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USGS2004

Temporal changes in nitrogen adsorption properties of single-walled carbon nanotubes

Temporal evolution of N2 adsorption (77 K) properties of as-produced and purified single-walled nanotubes (SWNTs) samples is described here. The N2 adsorption isotherms are used to characterize the samples' surface areas and porosities. The as-produced samples demonstrate a temporal increase in surface area and pore volumes for up to 16 months. The purified samples, however, reached their stable values of surface area and pore volumes within four to seven months. N2 adsorption capacity of the purified SWNTs also increased when the fresh samples were subjected to thermal pre-processing, with diminishing changes in adsorption capacity with increased age. These observations indicate that the freshly prepared SWNTs, both as-produced and purified, were in an unstable state with their porosity changing with increasing sample age and thermal treatments. It is hypothesized that SWNTs undergo slow but progressive changes in their surface chemistry which causes their N2 adsorption properties to change over several months. ?? 2004 Elsevier Ltd. All rights reserved.

Carbon↗

USGS2012

Physical setting and natural sources of exposure to carcinogenic trace elements and radionuclides in Lahontan Valley, Nevada

In Lahontan Valley, Nevada, arsenic, cobalt, tungsten, uranium, radon, and polonium-210 are carcinogens that occur naturally in sediments and groundwater. Arsenic and cobalt are principally derived from erosion of volcanic rocks in the local mountains and tungsten and uranium are derived from erosion of granitic rocks in headwater reaches of the Carson River. Radon and 210Po originate from radioactive decay of uranium in the sediments. Arsenic, aluminum, cobalt, iron, and manganese concentrations in household dust suggest it is derived from the local soils. Excess zinc and chromium in the dust are probably derived from the vacuum cleaner used to collect the dust, or household sources such as the furnace. Some samples have more than 5 times more cobalt in the dust than in the local soil, but whether the source of the excess cobalt is anthropogenic or natural cannot be determined with the available data. Cobalt concentrations are low in groundwater, but arsenic, uranium, radon, and 210 Po concentrations often exceed human-health standards, and sometime greatly exceed them. Exposure to radon and its decay products in drinking water can vary significantly depending on when during the day that the water is consumed. Although the data suggests there have been no long term changes in groundwater chemistry that corresponds to the Lahontan Valley leukemia cluster, the occurrence of the very unusual leukemia cluster in an area with numerous 210 Po and arsenic contaminated wells is striking, particularly in conjunction with the exceptionally high levels of urinary tungsten in Lahontan Valley residents. Additional research is needed on potential exposure pathways involving food or inhalation, and on synergistic effects of mixtures of these natural contaminants on susceptibility to development of leukemia.

Nevada↗

USGS2003

Helium isotope studies in the Mojave Desert, California: Implications for groundwater chronology and regional seismicity

We report helium isotope and concentration results for groundwaters from the western Mojave River Basin (MRB), 130 km east of Los Angeles, CA. The basin lies adjacent to the NW-SE trending San Andreas Fault (SAF) system. Samples were collected along two groundwater flowpaths that originate in the San Gabriel Mountains and discharge to the Mojave River located ???32 km to the northeast. Additional groundwater samples were collected from Mojave River Deposits underlying the Mojave River. The primary objective of this study is to identify and quantify crustal and mantle helium contributions to the regional groundwater system. A total of 27 groundwaters, sampled previously for chemistry and isotope systematics (including 14C activity) have measured helium concentrations that increase along flowpaths from 9.9??10-8 to 1.0??10-4 cm3 STP g-1 H2O. Concomitantly, 3He/4He ratios decrease from 0.84RA to 0.11RA (RA equals the 3He/4He ratio in air=1.4??10-6). We did not record 3He/4He ratios equivalent to crustal-production values (???0.02RA) in any sample. Dissolved helium concentrations were resolved into components associated with solubility equilibration, air entrainment, mantle-derivation, in-situ production within the aquifer, and extraneous crustal fluxes. All samples contained the first four components, but only older samples had the superimposed effects of helium derived from a crustal flux. The radiogenic He component has chronological significance, and good concordance between 4He and 14C ages for younger groundwaters (<25,000 year) demonstrates the integrity of the 4 He-chronometer in this setting. Helium-rich waters could also be dated with the 4He technique, but only by first isolating the whole crustal flux (3-10??10-6 cm3 STP cm-2 year-1). Mantle-derived 3He (3Hem) is present in all MRB samples irrespective of distance from the SAF. However, regional-aquifer groundwaters near the terminus of the flowpath have a significantly greater content of mantle-derived 3He in comparison with more modern samples. We propose that faults in the basin other than the SAF may be an additional source of mantle-derived helium. The large range in 3He m concentrations may be related to fault activity; however, groundwaters with lower and more constant 3Hem contents may indicate that seismic activity along the SAF has been relatively constant for the past 30,000 years, demonstrating that ancient groundwaters may serve as an archive for paleo-seismic events. ?? 2003 Elsevier B.V. All rights reserved. All rights reserved.

Chemical Geology↗

USGS2004

Borehole petrophysical chemostratigraphy of Pennsylvanian black shales in the Kansas subsurface

Pennsylvanian black shales in Kansas have been studied on outcrop for decades as the core unit of the classic Midcontinent cyclothem. These shales appear to be highstand condensed sections in the sequence stratigraphic paradigm. Nuclear log suites provide several petrophysical measurements of rock chemistry that are a useful data source for chemostratigraphic studies of Pennsylvanian black shales in the subsurface. Spectral gamma-ray logs partition natural radioactivity between contributions by U, Th, and K sources. Elevated U contents in black shales can be related to reducing depositional environments, whereas the K and Th contents are indicators of clay-mineral abundance and composition. The photoelectric factor log measurement is a direct function of aggregate atomic number and so is affected by clay-mineral volume, clay-mineral iron content, and other black shale compositional elements. Neutron porosity curves are primarily a response to hydrogen content. Although good quality logs are available for many black shales, borehole washout features invalidate readings from the nuclear contact devices, whereas black shales thinner than tool resolution will be averaged with adjacent beds. Statistical analysis of nuclear log data between black shales in successive cyclothems allows systematic patterns of their chemical and petrophysical properties to be discriminated in both space and time. ?? 2004 Elsevier B.V. All rights reserved.

Chemical Geology↗

USGS2005

Secondary sulfate minerals associated with acid drainage in the eastern US: Recycling of metals and acidity in surficial environments

Weathering of metal-sulfide minerals produces suites of variably soluble efflorescent sulfate salts at a number of localities in the eastern United States. The salts, which are present on mine wastes, tailings piles, and outcrops, include minerals that incorporate heavy metals in solid solution, primarily the highly soluble members of the melanterite, rozenite, epsomite, halotrichite, and copiapite groups. The minerals were identified by a combination of powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and electron-microprobe. Base-metal salts are rare at these localities, and Cu, Zn, and Co are commonly sequestered as solid solutions within Fe- and Fe-Al sulfate minerals. Salt dissolution affects the surface-water chemistry at abandoned mines that exploited the massive sulfide deposits in the Vermont copper belt, the Mineral district of central Virginia, the Copper Basin (Ducktown) mining district of Tennessee, and where sulfide-bearing metamorphic rocks undisturbed by mining are exposed in Great Smoky Mountains National Park in North Carolina and Tennessee. Dissolution experiments on composite salt samples from three minesites and two outcrops of metamorphic rock showed that, in all cases, the pH of the leachates rapidly declined from 6.9 to <3.7, and specific conductance increased gradually over 24 h. Leachates analyzed after 24-h dissolution experiments indicated that all of the salts provided ready sources of dissolved Al (>30 mg L-1), Fe (>47 mg L-1), sulfate (>1000 mg L-1), and base metals (>1000 mg L-1 for minesites, and 2 mg L-1 for other sites). Geochemical modeling of surface waters, mine-waste leachates, and salt leachates using PHREEQC software predicted saturation in the observed ochre minerals, but significant concentration by evaporation would be needed to reach saturation in most of the sulfate salts. Periodic surface-water monitoring at Vermont minesites indicated peak annual metal loads during spring runoff. At the Virginia site, where no winter-long snowpack develops, metal loads were highest during summer months when salts were dissolved periodically by rainstorms following sustained evaporation during dry spells. Despite the relatively humid climate of the eastern United States, where precipitation typically exceeds evaporation, salts form intermittently in open areas, persist in protected areas when temperature and relative humidity are appropriate, and contribute to metal loadings and acidity in surface waters upon dissolution, thereby causing short-term perturbations in water quality.

Chemical Geology↗

USGS2005

Major and trace element composition of copiapite-group minerals and coexisting water from the Richmond mine, Iron Mountain, California

Copiapite-group minerals of the general formula AR 4 (SO 4 ) 6 (OH) 2 · n H 2 O, where A is predominantly Mg, Fe 2+ , or 0.67Al 3+ , R is predominantly Fe 3+ , and n is typically 20, are among several secondary hydrous Fe sulfates occurring in the inactive mine workings of the massive sulfide deposit at Iron Mountain, CA, a USEPA Superfund site that produces extremely acidic drainage. Samples of copiapite-group minerals, some with coexisting water, were collected from the Richmond mine. Approximately 200 mL of brownish pore water with a pH of −0.9 were extracted through centrifugation from a 10-L sample of moist copiapite-group minerals taken from pyritic muck piles. The pore water is extremely rich in ferric iron (Fe 3+ =149 g L −1 , Fe T =162 g L −1 ) and has a density of 1.52 g mL −1 . The composition of the pore water is interpreted in the context of published phase relations in the Fe 2 O 3 –SO 3 –H 2 O system and previous work on the chemistry of extremely acid mine waters and associated minerals in the Richmond mine. Two distinct members of the copiapite mineral group were identified in the samples with coexisting water: (1) abundant magnesiocopiapite consisting of platy crystals 10 to 50 μm and (2) minor aluminocopiapite present as smaller platy crystals that form spheroidal aggregates. The average composition ( n =5) of the magnesiocopiapite is (Mg 0.90 Fe 2+ 0.17 Zn 0.02 Cu 0.01 ) ∑1.10 (Fe 3+ 3.83 Al 0.09 ) ∑3.92 (SO 4 ) 6.00 (OH) 1.96 ·20H 2 O. Bulk compositions determined by digestion and wet-chemical analysis are consistent with the microanalytical results. These results suggest that magnesiocopiapite is the least soluble member of the copiapite group under the prevailing conditions. Micro-PIXE analysis indicates that the copiapite-group minerals in this sample sequester Zn (average 1420 ppm), with lesser amounts of Cu (average 270 ppm) and As (average 64 ppm).

Chemical Geology↗

USGS2007

Hydrothermal nontronite formation at Eolo Seamount (Aeolian volcanic arc, Tyrrhenian Sea)

A sediment core containing a yellowish-green clay bed was recovered from an area of extensive hydrothermal deposition at the SE slope of the Eolo Seamount, Tyrrhenian Sea. The clay bed is composed of pure nontronite (described for the first time in the Tyrrhenian Sea), which appears to be the most aluminous nontronite ever found among the seafloor hydrothermal deposits. The high Al content suggests precipitation from Al-containing hydrothermal solutions. The REE distribution of the Eolo nontronite has a V-shape pattern. The heavy REE enrichment is in part due to their preferential partitioning in the nontronite structure. This enrichment was possibly further enhanced by the HREE preferential sorption on bacterial cell walls. The light REE enrichment is the result of scavenging uptake by one of the nontronite precursors, i.e., poorly-ordered Fe-oxyhydroxides, from the hydrothermal fluids. Oxygen isotopic composition of the nontronite yields a formation temperature of 30????C, consistent with a low-temperature hydrothermal origin. The relatively radiogenic Nd isotopic signature of the nontronite compared to the present-day Mediterranean seawater indicates that approximately half of Nd, and presumably the rest of the LREE, are derived from local volcanic sources. On the other hand, 87Sr/86Sr is dominated by present-day seawater Sr. Scanning electron microscopy investigation revealed that the nontronite is composed of aggregates of lepispheres and tube-like filaments, which are indicative of bacteria assisted precipitation. Bacteria inhabiting this hydrothermal site likely acted as reactive geochemical surfaces on which poorly-ordered hydrothermal Fe-oxyhydroxides and silica precipitated. Upon aging, the interactions of these primary hydrothermal precipitates coating bacterial filaments and cell walls likely led to the formation of nontronite. Finally, the well-balanced interlayer and layer charges of the crystal lattice of seafloor hydrothermal nontronite decrease its sorption capacity to zero. Thus the ubiquitous nontronite precipitation along the active plate boundaries and around the hot spots has no significant impact on oceanic trace element chemistry. ?? 2007 Elsevier B.V. All rights reserved.

Chemical Geology↗

USGS2008

Deposition of talc - kerolite-smectite - smectite at seafloor hydrothermal vent fields: Evidence from mineralogical, geochemical and oxygen isotope studies

Talc, kerolite-smectite, smectite, chlorite-smectite and chlorite samples from sediments, chimneys and massive sulfides from six seafloor hydrothermal areas have been analyzed for mineralogy, chemistry and oxygen isotopes. Samples are from both peridotite- and basalt-hosted hydrothermal systems, and basaltic systems include sediment-free and sediment-covered sites. Mg-phyllosilicates at seafloor hydrothermal sites have previously been described as talc, stevensite or saponite. In contrast, new data show tri-octahedral Mg-phyllosilicates ranging from pure talc and Fe-rich talc, through kerolite-rich kerolite-smectite to smectite-rich kerolite-smectite and tri-octahedral smectite. The most common occurrence is mixed-layer kerolite-smectite, which shows an almost complete interstratification series with 5 to 85% smectitic layers. The smectite interstratified with kerolite is mostly tri-octahedral. The degree of crystal perfection of the clay sequence decreases generally from talc to kerolite-smectite with lower crystalline perfection as the proportion of smectite layers in kerolite-smectite increases. Our studies do not support any dependence of the precipitated minerals on the type/subtype of hydrothermal system. Oxygen isotope geothermometry demonstrates that talc and kerolite-smectite precipitated in chimneys, massive sulfide mounds, at the sediment surface and in open cracks in the sediment near seafloor are high-temperature (> 250????C) phases that are most probably the result of focused fluid discharge. The other end-member of this tri-octahedral Mg-phyllosilicate sequence, smectite, is a moderate-temperature (200-250????C) phase forming deep within the sediment (??? 0.8??m). Chlorite and chlorite-smectite, which constitute the alteration sediment matrix around the hydrothermal mounds, are lower-temperature (150-200????C) phases produced by diffuse fluid discharge through the sediment around the hydrothermal conduits. In addition to temperature, other two controls on the precipitation of this sequence are the silica activity and Mg/Al ratio (i.e. the degree of mixing of seawater with hydrothermal fluid). Higher silica activity favors the formation of talc relative to tri-octahedral smectite. Vent structures and sedimentary cover preclude complete mixing of hydrothermal fluid and ambient seawater, resulting in lower Mg/Al ratios in the interior parts of the chimneys and deeper in the sediment which leads to the precipitation of phyllosilicates with lower Mg contents. Talc and kerolite-smectite have very low trace- and rare earth element contents. Some exhibit a negative or flat Eu anomaly, which suggests Eu depletion in the original hydrothermal fluid. Such Eu depletion could be caused by precipitation of anhydrite or barite (sinks for Eu2+) deeper in the system. REE abundances and distribution patterns indicate that chlorite and chlorite-smectite are hydrothermal alteration products of the background turbiditic sediment. ?? 2007 Elsevier B.V. All rights reserved.

Chemical Geology↗

USGS2008

Photoreduction fuels biogeochemical cycling of iron in Spain's acid rivers

A number of investigations have shown that photoreduction of Fe(III) causes midday accumulations of dissolved Fe(II) in rivers and lakes, leading to large diel (24-h) fluctuations in the concentration and speciation of total dissolved iron. Less well appreciated is the importance of photoreduction in providing chemical energy for bacteria to thrive in low pH waters. Diel variations in water chemistry from the highly acidic (pH 2.3 to 3.1) Río Tinto, Río Odiel, and Río Agrio of southwestern Spain (Iberian Pyrite Belt) resulted in daytime increases in Fe(II) concentration of 15 to 66 µM at four diel sampling locations. Dissolved Fe(II) concentrations increased with solar radiation, and one of the stream sites showed an antithetic relationship between dissolved Fe(II) and Fe(III) concentrations; both results are consistent with photoreduction. The diel data were used to estimate rates of microbially catalyzed Fe(II) oxidation (1 to 3 nmol L − 1 s − 1 ) and maximum rates of Fe(III) photoreduction (1.7 to 4.3 nmol L − 1 s − 1 ). Bioenergetic calculations indicate that the latter rates are sufficient to build up a population of Fe-oxidizing bacteria to the levels observed in the Río Tinto in about 30 days. We conclude that photoreduction plays an important role in the bioenergetics of the bacterial communities of these acidic rivers, which have previously been shown to be dominated by autotrophic Fe(II)-oxidizers such as Acidithiobacillus ferrooxidans and Leptospirillum ferrooxidans . Given the possibility of the previous existence of acidic, Fe(III)-rich water on Mars, photoreduction may be an important process on other planets, a fact that could have implications to astrobiological research.

Chemical Geology↗

USGS2008

Geochemical controls of elevated arsenic concentrations in groundwater, Ester Dome, Fairbanks district, Alaska

Ester Dome, an upland area near Fairbanks, Alaska, was chosen for a detailed hydrogeochemical study because of the previously reported elevated arsenic in groundwater, and the presence of a large set of wells amenable to detailed sampling. Ester Dome lies within the Fairbanks mining district, where gold-bearing quartz veins, typically containing 2–3 vol.% sulfide minerals (arsenopyrite, stibnite, and pyrite), have been mined both underground and in open cuts. Gold-bearing veins on Ester Dome occur in shear zones and the sulfide minerals in these veins have been crushed to fine-grained material by syn- or post-mineralization movement. Groundwater at Ester Dome is circumneutral, Ca–HCO 3 to Ca–SO 4 type, and ranges from dilute (specific conductance of 48 µS/cm) to more concentrated (specific conductance as high as 2070 µS/cm). In general, solute concentrations increase down hydrologic gradient. Redox species indicate that the groundwaters range from oxic to sub-oxic (low dissolved oxygen, Fe(III) reduction, no SO 4 reduction). Waters with the highest Fe concentrations, as high as 10.7 mg/L, are the most anoxic. Dissolved As concentrations range from < 1 to 1160 µg/L, with a median value of 146 µg/L. Arsenic concentrations are not correlated with specific conductance or Fe concentrations, suggesting that neither groundwater residence time, nor reductive dissolution of iron oxyhydroxides, control the arsenic chemistry. Furthermore, As concentrations do not covary with other constituents that form anions and oxyanions in solution (e.g., HCO 3 , Mo, F, or U) such that desorption of arsenic from clays or oxides also does not control arsenic mobility. Oxidation of arsenopyrite and dissolution of scorodite, in the near-surface environment appears to be the primary control of dissolved As in this upland area. More specifically, the elevated As concentrations are spatially associated with sulfidized shear zones and localities of gold-bearing quartz veins. Consistent with this interpretation, elevated dissolved Sb concentrations (as high as 59 µg/L), also correlated with occurrences of hypogene sulfide minerals, were measured in samples with high dissolved As concentrations.

Chemical Geology↗

USGS2009

In situ measurements of microbially-catalyzed nitrification and nitrate reduction rates in an ephemeral drainage channel receiving water from coalbed natural gas discharge, Powder River Basin, Wyoming, USA

Nitrification and nitrate reduction were examined in an ephemeral drainage channel receiving discharge from coalbed natural gas (CBNG) production wells in the Powder River Basin, Wyoming. CBNG co-produced water typically contains dissolved inorganic nitrogen (DIN), primarily as ammonium. In this study, a substantial portion of discharged ammonium was oxidized within 50 m of downstream transport, but speciation was markedly influenced by diel fluctuations in dissolved oxygen (> 300 µM). After 300 m of transport, 60% of the initial DIN load had been removed. The effect of benthic nitrogen-cycling processes on stream water chemistry was assessed at 2 locations within the stream channel using acrylic chambers to conduct short-term (2–6 h), in-stream incubations. The highest ambient DIN removal rates (2103 µmol N m − 2 h − 1 ) were found at a location where ammonium concentrations > 350 µM. This occurred during light incubations when oxygen concentrations were highest. Nitrification was occurring at the site, however, net accumulation of nitrate and nitrite accounted for < 12% of the ammonium consumed, indicating that other ammonium-consuming processes were also occurring. In dark incubations, nitrite and nitrate consumption were dominant processes, while ammonium was produced rather than consumed. At a downstream location nitrification was not a factor and changes in DIN removal rates were controlled by nitrate reduction, diel fluctuations in oxygen concentration, and availability of electron donor. This study indicates that short-term adaptation of stream channel processes can be effective for removing CBNG DIN loads given sufficient travel distances, but the long-term potential for nitrogen remobilization and nitrogen saturation remain to be determined.

Chemical Geology↗

USGS2009

Processes affecting δ34S and δ18O values of dissolved sulfate in alluvium along the Canadian River, central Oklahoma, USA

The δ 34 S and δ 18 O values for dissolved sulfate in groundwater are commonly used in aquifer studies to identify sulfate reservoirs and describe biogeochemical processes. The utility of these data, however, often is compromised by mixing of sulfate sources within reservoirs and isotope fractionation during sulfur redox cycling. Our study shows that, after all potential sulfate sources are identified and isotopically characterized, the δ 34 S SO4 and δ 18 O SO4 values differentiate processes such as sulfate-source mixing, sulfide oxidation, barite dissolution, and organosulfur decomposition. During bacterial reduction of sulfate, the values reflect kinetic sulfur isotope fractionation and exchange of oxygen isotopes between sulfate and water. Detailed analysis of the chemistry (Cl and SO 4 concentrations) and isotopic composition (δ 2 H H2O and δ 18 O H2O ) of groundwater in an alluvial aquifer in Central Oklahoma, USA allowed the identification of five distinct end members that supply water to the aquifer (regional groundwater flowing into the study area, river water, leachate from a closed landfill that operated within the site, rain, and surface runoff). The δ 34 S SO4 and δ 18 O SO4 values in each end member differentiated three sources of sulfate: sulfate dissolved from Early to Late Permian rocks within the drainage basin (δ 34 S SO4 = 8–12&permil; and δ 18 O SO4 = 10&permil;), iron sulfides oxidized by molecular oxygen during low water-table levels (δ 34 S SO4 = − 16&permil; and δ 18 O SO4 = 10&permil;), and organosulfur compounds (predominately ester sulfates) from decomposition of vegetation on the surface and from landfill trash buried in the alluvium (δ 34 S SO4 = 8&permil; and δ 18 O SO4 = 6&permil;). During bacterial reduction of these sulfate sources, similar isotope fractionation processes are recorded in the parallel trends of increasing δ 34 S SO4 and δ 18 O SO4 values. When extensive reduction occurs, the kinetic sulfur isotope fractionation (estimated by ε H2S–SO4 = − 23&permil;) results in the steady increase of δ 34 S SO4 values to greater than 70&permil;. Equilibrium isotope fractionation during exchange of sulfate oxygen and water oxygen, a process not commonly observed in field-based studies, is documented in δ 18 O SO4 values asymptotically approaching 21&permil;, the value predicted for conditions at the study site ( ε SO4–H2O = 27&permil;). These results show that recognition of all potential sulfate sources is a critical first step to resolving complexities in δ 34 S SO4 and δ 18 O SO4 data. The approach taken in this study can be used in other aquifer systems where the identification of multiple sulfate sources and sulfur redox cycling is important to understanding natural processes and anthropogenic influences.

Oklahoma↗

USGS2010

Dissolution-reprecipitation of igneous zircon in mid-ocean ridge gabbro, Atlantis Bank, Southwest Indian Ridge

Zircons recovered from oceanic gabbro exposed on Atlantis Bank, Southwest Indian Ridge, typically display oscillatory and sector zoning consistent with igneous crystallization from mafic magmas. In one rock (of twenty investigated), weak-oscillatory-zonation patterns are overprinted by secondary textural features characterized by mottled, convoluted and wavy internal zonation patterns that are frequently associated with secondary micron- to submicron-scale micro-porosity. These zircons are hosted in a felsic vein that intruded an oxide gabbro, both of which are cross-cut by monomineralic amphibole- and quartz-rich veinlets. Zircons with weak-oscillatory-zonation patterns record a weighted-average 206 Pb/ 238 U age of 12.76 ± 0.20 Ma (mswd = 1.5), and have high trace element concentrations [e.g., ΣREEs (∼ 0.4–2.2 wt.%), Y (∼ 0.6–2.8 wt.%), P (∼ 0.4–0.9 wt.%)], and Th/U (0.1–0.5). These zircons are anomalously old (≥1 Myr) relative to the magnetic age for this portion of oceanic crust (11.75 Ma). In contrast, zircons with non-igneous, secondary textures have a younger weighted-average 206 Pb/ 238 U age of 12.00 ± 0.16 Ma (mswd = 1.7), and have lower trace element concentrations [e.g., ΣREEs (∼ 0.2–0.8 wt.%), Y (∼ 0.3–1.0 wt.%), P (∼ 0.1–0.3 wt.%)], and slightly lower Th/U (0.1–0.3). The weighted-average age of these zircons is similar to the magnetic anomaly age, and other 206 Pb/ 238 U ages of nearby rocks. We do not observe a correlation between crystallographic misorientation, internal texture, or trace element chemistry. We suggest that the decrease in trace element concentrations associated with the development of non-igneous alteration textures is attributed to the purging of non-essential structural constituent cations from the zircon crystal lattice at amphibolite-facies conditions. The mechanism of alteration/re-equilibration was likely an interface-coupled dissolution–reprecipitation processes that affected pre-existing, anomalously old zircons during shallow-level magmatic construction of Atlantis Bank at ∼ 12.0 Ma.

Chemical Geology↗

USGS2012

CO 2 –rock–brine interactions in Lower Tuscaloosa Formation at Cranfield CO 2 sequestration site, Mississippi, U.S.A.

A highly integrated geochemical program was conducted at the Cranfield CO 2 -enhanced oil recovery (EOR) and sequestration site, Mississippi, U.S.A.. The program included extensive field geochemical monitoring, a detailed petrographic study, and an autoclave experiment under in situ reservoir conditions. Results show that mineral reactions in the Lower Tuscaloosa reservoir were minor during CO 2 injection. Brine chemistry remained largely unchanged, which contrasts with significant changes observed in other field tests. Field fluid sampling and laboratory experiments show consistently slow reactions. Carbon isotopic composition and CO 2 content in the gas phase reveal simple two-end-member mixing between injected and original formation gas. We conclude that the reservoir rock, which is composed mainly of minerals with low reactivity (average quartz 79.4%, chlorite 11.8%, kaolinite 3.1%, illite 1.3%, concretionary calcite and dolomite 1.5%, and feldspar 0.2%), is relatively unreactive to CO 2 . The significance of low reactivity is both positive, in that the reservoir is not impacted, and negative, in that mineral trapping is insignificant.

Mississippi↗

USGS2014

Hydrogeochemistry of prairie pothole region wetlands: Role of long-term critical zone processes

This study addresses the geologic and hydrogeochemical processes operating at a range of scales within the prairie pothole region (PPR). The PPR is a 750,000 km 2 portion of north central North America that hosts millions of small wetlands known to be critical habitat for waterfowl and other wildlife. At a local scale, we characterized the geochemical evolution of the 92-ha Cottonwood Lake study area (CWLSA), located in North Dakota, USA. Critical zone processes are the long-term determinant of wetland water and groundwater geochemistry via the interaction of oxygenated groundwater with pyrite in the underlying glacial till. Pyrite oxidation produced a brown, iron oxide-bearing surface layer locally over 13 m thick and an estimated minimum of 1.3 × 10 10 g sulfate (SO 4 2 − ) at CWLSA. We show that the majority of this SO 4 2− now resides in solid-phase gypsum (CaSO 4 •2H 2 O) and gypsum-saturated groundwater. Results from the CWLSA were scaled up to a 9700 km 2 area surrounding CWLSA using ~ 1800 drill logs and literature data on wetland water chemistry for 178 wetlands within this larger area. The oxidized brown zone depth and wetland water compositional trends are very similar to the CWLSA. Additionally, surface water data from 176 southern Canadian pothole wetlands that conform to the same wetland water geochemical trends as those recorded in the CWLSA further corroborate that SO 4 2 − accumulation driven by pyrite oxidation is a nearly ubiquitous process in the prairie pothole region and distinguishes PPR wetlands from other wetlands worldwide that have a similar overall hydrology.

Manitoba, North Dakota, Saskatchewan↗

USGS2016

Ca, Sr and Ba stable isotopes reveal the fate of soil nutrients along a tropical climosequence

Nutrient biolifting is an important pedogenic process in which plant roots obtain inorganic nutrients such as phosphorus (P) and calcium (Ca) from minerals at depth and concentrate those nutrients at the surface. Here we use soil chemistry and stable isotopes of the alkaline earth elements Ca, strontium (Sr) and barium (Ba) to test the hypothesis that biolifting of P has been an important pedogenic process across a soil climosequence developed on volcanic deposits at Kohala Mountain, Hawaii. The geochemical linkage between these elements is revealed as generally positive site-specific relationships in soil mass gains and losses, particularly for P, Ba and Ca, using the ratio of immobile elements titanium and niobium (Ti/Nb) to link individual soil samples to a restricted compositional range of the chemically and isotopically diverse volcanic parent materials. At sites where P is enriched in surface soils relative to abundances in deeper soils, the isotope compositions of exchangeable Ca, Sr and Ba in the shallowest soil horizons (< 10 cm depth) are lighter than those of the volcanic parent materials and trend toward those of plants growing on fresh volcanic deposits. In contrast the isotope composition of exchangeable Ba in deeper soil horizons (> 10 cm depth) at those sites is consistently heavier than the volcanic parent materials. The isotope compositions of exchangeable Ca and Sr trend toward heavier compositions with depth more gradually, reflecting increasing leakiness from these soils in the order Ba < Sr < Ca and downward transfer of light biocycled Ca and Sr to deeper exchange sites. Given the long-term stability of ecosystem properties at the sites where P is enriched in surface soils, a simple box model demonstrates that persistence of isotopically light exchangeable Ca, Sr and Ba in the shallowest soil horizons requires that the uptake flux to plants from those near-surface layers is less than the recycling flux returned to the surface as litterfall. This observation implicates an uptake flux from an additional source which we attribute to biolifting. We view the heavy exchangeable Ba relative to soil parent values in deeper soils at sites where P is enriched in surface soils, and indeed at all but the wettest site across the climosequence, to represent the complement of an isotopically light Ba fraction removed from these soils by plant roots consistent with the biolifting hypothesis. We further suggest that decreasing heaviness of depth-integrated exchangeable Ba in deeper soils with increasing median annual precipitation across the climosequence reflects greater reliance on shallow nutrient sources as site water balance increases. While the Ca, Sr and Ba isotopes considered together were useful in confirming an important role for nutrient biolifting across the climosequence, the Ba isotopes provided the most robust tracer of biolifting and have the greatest potential to find application as an isotopic proxy for P dynamics in soils.

Hawaii↗

USGS2016

Geochemistry of formation waters from the Wolfcamp and “Cline” shales: Insights into brine origin, reservoir connectivity, and fluid flow in the Permian Basin, USA

Despite being one of the most important oil producing provinces in the United States, information on basinal hydrogeology and fluid flow in the Permian Basin of Texas and New Mexico is lacking. The source and geochemistry of brines from the basin were investigated (Ordovician- to Guadalupian-age reservoirs) by combining previously published data from conventional reservoirs with geochemical results for 39 new produced water samples, with a focus on those from shales. Salinity of the Ca–Cl-type brines in the basin generally increases with depth reaching a maximum in Devonian (median = 154 g/L) reservoirs, followed by decreases in salinity in the Silurian (median = 77 g/L) and Ordovician (median = 70 g/L) reservoirs. Isotopic data for B, O, H, and Sr and ion chemistry indicate three major types of water. Lower salinity fluids (<70 g/L) of meteoric origin in the middle and upper Permian hydrocarbon reservoirs (1.2–2.5 km depth; Guadalupian and Leonardian age) likely represent meteoric waters that infiltrated through and dissolved halite and anhydrite in the overlying evaporite layer. Saline (>100 g/L), isotopically heavy (O and H) water in Leonardian [Permian] to Pennsylvanian reservoirs (2–3.2 km depth) is evaporated, Late Permian seawater. Water from the Permian Wolfcamp and Pennsylvanian “Cline” shales, which are isotopically similar but lower in salinity and enriched in alkalis, appear to have developed their composition due to post-illitization diffusion into the shales. Samples from the “Cline” shale are further enriched with NH 4 , Br, I and isotopically light B, sourced from the breakdown of marine kerogen in the unit. Lower salinity waters (<100 g/L) in Devonian and deeper reservoirs (>3 km depth), which plot near the modern local meteoric water line, are distinct from the water in overlying reservoirs. We propose that these deep meteoric waters are part of a newly identified hydrogeologic unit: the Deep Basin Meteoric Aquifer System. Chemical, isotopic, and pressure data suggest that despite over-pressuring in the Wolfcamp shale, there is little potential for vertical fluid migration to the surface environment via natural conduits.

New Mexico, Texas↗

USGS2018

In situ LA-ICPMS U–Pb dating of cassiterite without a known-age matrix-matched reference material: Examples from worldwide tin deposits spanning the Proterozoic to the Tertiary

Cassiterite (SnO 2 ), a main ore mineral in tin deposits, is suitable for U–Pb isotopic dating because of its relatively high U/Pb ratios and typically low common Pb. We report a LA-ICPMS analytical procedure for U–Pb dating of this mineral with no need for an independently dated matrix-matched cassiterite standard. LA-ICPMS U-Th-Pb data were acquired while using NIST 612 glass as a primary non-matrix-matched standard. Raw data are reduced using a combination of Iolite™ and other off-line data reduction methods. Cassiterite is extremely difficult to digest, so traditional approaches in LA-ICPMS U-Pb geochronology that utilize well-characterized matrix-matched reference materials (e.g., age values determined by ID-TIMS) cannot be easily implemented. We propose a new approach for in situ LA-ICPMS dating of cassiterite, which benefits from the unique chemistry of cassiterite with extremely low Th concentrations (Th/U ratio of 10 −4 or lower) in some cassiterite samples. Accordingly, it is assumed that 208 Pb measured in cassiterite is mostly of non-radiogenic origin—it was initially incorporated in cassiterite during mineral formation, and can be used as a proxy for common Pb. Using 208 Pb as a common Pb proxy instead of 204 Pb is preferred as 204 Pb is much less abundant and is also compromised by 204 Hg interference during the LA-ICPMS analyses. Our procedure relies on 208 Pb/ 206 Pb vs 207 Pb/ 206 Pb (Pb-Pb) and Tera-Wasserburg 207 Pb/ 206 Pb vs 238 U/ 206 Pb (U-Pb) isochron dates that are calculated for a ~1.54 Ga low-Th cassiterite reference material with varying amounts of common Pb that we assume remained a closed U-Pb system. The difference between the NIST 612 glass normalized biased U-Pb date and the Pb-Pb age of the reference material is used to calculate a correction factor (F) for instrumental U-Pb fractionation. The correction factor (F) is then applied to measured U/Pb ratios and Tera-Wasserburg isochron dates are obtained for the unknown cassiterite analyzed in the same analytical session. This allows for U-Pb dating of cassiterite of any age with no need for an independently dated matrix-matched reference material, nor assumptions about the isotopic composition o f common Pb. Results for cassiterite from tin deposits in Bolivia, Brazil, China, Russia, Saudi Arabia, South Africa, Spain, and the United Kingdom, with ages ranging from ~20 Ma to ~2060 Ma, demonstrate the applicability of this approach across a broad range of geologic time. These ages are in good agreement with published geochronology of the host rocks assoc iated with the tin deposits and with previously published U-Pb ages of some cassiterites from the same deposits. Thus, our in situ LA-ICPMS methodology verifies the use of cassiterite as a reliable U-Pb mineral-geochronometer with the advantages of fast and relatively low cost in situ analyses with moderate spatial resolution.

Chemical Geology↗