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At least 343 records · Page 19Linked to original sources
USGS2009

Carbon isotope chemostratigraphy and precise dating of middle Frasnian (lower Upper Devonian) Alamo Breccia, Nevada, USA

At Hancock Summit West, Nevada, western USA, uppermost Givetian (upper Middle Devonian) and lower and middle Frasnian (lower Upper Devonian) rocks of the lower Guilmette Formation include, in stratigraphic sequence, carbonate-platform facies of the conodont falsiovalis , transitans , and punctata Zones; the type Alamo Breccia Member of the middle punctata Zone; and slope facies of the punctata and hassi Zones. The catastrophically deposited Alamo Breccia and related phenomena record the ~ 382 Ma Alamo event, produced by a km-scale bolide impact into a marine setting seaward of an extensive carbonate platform fringing western North America. Re-evaluation of conodonts from the lower Guilmette Formation and Alamo Breccia Member, together with regional sedimentologic and conodont biofacies comparisons, now firmly locates the onset of the Johnson et al. (1985) transgressive–regressive (T–R) cycle IIc, which occurred after the start of the punctata Zone, within a parautochthonous megablock low in the Alamo Breccia. Whole-rock carbon isotope analyses through the lower Guilmette Formation and Alamo Breccia Member reveal two positive δ 13 C carb excursions: (1) a small, 3‰ excursion, which is possibly correlative with the falsiovalis Event previously identified from sections in Western Europe and Australia, occurs below the breccia in the Upper falsiovalis Zone to early part of the transitans Zone; and (2) a large, multi-part excursion, dominated by a 6‰ positive shift, begins above the start of the punctata Zone and onset of T–R cycle IIc and continues above the Alamo Breccia, ending near the punctata – hassi zonal boundary. This large excursion correlates with the punctata Event, a major positive δ 13 C excursion previously recognized in eastern Laurussia and northern Gondwana. Consistent with previous studies, at Hancock Summit West the punctata Event is apparently not associated with any regional extinctions or ecosystem reorganizations. In the study area, onset of the main punctata Event began after the start of both the punctata Zone and T–R cycle IIc, and preceded the Alamo impact by less than 650 k.y., as inferred from conodont biochronologic and regional rock-accumulation rate estimates. Although complicated by the heterolithic, high-energy deposits of the Alamo Breccia, the carbon isotope record of the breccia and post-breccia beds does not indicate a major impact-correlative perturbation to the carbon cycle. This study extends recognition of the punctata Event to western Laurussia, further reinforcing the potential global scale of the event and its potential importance to understanding early to middle Frasnian marine geochemistry and palaeoenvironments. Based on previous models and our observations, increased tectonic activity, increased nutrient flux to oceans, increased marine bioproductivity, widespread anoxia, and increased organic carbon burial were all likely key factors in driving the punctata Event excursion. Furthermore, periodic eustatic and regional relative sea-level rises may have played an important role in promoting organic carbon burial and in maintaining a link between the primary open-marine geochemical signal and that recorded on the shallow-marine, lower Guilmette carbonate platform.

Nevada↗
USGS2015

Annual and seasonal distribution of intertidal foraminifera and stable carbon isotope geochemistry, Bandon Marsh, Oregon, USA

We investigated the influence of inter-annual and seasonal differences on the distribution of live and dead foraminifera, and the inter-annual variability of stable carbon isotopes (d13C), total organic carbon (TOC) values and carbon to nitrogen (C/N) ratios in bulk sediments from intertidal environments of Bandon Marsh (Oregon, USA). Living and dead foraminiferal species from 10 stations were analyzed over two successive years in the summer (dry) and fall (wet) seasons. There were insignificant inter-annual and seasonal variations in the distribution of live and dead species. But there was a noticeable decrease in calcareous assemblages (Haynesina sp.) between live populations and dead assemblages, indicating that most of the calcareous tests were dissolved after burial; the agglutinated assemblages were comparable between constituents. The live populations and dead assemblages were dominated by Miliammina fusca in the tidal flat and low marsh, Jadammina macrescens, Trochammina inflata and M. fusca in the high marsh, and Trochamminita irregularis and Balticammina pseudomacrescens in the highest marsh to upland. Geochemical analyses (d13C, TOC and C/N of bulk sedimentary organic matter) show no significant influence of inter-annual variations but a significant correlation of d13C values (R = 20.820, p , 0.001), TOC values (R = 0.849, p , 0.001) and C/N ratios (R = 0.885, p , 0.001) to elevation with respect to the tidal frame. Our results suggest that foraminiferal assemblages and d13C and TOC values, as well as C/N ratios, in Bandon Marsh are useful in reconstructing paleosea-levels on the North American Pacific coast.

Oregon↗
USGS1983

Geology of the Devonian black shales of the Appalachian basin

Black shales of Devonian age in the Appalachian basin are a unique rock sequence. The high content of organic matter, which imparts the characteristic lithology, has for years attracted considerable interest in the shales as a possible source of energy. Concurrent with periodic and varied economic exploitations of the black shales are geologic studies. The recent energy shortage prompted the U.S. Department of Energy through the Eastern Gas Shales Project of the Morgantown Energy Technology Center to underwrite a research program to determine the geologic, geochemical, and structural characteristics of the Devonian black shales in order to enhance the recovery of gas from the shales. Geologic studies produced a regional stratigraphic network that correlates the 15-foot sequence in Tennessee with 3,000 feet of interbedded black and gray shales in central New York. The classic Devonian black-shale sequence in New York has been correlated with the Ohio Shale of Ohio and Kentucky and the Chattanooga Shale of Tennessee and southwestern Virginia. Biostratigraphic and lithostratigraphic markers in conjunction with gamma-ray logs facilitated long range correlations within the Appalachian basin and provided a basis for correlations with the black shales of the Illinois and Michigan basins. Areal distribution of selected shale units along with paleocurrent studies, clay mineralogy, and geochemistry suggests variations in the sediment source and transport directions. Current structures, faunal evidence, lithologic variations, and geochemical studies provide evidence to support interpretation of depositional environments. In addition, organic geochemical data combined with stratigraphic and structural characteristics of the shale within the basin allow an evaluation of the resource potential of natural gas in the Devonian shale sequence.

Conference Paper↗
USGS1991

Geochemistry of dissolved inorganic carbon in a Coastal Plain aquifer. 2. Modeling carbon sources, sinks, and δ13C evolution

Stable isotope data for dissolved inorganic carbon (DIC), carbonate shell material and cements, and microbial CO 2 were combined with organic and inorganic chemical data from aquifer and confining-bed pore waters to construct geochemical reaction models along a flowpath in the Black Creek aquifer of South Carolina. Carbon-isotope fractionation between DIC and precipitating cements was treated as a Rayleigh distillation process. Organic matter oxidation was coupled to microbial fermentation and sulfate reduction. All reaction models reproduced the observed chemical and isotopic compositions of final waters. However, model 1, in which all sources of carbon and electron-acceptors were assumed to be internal to the aquifer, was invalidated owing to the large ratio of fermentation CO 2 to respiration CO 2 predicted by the model (5–49) compared with measured ratios (two or less). In model 2, this ratio was reduced by assuming that confining beds adjacent to the aquifer act as sources of dissolved organic carbon and sulfate. This assumption was based on measured high concentrations of dissolved organic acids and sulfate in confining-bed pore waters (60–100 μM and 100–380 μM, respectively) relative to aquifer pore waters (from less than 30 μM and 2–80 μM, respectively). Sodium was chosen as the companion ion to organic-acid and sulfate transport from confining beds because it is the predominant cation in confining-bed pore waters. As a result, excessive amounts of Na-for-Ca ion exchange and calcite precipitation (three to four times more cement than observed in the aquifer) were required by model 2 to achieve mass and isotope balance of final water. For this reason, model 2 was invalidated. Agreement between model-predicted and measured amounts of carbonate cement and ratios of fermentation CO 2 to respiration CO 2 were obtained in a reaction model that assumed confining beds act as sources of DIC, as well as organic acids and sulfate. This assumption was supported by measured high concentrations of DIC in confining beds (2.6–2.7 mM). Results from this study show that geochemical models of confined aquifer systems must incorporate the effects of adjacent confining beds to reproduce observed groundwater chemistry accurately.

South Carolina↗
USGS1993

Geochemistry of surface sediments of Minnesota lakes

Analyses of 36 trace, minor, and major elements were used to classify the sediments of 46 Minnesota lakes. Q-mode factor analyses grouped Minnesota lake sediments according to clastic-, carbonate-, organic-, and redox-related elements. Carbonate lakes occur in west-central Minnesota; their sediments have relatively high concentrations of CaCO 3 , Ba, and Sr. Lakes with sediments containing more than 30% organic matter occur in east-central and northeastern Minnesota; these sediments have high concentrations of organic C, N, and H, and slightly elevated concentrations of Pb. Only three lakes have sediments included in the “redox” group, with relatively high concentrations of Fe, Mn, Mo, La, and Zn. High concentrations of redox-sensitive elements appear to be associated with oxidized iron and manganese minerals, but in Elk Lake, one of the three lakes in this group, a significant amount of iron and manganese is contained in iron phosphate, iron sulfide, and manganese carbonate. Clastic lake sediments are not diluted by large amounts of organic matter, carbonate minerals, or iron-manganese minerals, and are of two types: a western group derived largely from Cretaceous shales in the prairie regions, and a northeastern group derived from Precambrian crystalline rocks in the forested arrowhead region. Western clastic lake sediments have higher concentrations of Al, Na, K, B, Ba, V, Mg, and Sr. Most northeastern clastic lake sediments contain higher concentrations of Cu, Y, Be, and Ni, but several are chemically more similar to those of western prairie lakes.

Minnesota↗
USGS1974

Red Sea geochemistry

The Red Sea drillings reveal a number of new facets of the hot-brine-metalliferous system and other geochemical aspects of the sea, its sediments, and its past history as follows: 1) Dark shales rich in organic material, and containing enhanced Mo and V concentrations, are characteristic of Plio-Pleistocene strata in the Red Sea. Values as high as 1500 ppm V and 500 ppm Mo were obtained in sediments containing up to 8 percent organic carbon. 2) Metalliferous sediments in the hot brine deep (Site 226) are similar in composition in both solids and interstitial water to previously analyzed sediments. However, one site (228) well south of the known hot-brine deeps shows zinc mineralization reaching 5 percent Zn in late Miocene shale-anhydrite breccias. 3) Pore fluid studies show that near-saturated (NaCl) brines having similar total salt concentration to the hot-brine fluids are associated with Miocene evaporites at Sites 225, 227, and 228. However, their chemical and isotopic composition precludes such fluids being part of the "hot brine plumbing system." Hydrogen and oxygen isotope studies demonstrate that fluids trapped between and among the evaporitic rocks have a strong meteoric water component, presumed to have entered the rocks during or shortly after formation in shallow evaporating pans. The composition of pore fluid at Site 227 suggests the presence of late-stage evaporite minerals of the tachyhydrite CaMg 2 Cl 6 • 12H 2 O series in the in situ rocks. 4) Diffusivity measurements show that the pre-Miocene strata permit dissolved salt or gas diffusion to the extent of from 1/2 to about 1/10 the rate in free solution. However, in anhydrites diffusivity is reduced more than 100-fold, and no diffusion could be detected through halite rock. The rates applied to interstitial salt gradients at Site 225 suggest that less than 1 meter of rock salt is removed per million years by diffusion processes. The diffusion of salt can already be detected a few meters below the sediment-water interface, and based on the interstitial water studies, one can affirm the presence of salt at depth at Sites 228, 230, and possibly 229, where rock salt was not encountered by the drill. 5) Isotopic measurements on leads show that both leads from Site 228 and the hot brine deep (Site 226) require input from igneous or volcanic sources (e.g., volcanic ash). Elsewhere, however, leads of sedimentary-pelagic origin are noted. 6) Isotopic and other evidence indicates that the long-distance transport of subterranean brines advocated by Craig (1969) is unlikely. Instead, it is proposed that the source of the hot brines is subevaporite clastic or other aquifers of early to middle Miocene age that have been disrupted by rifting. These discharge in the deeps by virtue of hydrodynamic continuity with heavy brines at higher positions on the nearby flanks of the Red Sea. In this case, the waters might be fossil (middle Miocene) Red Sea waters of relatively normal salinity that have acquired greater salt concentration by diffusion from overlying late Miocene evaporites. The model is consistent with the isolated nature of the brine deeps and suggests that flow might have been enhanced by increased hydraulic gradients during periods of lowered Red Sea levels. 7) Interstitial water evidence indicates that Pleistocene lowerings of sea level did not cause evaporative conditions leading to actual gypsum or other evaporite deposition in the deeper water zones, as has been postulated. This in turn suggests that sill depths were greater than have been assumed.

Initial reports of the Deep Sea Drilling Project↗
USGS1984

Origin and geochemistry of Cretaceous deep-sea black shales and multicolored claystones, with emphasis on Deep Sea Drilling Project Site 530, southern Angola Basin

Deep-water sedimentary sequences of mid-Cretaceous age, rich in organic carbon, have been recovered at many DSDP sites in the Atlantic Ocean. Most of these sequences have a marked cyclicity in amount of organic carbon resulting in interbedded multicolored shale, marlstone, and (or) limestone that have cycle periods of 20,000 to 100,000 years and average 40,000 to 50,000 years. These cycles may be related to some climatic control on influx of terrigenous organic matter and sediment, rates of upwelling and sea-surface production of organic matter, and preservation of organic matter related to deeper-water dissolved oxygen concentration. These variations in supply of organic matter had pronounced effects on the potential of the sediment for subsequent diagenetic changes and geochemical partitioning in adjacent beds. Many trace elements are enriched in organic-carbon-rich lithologies relative to interbedded organic-carbon-poor lithologies. Elements that are most commonly enriched are Cr, Ni, V, Cu, Zn, and Mo. The association of high traceelement concentrations with organic matter may be the result of concentration of these elements by organisms or by chemical sorption and precipitation processes under anoxic conditions. Detailed trace-element profiles from organiccarbon-rich strata at Site 530 suggest that there may be differential mobility of trace elements, with diffusion of some elements over distances of at least tens of meters. The sequence of trace-element mobility, from highest to lowest, is approximately Ba, Mn, Pb, Ni, Co, Cr, Cu, Zn, V, Cd, and Mo. Slowly deposited, oxidized clays directly overlying some black shale sequences are enriched in some metals, particularly Fe, Mn, Zn, and Cu, relative to normal pelagic clays, and this enrichment may be the result of upward migration of metals in pore waters during compaction or diffusion from the underlying black shale. Most depositional models that have been used to explain the accumulation of the organic-carbon-rich strata imply that reducing conditions in the sediments (and therefore the increased degree of preservation of organic matter) were the result of anoxic or near-anoxic conditions in oceanic bottom waters, or in a midwater oxygen-minimum zone. Evidence from several DSDP sites in the Atlantic, however, indicate that some of these middle Cretaceous "black shale" beds may be the result of variations in rate of supply of organic matter that produced anoxia or near-anoxia within midwater oxygen-minimum zones and possibly, under extreme conditions, throughout much of the bottomwater mass. Although bottom-water anoxia may have occurred during periods of organic-carbon-rich strata, it was not necessarily the only cause for accumulation of these strata. The main reason for the accumulation of organic-carbonrich strata was an increase in the relative amount of organic debris being deposited. Some of this organic debris was derived from continental-margin areas of increased production, accumulation, and preservation of organic matter from marine, terrestrial, or mixed sources and transported to slope and basinal sites by turbidity currents.

Initial Reports of the D.S.D.P.↗
USGS2015

Using biotic ligand models to predict metal toxicity in mineralized systems

The biotic ligand model (BLM) is a numerical approach that couples chemical speciation calculations with toxicological information to predict the toxicity of aquatic metals. This approach was proposed as an alternative to expensive toxicological testing, and the U.S. Environmental Protection Agency incorporated the BLM into the 2007 revised aquatic life ambient freshwater quality criteria for Cu. Research BLMs for Ag, Ni, Pb, and Zn are also available, and many other BLMs are under development. Current BLMs are limited to ‘one metal, one organism’ considerations. Although the BLM generally is an improvement over previous approaches to determining water quality criteria, there are several challenges in implementing the BLM, particularly at mined and mineralized sites. These challenges include: (1) historically incomplete datasets for BLM input parameters, especially dissolved organic carbon (DOC), (2) several concerns about DOC, such as DOC fractionation in Fe- and Al-rich systems and differences in DOC quality that result in variations in metal-binding affinities, (3) water-quality parameters and resulting metal-toxicity predictions that are temporally and spatially dependent, (4) additional influences on metal bioavailability, such as multiple metal toxicity, dietary metal toxicity, and competition among organisms or metals, (5) potential importance of metal interactions with solid or gas phases and/or kinetically controlled reactions, and (6) tolerance to metal toxicity observed for aquatic organisms living in areas with elevated metal concentrations.

Applied Geochemistry↗
USGS2024

Uranium redox and deposition transitions embedded in deep-time geochemical models and mineral chemistry networks

Uranium (U) is an important global energy resource and a redox sensitive trace element that reflects changing environmental conditions and geochemical cycling. The redox evolution of U mineral chemistry can be interrogated to understand the formation and distribution of U deposits and the redox processes involved in U geochemistry throughout Earth history. In this study, geochemical modeling using thermodynamic data, and mineral chemistry network analysis are used to investigate U geochemistry and deposition through time. The number of U 6+ mineral localities surpasses the number of U 4+ mineral localities in the Paleoproterozoic. Moreover, the number of sedimentary U 6+ mineral localities increases earlier in the Phanerozoic than the number of U 4+ sedimentary mineral localities, likely due to the necessity of sufficient sedimentary organic matter to reduce U 6+ –U 4+ . Indeed, modeling calculations indicate that increased oxidative weathering due to surface oxygenation limited U 4+ uraninite (UO 2 ) formation from weathered granite and basalt. Louvain network community detection shows that U 6+ forms minerals with many more shared elements and redox states than U 4+ . The range of weighted Mineral Element Electronegativity Coefficient of Variation (wMEE CV ) values of U 6+ minerals increases through time, particularly during the Phanerozoic. Conversely, the range of wMEE CV values of U 4+ minerals is consistent through time due to the relative abundance of uraninite, coffinite, and brannerite. The late oxidation and formation of U 6+ minerals compared to S 6+ minerals illustrates the importance of the development of land plants, organic matter deposition, and redox-controlled U deposition from ground water in continental sediments during this time-period.

Geochemistry, Geophysics, Geosystems↗
USGS2004

Late Pleistocene to Holocene environmental changes as recorded in the sulfur geochemistry of coastal plain sediments, southwestern Taiwan

A core, drilled at San-liao-wan in the southwestern coastal plain of Taiwan, has been analyzed for total sulfur contents, isotopic values, as well as ratios of pyritic sulfur to organic carbon. Our results demonstrate a close relationship between late Pleistocene sea-level change and the proxies generated in this study. The inorganic sulfur contents indicate that at our study site, the Holocene transgression started at ???11 ka and remained under seawater for thousands of years until the late Holocene, corresponding to a depth of 20 m in the study core. The uppermost 20 m of core shows relatively high total organic carbon (TOC) and ??34S of inorganic sulfur, suggesting a transitional environment such as muddy lagoon or marsh, before the site turned into a modern coastal plain. In the lower part of the core, at depths of 110-145 m (corresponding ages of ???12-30 ka), low sulfur contents are recorded, probably indicating fluvial sediments deposited during the oceanic isotope stage (OIS) 2, a sea-level lowstand. The lower part of the core, roughly within OIS 3, records at least two transgressions, although the transgressional signals may be somewhat obscured by subsequent weathering. The reworked origin of organic matter reported in previous studies is confirmed by our organic sulfur data; however, the marine organic source was periodically dominant. The modern high sulfate concentrations in pore water have no correlation to the other sulfur species in the sediments, probably indicating that the sulfate migrated into the site subsequent to early diagenesis. ?? 2003 Elsevier Ltd. All rights reserved.

Journal of Asian Earth Sciences↗
USGS2003

Interactions between dissolved organic matter and mercury in the Florida Everglades

Experiments were conducted using organic matter isolated from various surface waters in the Florida Everglades to study the interactions between dissolved organic matter (DOM) and Hg (II). Conditional distribution coefficients ( ), obtained using an equilibriurn dialysis ligand exchange method, were strongly affected by the Hg/DOM concentration ratio. Very strong interactions ( = 10 L kg -1 ), indicative of Hg-thiol bonds, were observed at Hg/DOM ratios below approximately 1 g Hg per mg DOM. Above approximately 10 g Hg per mg DOM much lower values ( L kg -1 ) were obtained. DOM-Hg interactions were also studied by HgS (log K ) dissolution and precipitation experiments. In the dissolution experiments, a significant amount of Hg was released from cinnabar in the presence of DOM, suggesting strong interactions. Conversely, precipitation of HgS was strongly inhibited in the presence of low concentrations ( 3 mg C/L) of DOM. In both the dissolution and precipitation experiments, organic matter rich in aromatic moities was more reactive with HgS than less aromatic fractions and sulfur-containing model compounds. These results suggest that DOM can influence the geochemistry of inorganic complexes of Hg in the Everglades, especially HgS, by strong Hg-DOM binding and colloidal stabilization.

Florida↗
USGS1983

Geochemistry of the Chattanooga shale, Dekalb County, central Tennessee.

This Upper Devonian shale is of interest because of its unusual enrichment in trace elements, especially U; a new chemical analysis for major, minor and trace elements is presented. Stable isotopes of carbon (organic) show delta 13C approx -29per mille and for total sulphur show -21 to -27per mille delta 34S. The organic matter was found to range from dominantly marine (Dowelltown member) to dominantly terrestrial (Gassaway member) by extraction-column chromatography-GS and also by pyrolysis-GS of kerogen. Trace elements U, Mo, Co, Zn, Cu, Ni, V, As and Hg are enriched in the organic- and sulphide-rich units. This enrichment can be related to a euxinic depositional environment, to a very slow sedimentation rate (approx 2 mm/1000 years), to the type of organic matter that varied from mainly marine to terrestrial, and to the source of the metals, which shows abundance variations that originated, at least in part, from volcanic ash layers.-R.S.M.

Southeastern Geology↗
USGS2012

The significance of 24-norcholestanes, triaromatic steroids and dinosteroids in oils and Cambrian-Ordovician source rocks from the cratonic region of the Tarim Basin, NW China

Two oil families in Ordovician reservoirs from the cratonic region of the Tarim Basin are distinguished by the distribution of regular steranes, triaromatic steroids, norcholestanes and dinosteroids. Oils with relatively lower contents of C 28 regular steranes, C 26 20S, C 26 20R + C 27 20S and C 27 20R regular triaromatic steroids, dinosteranes, 24-norcholestanes and triaromatic dinosteroids originated from Middle–Upper Ordovician source rocks. In contrast, oils with abnormally high abundances of the above compounds are derived from Cambrian and Lower Ordovician source rocks. Only a few oils have previously been reported to be of Cambrian and Lower Ordovician origin, especially in the east region of the Tarim Basin. This study further reports the discovery of oil accumulations of Cambrian and Lower Ordovician origin in the Tabei and Tazhong Uplifts, which indicates a potential for further discoveries involving Cambrian and Lower Ordovician sourced oils in the Tarim Basin. Dinosteroids in petroleum and ancient sediments are generally thought to be biomarkers for dinoflagellates and 24-norcholestanes for dinoflagellates and diatoms. Therefore, the abnormally high abundance of these compounds in extracts from the organic-rich sediments in the Cambrian and Lower Ordovician and related oils in the cratonic region of the Tarim Basin suggests that phytoplankton algae related to dinoflagellates have appeared and might have flourished in the Tarim Basin during the Cambrian Period. Steroids with less common structural configurations are underutilized and can expand understanding of the early development history of organisms, as well as define petroleum systems.

Tarim Basin↗
USGS2018

Regional patterns in the geochemistry of oil-field water, southern San Joaquin Valley, California, USA

Chemical and isotopic data for water co-extracted with hydrocarbons in oil and gas fields are commonly used to examine the source of the formation water and possible impacts on groundwater in areas of oil and gas development. Understanding the geochemical variability of oil-field water could help to evaluate its origin and delineate possible contamination of shallow aquifers in cases where oil-field water is released to the environment. Here we report geochemical and multiple isotope (H, C, O, Sr, Ra) data from 22 oil wells, three sources of produced water that are disposed of in injection wells, and two surface disposal ponds in four oil fields in the southern San Joaquin Valley, California (Fruitvale, Lost Hills, North and South Belridge). Correlations between Cl and δ 18 O, as well as other ions, and gradual increases in salinity with depth, indicate dilution of one or more saline end-members by meteoric water. The saline end-members, represented by deep samples (610 m–2621 m) in three oil-bearing zones, are characterized by Na Cl composition, near-seawater Cl concentrations (median 20,000 mg/L), enriched δ 18 O H 2 O (median 3.4‰), high ammonium(up to 460 mg-N/L), and relatively high radium activity ( 226 Ra+ 228 Ra = 12.3 Bq/L). The deepest sample has low Na/Cl (0.74), high Ca/Mg (5.0), and low 87 Sr/ 86 Sr (0.7063), whereas the shallower samples have higher Na/Cl (0.86–1.2), Ca/Mg near 1, and higher 87 Sr/ 86 Sr (∼0.7083). The data are consistent with an original seawater source being modified by various depth and lithology dependent diagenetic processes. Dilution by meteoric water occurs naturally on the east side of the valley, and in association with water-injectionactivities on the west side. Meteoric-water flushing, particularly on the east side, results in lower solute concentrations (minimum total dissolved solids 2730 mg/L) and total radium (minimum 0.27 Bq/L) in oil-field water, and promotes biodegradation of dissolved organic carbon and hydrocarbon gases like propane. Acetate concentrations and δ 13 C of dissolved inorganic carbon indicate biogenic methane production occurs in some shallow oil zones. Natural and human processes produce substantial variability in the geochemistry of oil-field water that should be considered when evaluating mixing between oil-field waters and groundwater. The variability could result in uncertainty as to detecting the potential source and impact of oil-field water on groundwater.

California↗
USGS2013

A unified assessment of hydrological and biogeochemical responses in research watersheds in Eastern Puerto Rico using runoff-concentration relations

An examination of the relation between runoff rate, R , and concentration, C , of twelve major constituents in four small watersheds in eastern Puerto Rico demonstrates a consistent pattern of responses. For solutes that are not substantially bioactive (alkalinity, silica, calcium, magnesium, sodium, and chloride), the log( R )–log( C ) relation is almost linear and can be described as a weighted average of two sources, bedrock weathering and atmospheric deposition. The slope of the relation for each solute depends on the respective source contributions to the total river load. If a solute were strictly derived from bedrock weathering, the slope would be −0.3 to −0.4, whereas if strictly derived from atmospheric deposition, the slope would be approximately −0.1. The bioactive constituents (dissolved organic carbon, nitrate, sulfate, and potassium), which are recycled by plants and concentrated in shallow soil, demonstrate nearly flat or downward-arched log( R )–log( C ) relations. The peak of the arch represents a transition from dominantly soil-matrix flow to near-surface macropore flow, and finally to overland flow. At highest observed R (80 to >90 mm/h), essentially all reactive surfaces have become wetted, and the input rate of C becomes independent of R (log( R )–log( C ) slope of –1). The highest R are tenfold greater than any previous study. Slight clockwise hysteresis for many solutes in the rivers with riparian zones or substantial hyporheic flows indicates that these settings may act as mixing end-members. Particulate constituents (suspended sediment and particulate organic carbon) show slight clockwise hysteresis, indicating mobilization of stored sediment during rising stage.

Aquatic Geochemistry↗
USGS2004

Chapter 21 Western phosphate field - Depositional and economic deposit models

The Western Phosphate Field (WPF), composed of Permian marine sedimentary strata that cover over 300,000 km 2 in the middle Rocky Mountains of Idaho, Montana, Utah, and Wyoming in the United States, contains vast resources of phosphate mined for fertilizer and a range of other industrial applications. The richest deposits of phosphate in the WPF occur in the Meade Peak Phosphatic Shale Member of the Phosphoria Formation in southeast Idaho. Phosphate is an essential and even limiting nutrient of algal production, which occurs at the bottom of the marine food web in the oceanic photic zone. The high concentrations of phosphate and trace elements in the Phosphoria Formation reflect a low accumulation rate of diluting phases, such as terrigenous siliciclastic debris and carbonate, rather than an unusually high level of primary productivity at the time of deposition. Indeed, the mean rate of accumulation of PO 4 3 required a continuous flux of PO 4 3 into the basin and the photic zone of the water column, but only at a moderate level. This flux was maintained by upwelling of nutrient-rich seawater, imported at depth from the open ocean. Although only a fraction of the organic matter that hosted the PO 4 3 and other nutrients (NO 3 , Cd, Cu, Mo, Ni, and Zn) actually escaped oxidation in the water column, their rate of accu- mulation on the sea floor defined the basin hydrography. Rates of accumulation of Cr, U, V, and rare-earth elements by precipitation and adsorp- tion reactions identify redox conditions in the bottom water as having been denitrifying, maintained by a balance between the rate of oxidation of organic matter settling through the water column and the flux of open-ocean seawater at depth. Atmospheric mixing maintained oxygen respiration in the uppermost several tens of meters of the water column. This hydrography and seawater chemistry are present in several sedimentary envi- ronments in the ocean today. In the WPF, there is an estimated surface mineable reserve base and subeconomic resource of 7.6 billion mt, at an average grade of 24% P 2 O 5 ; a subeconomic underground- mineable resource of 17 billion mt, at a grade of 28%; and 507 billion mt of subresource- grade phosphatic material that underlie the WPF at a depth greater than 305 m. The relationship between phosphate-ore specifications and weathering suggests that significant changes in processing, with associated cost increases, will be required to extend recovery of ore below the relatively strongly weathered zone near the surface. Four open pit mines currently extract phosphate from two moderately to steeply dipping ore zones that typically contain between 20% and 35% P 2 O 5 . Although the shales are enriched in trace elements, especially As, Cd, Cr, Cu, Mo, Se, U, V, Zn, and rare-earth elements, the relative concentration of organic carbon and selected major element oxides determines the suitability of phosphate-rich rock for feed to processing plants and its other applications. Selected specifications from the four operating mines include the following: minimum P 2 O 5 of 18-20% and average of 26-27%; maximum A1 2 O 3 of 1.6-5.0%; maximum MgO of 0.3-0.6%; a CaO/P 2 O 5 ratio of 1.5-1.6; and total carbon content of 4%-5%. Weathering to a depth of as much as 100 m significantly enhances ore quality by decreasing the proportions of calcite, dolomite, and organic matter relative to carbonate fluorapatite, the primary ore mineral

Colorado, Idaho, Montana, Nebraska, North Dakota, ↗
USGS1991

Vanadium accumulation in carbonaceous rocks: A review of geochemical controls during deposition and diagenesis

Published data relevant to the geochemistry of vanadium were used to evaluate processes and conditions that control vanadium accumulation in carbonaceous rocks. Reduction, adsorption, and complexation of dissolved vanadium favor addition of vanadium to sediments rich in organic carbon. Dissolved vanadate (V(V)) species predominate in oxic seawater and are reduced to vanadyl ion (V(IV)) by organic compounds or H2S. Vanadyl ion readily adsorbs to particle surfaces and is added to the sediment as the particles settle. The large vanadium concentrations of rocks deposited in marine as compared to lacustrine environments are the result of the relatively large amount of vanadium provided by circulating ocean water compared to terrestrial runoff. Vanadium-rich carbonaceous rocks typically have high contents of organically bound sulfur and are stratigraphically associated with phosphate-rich units. A correspondence between vanadium content and organically bound sulfur is consistent with high activities of H2S during sediment deposition. Excess H2S exited the sediment into bottom waters and favored reduction of dissolved V(V) to V(IV) or possibly V(III). The stratigraphic association of vanadiferous and phosphatic rocks reflects temporal and spatial shifts in bottom water chemistry from suboxic (phosphate concentrated) to more reducing (euxinic?) conditions that favor vanadium accumulation. During diagenesis some vanadium-organic complexes migrate with petroleum out of carbonaceous rocks, but significant amounts of vanadium are retained in refractory organic matter or clay minerals. As carbon in the rock evolves toward graphite during metamorphism, vanadium is incorporated into silicate minerals. ?? 1991.

Chemical Geology↗
USGS2003

Selected natural attenuation monitoring data, Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington, June 2001

Previous investigations have shown that natural attenuation and biodegradation of chlorinated volatile organic compounds (CVOCs) are substantial in shallow ground water beneath the 9-acre former landfill at Operable Unit 1 (OU 1), Naval Undersea Warfare Center (NUWC), Division Keyport, Washington. The U.S. Geological Survey (USGS) has continued to monitor ground-water geochemistry to assure that conditions remain favorable for contaminant biodegradation. This report presents the ground-water geochemical and selected CVOC data collected at OU 1 by the USGS during June 11-14, 2001 in support of the long-term monitoring for natural attenuation. Overall, the June 2001 data indicate that redox conditions in the upper aquifer remain favorable for reductive dechlorination of CVOCs because strongly reducing conditions persisted beneath much of the former landfill. Redox conditions in the intermediate aquifer down gradient of the landfill appear to have become more favorable for reductive dechlorination because June 2001 dissolved hydrogen concentrations indicated strongly reducing conditions there for the first time. Although changes in redox conditions were observed at certain wells during 2001, a longer monitoring period is needed to ascertain if phytoremediation activities are affecting the ground-water chemistry. A minor change to future monitoring is proposed. Filtered organic carbon (previously referred to as dissolved, and defined as that which passes through a 0.45-micrometer membrane filter) should be analyzed in the future rather than unfiltered (previously referred to as total) organic carbon because the filtered analysis may be a better measure of bioavailable organic carbon. Unfiltered and filtered organic carbon data were collected during June 2001 for comparison. Filtered organic carbon data collected in the future could be reasonably compared with historical unfiltered organic carbon data by multiplying the historical data by a factor of about 0.9.

Open-File Report↗