vent and tube vesicle populations, we suggest that, in addition to coalescence, the observed vesicle populations in the breakout samples have experienced a rapid loss of small vesicles consistent with ‘ripening’ of the VSD resulting from interbubble diffusion of volatiles. Confinement of ripening features to surface flows suggests that the thin skin that forms on surface breakouts may play a role in the observed VSD modification.

Journal of Volcanology and Geothermal Research↗

A benthic foraminiferal record of middle to late Pliocene (3.15-2.85 Ma) deep water change in the North Atlantic

Records of benthic foraminifera from North Atlantic DSDP Site 607 and Hole 610A indicate changes in deep water conditions through the middle to late Pliocene (3.15 to 2.85 Ma). Quantitative analyses of modern associations in the North Atlantic indicate that seven species, Fontbotia wuellerstorfi, Cibicidoides kullenbergi, Uvigerina peregrina, Nuttallides umboniferus, Melonis pompilioides, Globocassidulina subglobosa and Epistominella exigua are useful for paleoenvironmental interpretation. The western North Atlantic basin (Site 607) was occupied by North Atlantic Deep Water (NADW) until ~2.88 Ma. At that time, N. umboniferus increased, indicating an influx of Southern Ocean Water (SOW). The eastern North Atlantic basin (Hole 610A) was occupied by a relatively warm water mass, possibly Northeastern Atlantic Deep Water (NEADW), through ~2.94 Ma when SOW more strongly influenced the site. These interpretations are consistent with benthic δ 18 O and δ 13 C records from 607 and 610A (Raymo et al., 1992). The results presented in this paper suggest that the North Atlantic was strongly influenced by northern component deep water circulation until 2.90–2.95 Ma. After that there was a transition toward a glacially driven North Atlantic circulation more strongly influenced by SOW associated with the onset of Northern Hemisphere glaciation. The circulation change follows the last significant SST and atmospheric warming prior to ~2.6 Ma.

Marine Micropaleontology↗

40Ar/39Ar systematics and argon diffusion in amber: Implications for ancient earth atmospheres

Argon isotope data indicate retained argon in bulk amber (matrix gas) is radiogenic [ 40 Ar/ 39 Ar ≃32o] than the much more abundant surface absorbed argon [ 40 Ar/ 39 Ar ≃295.5]. Neutron-induced 39 Ar is retained in amber during heating experiments to 150° -250°C, with no evidence of recoiled 39 Ar found after irradiation. A maximum permissible volume diffusion coefficient of argon in amber (at ambient temperature) D≤1.5 x 10 −17 cm 2 S −1 is calculated from 39 Ar retention. 40 Ar/ 39 Ar age calculations indicate Dominican Republic amber is ≃ 45 Ma and North Dakota amber is ≃ 89 Ma, both at least reasonable ages for the amber based upon stratigraphic and paleontological constraints and upon the small amount of radiogenic 40 Ar. To date, over 300 gas analyses of ambers and resins of Cretaceous to Recent age that are geographically distributed among fifteen noted world locations identify mixtures of gases in different sites within amber (Berner and Landis, 1988). The presence of multiple mixing trends between compositionally distinct end-members gases within the same sample and evidence for retained radiogenic argon within the amber argue persuasivley against rapid exchange by diffusion of amber-contained gases with moder air. Only gas in primary bubbles entrapped between successive flows of tree resin has been interpreted as original “ancient air”, which is an O 2 -rich end-member gas with air-like N 2 /Ar ratios. Gas analyses of these primary bubbles indicate atmospheric O 2 levels in the Late Cretaceous of ≃ 35%, and that atmospheric O 2 dropped by early Tertiary time to near a present atmospheric level of 21% O 2 . A very low argon diffusion coefficient in amber persuasively argues for a gas in primary bubbles trapped in amber being ancient air (possibly modified only by O 2 reaction with amber).

North Dakota↗

Geological and technological assessment of artificial reef sites, Louisiana outer continental shelf

This paper describes the general procedures used to select sites for obsolete oil and gas platforms as artificial reefs on the Louisiana outer continental shelf (OCS). The methods employed incorporate six basic steps designed to resolve multiple-use conflicts that might otherwise arise with daily industry and commercial fishery operations, and to identify and assess both geological and technological constraints that could affect placement of the structures. These steps include: (1) exclusion mapping; (2) establishment of artificial reef planning areas; (3) database compilation; (4) assessment and interpretation of database; (5) mapping of geological and man-made features within each proposed reef site; and (6) site selection. Nautical charts, bathymetric maps, and offshore oil and gas maps were used for exclusion mapping, and to select nine regional planning areas. Pipeline maps were acquired from federal agencies and private industry to determine their general locations within each planning area, and to establish exclusion fairways along each pipeline route. Approximately 1600 line kilometers of high-resolution geophysical data collected by federal agencies and private industry was acquired for the nine planning areas. These data were interpreted to determine the nature and extent of near-surface geologic features that could affect placement of the structures. Seismic reflection patterns were also characterized to evaluate near-bottom sedimentation processes in the vicinity of each reef site. Geotechnical borings were used to determine the lithological and physical properties of the sediment, and for correlation with the geophysical data. Since 1987, five sites containing 10 obsolete production platforms have been selected on the Louisiana OCS using these procedures. Industry participants have realized a total savings of approximately US $1 500 000 in salvaging costs by converting these structures into artificial reefs. ?? 1993.

Ocean and Coastal Management↗

Ground water chemistry and geochemical modeling of water-rock interactions at the Osamu Utsumi mine and the Morro do Ferro analogue study sites, Poços de Caldas, Minas Gerais, Brazil

Surface and ground waters, collected over a period of three years from the Osamu Utsumi uranium mine and the Morro do Ferro thorium/rare-earth element (Th/REE) deposits, were analyzed and interpreted to identify the major hydrogeochemical processes. These results provided information on the current geochemical evolution of ground waters for two study sites within the Poços de Caldas Natural Analogue Project. The ground waters are a K–Fe–SO 4 –F type, a highly unusual composition related to intense weathering of a hydrothermally altered and mineralized complex of phonolites. Tritium and stable isotope data indicate that ground waters are of meteoric origin and are not affected significantly by evaporation or water–rock interactions. Recharging ground waters at both study sites demonstrate water of less than about 35 years in age, whereas deeper, more evolved ground waters are below 1 TU but still contain in most cases detectable tritium. These deeper ground waters may be interpreted as being of 35 to 60 or more years in age, resulting mainly from an admixture of younger with older ground waters and/or indicating the influence of subsurface produced tritium. Geochemical processes involving water–rock–gas interactions have been modeled using ground water compositions, mineralogic data, ion plots and computations of speciation, non-thermodynamic mass balance and thermodynamic mass transfer. The geochemical reaction models can reproduce the water chemistry and mineral occurrences and they were validated by comparing the results of thermodynamic mass transfer calculations (using the PHREEQE program, Parkhurst et al., 1980). The results from the geochemical reaction models reveal that the dominant processes are production of CO 2 in the soil zone through aerobic decay of organic matter, dissolution of fluorite, calcite, K-feldspar, albite, chlorite and manganese oxides, oxidation of pyrite and sphalerite, and precipitation of ferric oxides, silica and kaolinite. Gibbsite precipitation can be modeled for the shallow (recharge) water chemistry at Morro do Ferro, consistent with known mineralogy. Recharge waters are undersaturated with respect to barite and discharging waters and deeper ground waters are saturated to supersaturated with respect to barite demonstrating a strong solubility control. Strontium isotope data demonstrate that sources other than calcium-bearing minerals are required to account for the dissolved strontium in the ground waters. These may include K-feldspar, smectite–chlorite mixed-layer clays and goyazite [SrAl 3 (PO 4 ) 2 (OH) 5 • H 2 O]. 1992.

Journal of Geochemical Exploration↗

Insights into controls on hexavalent chromium in groundwater provided by environmental tracers, Sacramento Valley, California, USA

Environmental tracers are useful for determining groundwater age and recharge source, yet their application in studies of geogenic Cr(VI) in groundwater has been limited. Environmental tracer data from 166 wells located in the Sacramento Valley, northern California, were interpreted and compared to Cr concentrations to determine the origin and age of groundwater with elevated Cr(VI), and better understand where Cr(VI) becomes mobilized and how it evolves along flowpaths. In addition to major ion and trace element concentrations, the dataset includes &delta; 18 O, &delta; 2 H, 3 H concentration, 14 C activity (of dissolved inorganic C), &delta; 13 C, 3 He/ 4 He ratio, and noble gas concentrations (He, Ne, Ar, Kr, Xe). Noble gas recharge temperatures (NGTs) were computed, and age-related tracers were interpreted in combination to constrain the age distribution in samples and sort them into six different age categories spanning from <60 yr old to >10,000 yr old. Nearly all measured Cr is in the form of Cr(IV). Concentrations range from <1 to 46 &mu;g L &minus;1 , with 10% exceeding the state of California&rsquo;s Cr(VI) maximum contaminant level of 10 &mu;g L &minus;1 . Two groups with elevated Cr(VI) (⩾5 &mu;g L &minus;1 ) were identified. Group 1 samples are from the southern part of the valley and contain modern (<60 yr old) water, have elevated NO 3 &minus; concentrations (>3 mg L &minus;1 ), and commonly have &delta; 18 O values enriched relative to local precipitation. These samples likely contain irrigation water and are elevated due to accelerated mobilization of Cr(VI) in the unsaturated zone (UZ) in irrigated areas. Group 2 samples are from throughout the valley and typically contain water 1000&ndash;10,000 yr old, have &delta; 18 O values consistent with local precipitation, and have unexpectedly warm NGTs. Chromium(VI) concentrations in Group 2 samples may be elevated for multiple reasons, but the hypothesis most consistent with all available data (notably, the warm NGTs) is a relatively long UZ residence time due to recharge through a deep UZ near the margin of the basin. A possible explanation for why Cr(VI) may be primarily mobilized in the UZ rather than farther along flowpaths in the oxic portion of the saturated zone is more dynamic cycling of Mn in the UZ due to transient moisture and redox conditions.

California↗

Manual hierarchical clustering of regional geochemical data using a Bayesian finite mixture model

Interpretation of regional scale, multivariate geochemical data is aided by a statistical technique called &ldquo;clustering.&rdquo; We investigate a particular clustering procedure by applying it to geochemical data collected in the State of Colorado, United States of America. The clustering procedure partitions the field samples for the entire survey area into two clusters. The field samples in each cluster are partitioned again to create two subclusters, and so on. This manual procedure generates a hierarchy of clusters, and the different levels of the hierarchy show geochemical and geological processes occurring at different spatial scales. Although there are many different clustering methods, we use Bayesian finite mixture modeling with two probability distributions, which yields two clusters. The model parameters are estimated with Hamiltonian Monte Carlo sampling of the posterior probability density function, which usually has multiple modes. Each mode has its own set of model parameters; each set is checked to ensure that it is consistent both with the data and with independent geologic knowledge. The set of model parameters that is most consistent with the independent geologic knowledge is selected for detailed interpretation and partitioning of the field samples.

Colorado↗

A geochemical examination of humidity cell tests

Humidity cell tests (HCTs) are long-term (20 to >300 weeks) leach tests that are considered by some to be the among the most reliable geochemical characterization methods for estimating the leachate quality of mined materials. A number of modifications have been added to the original HCT method, but the interpretation of test results varies widely. We suggest that the HCTs represent an underutilized source of geochemical data, with a year-long test generating approximately 2500 individual chemical data points. The HCT concentration peaks and valleys can be thought of as a “chromatogram” of reactions that may occur in the field, whereby peaks in concentrations are associated with different geochemical processes, including sulfate salt dissolution, sulfide oxidation, and dissolution of rock-forming minerals, some of which can neutralize acid. Some of these reactions occur simultaneously, some do not, and geochemical modeling can be used to help distinguish the dominant processes. Our detailed examination, including speciation and inverse modeling, of HCTs from three projects with different geology and mineralization shows that rapid sulfide oxidation dominates over a limited period of time that starts between 40 and 200 weeks of testing. The applicability of laboratory tests results to predicting field leachate concentrations, loads, or rates of reaction has not been adequately demonstrated, although early flush releases and rapid sulfide oxidation rates in HCTs should have some relevance to field conditions. Knowledge of possible maximum solute concentrations is needed to design effective treatment and mitigation approaches. Early flush and maximum sulfide oxidation results from HCTs should be retained and used in environmental models. Factors that complicate the use of HCTs include: sample representation, time for microbial oxidizers to grow, sample storage before testing, geochemical reactions that add or remove constituents, and the HCT results chosen for use in modeling the environmental performance at mine sites. Improved guidance is needed for more consistent interpretation and use of HCT results that rely on identifying: the geochemical processes; the mineralogy, including secondary mineralogy; the available surface area for reactions; and the influence of hydrologic processes on leachate concentrations in runoff, streams, and groundwater.

Applied Geochemistry↗

Cadmium isotope fractionation during coal combustion: Insights from two U.S. coal-fired power plants

Coal combustion, one of the principal energy sources of electricity in the United States, produces over 100 million tons of coal combustion products (CCPs) per year in the U.S. The reuse and disposal of CCPs has the potential to release toxic trace elements, including cadmium (Cd), into the environment. In this study, we investigated CCPs, including bottom ash (BA), economizer fly ash (EFA), and fly ash (FA), as well as feed coal (FC) and pulverized coal (PC) collected from two U.S. coal-fired power plants in New Mexico and Ohio with different coal supplies. The New Mexico plant uses high volatile C bituminous, low-sulfur coals mined from the San Juan Basin (Cretaceous Fruitland Formation) and the Ohio plant uses high volatile A bituminous, high-sulfur central Appalachian Basin coals (Upper Pennsylvanian Monongahela Formation). Mineralogical and elemental analysis showed that these CCP samples consist of ∼70% amorphous Al-Si-rich glasses and ∼30% mineral phases of quartz (SiO 2 ) and mullite (Ai 6 Si 2 O 13 ). The Cd isotope compositions (δ 114 Cd, normalized to NIST Cd standard 3108) of FA and EFA samples (ranging from −0.51 to +0.47‰) are distinctively heavier than those of BA samples (−0.75 to −0.52‰) in both power plants. We interpret this Cd isotope difference as a result of Cd condensation from the gas phase during flue gas cooling, instead of evaporation of Cd phase during coal combustion. Cd condensation is the main process to generate the isotopically heavy Cd signatures that preferentially partition on the fine FA particles. We also investigated Cd isotope compositions in different leachate products from a series of batch-leaching experiments with these CCPs, using diluted acetic acid, hydroxyl ammonium chloride, hydrogen peroxide followed by ammonium acetate, and 5% nitric acid, as a possible means to identify CCP-released Cd in the environment. Unusually and significantly heavier Cd isotope compositions were observed in each leachate of FA samples (+1.10 to +7.09‰), which fall far outside from the range of Cd isotope ratios observed in natural soils and rocks, but less so for the EFA samples (−0.43 to +1.18‰). Such an observation is consistent with the interpretation that isotopically heavy Cd preferentially partitions on the fine FA particles after coal combustion and is readily to be released during these leaching experiments. This study demonstrates that high-temperature coal combustion can lead to a very large degree of fractionation of Cd isotopes that can be used as a unique tracer for identifying anthropogenic metal inputs in the environment. The major Cd isotope fractionation process occurs as the Cd gas phase condenses on fine FA particles during the flue gas cooling stage after coal combustion.

New Mexico, Ohio↗

Report of the COSPAR mars special regions colloquium

In this paper we present the findings of a COSPAR Mars Special Regions Colloquium held in Rome in 2007. We review and discuss the definition of Mars Special Regions, the physical parameters used to define Mars Special Regions, and physical features on Mars that can be interpreted as Mars Special Regions. We conclude that any region experiencing temperatures > -25 ??C for a few hours a year and a water activity > 0.5 can potentially allow the replication of terrestrial microorganisms. Physical features on Mars that can be interpreted as meeting these conditions constitute a Mars Special Region. Based on current knowledge of the martian environment and the conservative nature of planetary protection, the following features constitute Mars Special regions: Gullies and bright streaks associated with them, pasted-on terrain, deep subsurface, dark streaks only on a case-by-case basis, others to be determined. The parameter definition and the associated list of physical features should be re-evaluated on a regular basis. ?? 2010 COSPAR. Published by Elsevier Ltd. All rights reserved.

Advances in Space Research↗

Trace metal records of regional paleoenvironmental variability in Pennsylvanian (Upper Carboniferous) black shales

Regional geochemical differences within a laterally continuous, cyclic Pennsylvanian (Upper Carboniferous) shale in midcontinent North America are interpreted in light of models of glacioeustatic forcing and new views on water-column paleoredox stability and trace-metal behavior in black shale environments. Specifically, we characterize differences in transition metal (Fe, Mn, Mo, V, Ni, Zn, Pb and U) concentrations in black shales of the Hushpuckney Shale Member of the Swope Limestone in Iowa and equivalent black shale beds of the Coffeyville Formation in Oklahoma. Although C-S-Fe systematics and uniform 34S-depleted isotope ratios of pyrite indicate pervasive euxinic deposition (anoxic and sulfidic bottom waters) for these shales, regional variations can be inferred for the efficiency of Mo scavenging and for the rates of siliciclastic sedimentation as expressed in spatially varying Fe/Al ratios. Black shales in Iowa show Mo enrichment roughly five times greater than that observed in coeval euxinic shales in Oklahoma. By contrast, Fe/Al ratios in Oklahoma shales are as much as five times greater than the continental ratio of 0.5 observed in the over- and underlying oxic facies and in the coeval black shales in Iowa. Recent work in modern marine settings has shown that enrichments in Fe commonly result from scavenging in a euxinic water column during syngenetic pyrite formation. In contrast to Fe, the concentrations of other transition metals (Mo, V, Ni, Pb, Zn, U) are typically more enriched in the black shales in Iowa relative to Oklahoma. The transition metal trends in these Paleozoic shales are reasonably interpreted in terms of early fixation in organic-rich sediments due to euxinic water-column conditions. However, regional variations in (1) rates of siliciclastic input, (2) organic reservoirs, including relative inputs of terrestrial versus marine organic matter, and (3) additional inputs of metals to bottom waters from contemporaneous hydrothermal vents are additional key controls that lead to geographic variation in the extent of metal enrichments preserved in ancient organic-rich sediments. Published by Elsevier B.V.

Chemical Geology↗

A graphical method to evaluate predominant geochemical processes occurring in groundwater systems for radiocarbon dating

A graphical method is described for identifying geochemical reactions needed in the interpretation of radiocarbon age in groundwater systems. Graphs are constructed by plotting the measured 14 C, δ 13 C, and concentration of dissolved inorganic carbon and are interpreted according to specific criteria to recognize water samples that are consistent with a wide range of processes, including geochemical reactions, carbon isotopic exchange, 14 C decay, and mixing of waters. The graphs are used to provide a qualitative estimate of radiocarbon age, to deduce the hydrochemical complexity of a groundwater system, and to compare samples from different groundwater systems. Graphs of chemical and isotopic data from a series of previously-published groundwater studies are used to demonstrate the utility of the approach. Ultimately, the information derived from the graphs is used to improve geochemical models for adjustment of radiocarbon ages in groundwater systems.

Chemical Geology↗

The triple argon isotope composition of groundwater on ten-thousand-year timescales

Understanding the age and movement of groundwater is important for predicting the vulnerability of wells to contamination, constraining flow models that inform sustainable groundwater management, and interpreting geochemical signals that reflect past climate. Due to both the ubiquity of groundwater with order ten-thousand-year residence times and its importance for climate reconstruction of the last glacial period, there is a strong need for improving geochemical dating tools on this timescale. Whereas 14 C of dissolved inorganic carbon and dissolved 4 He are common age tracers for Late Pleistocene groundwater, each is limited by systematic uncertainties related to aquifer composition and lithology, and the extent of water-rock interaction. In principle, radiogenic 40 Ar in groundwater acquired from decay of 40 K in aquifer minerals should be insensitive to some processes that impact 14 C and 4 He and thus represent a useful, complementary age tracer. In practice, however, detection of significant radiogenic 40 Ar signals in groundwater has been limited to a small number of studies of extremely old groundwater (>100 ka). Here we present the first high-precision (<1‰) measurements of triple Ar isotopes ( 40 Ar, 38 Ar, 36 Ar) in groundwater. We introduce a model that distinguishes radiogenic 40 Ar from atmospheric 40 Ar by using the non-radiogenic Ar isotopes ( 36 Ar, 38 Ar) to correct for mass-dependent fractionation. Using this model, we investigate variability in radiogenic 40 Ar excess (Δ 40 Ar) across 58 groundwater samples collected from 36 wells throughout California (USA). We find that Δ 40 Ar ranges from ~0‰ (the expected minimum value) to +4.2‰ across three study areas near Fresno, San Diego, and the western Mojave Desert. Based on measurements from a network of 23 scientific monitoring wells in San Diego, we find evidence for a strong dependence of Δ 40 Ar on aquifer lithology. We suggest that Δ 40 Ar is fundamentally controlled by the weathering of old K-bearing minerals and thus reflects both the degree of groundwater-rock interaction, which is related to groundwater age, and the integrated flow through different geological formations. Future studies of Late Pleistocene groundwater may benefit from high-precision triple Ar isotope measurements as a new tool to better interpret 14 C- and 4 He-based constraints on groundwater age and flow.

Chemical Geology↗