USGS Science⌕ Search

Geology topics

D.V. Vivit

Publications and source records attributed to D.V. Vivit.

11 recordsLinked to original sources
USGS2018

Solute profiles in soils, weathering gradients and exchange equilibrium/disequilibrium

The spatial and temporal changes in hydrology and pore water elemental and 87/86 Sr compositions were used to determine contemporary weathering rates in a 65 to 226 ky old soil chronosequence formed from granitic sediments deposited on marine terraces along coastal California. Cl-corrected Na, K and Si increased with depth denoting inputs from the weathering of plagioclase and K-feldspar. Solute 87/86 Sr exhibited progressive mixing of sea water-dominated precipitation with inputs from less radiogenic plagioclase. Linear approximations to these weathering gradients were used to determine plagioclase weathering rates of between 0.38 and 8.9×10 −15 moles m −2 s −1 . The lack of corresponding weathering gradients for Ca and Sr indicated short-term equilibrium with the clay ion exchange pool which requires periodic resetting by natural perturbations to maintain continuity, in spite of soil composition changes reflecting the effects of long-term weathering.

Mineralogical Magazine↗
USGS2012

The impact of biotic/abiotic interfaces in mineral nutrient cycling: A study of soils of the Santa Cruz chronosequence, California

Biotic/abiotic interactions between soil mineral nutrients and annual grassland vegetation are characterized for five soils in a marine terrace chronosequence near Santa Cruz, California. A Mediterranean climate, with wet winters and dry summers, controls the annual cycle of plant growth and litter decomposition, resulting in net above-ground productivities of 280–600 g m −2 yr −1 . The biotic/abiotic (A/B) interface separates seasonally reversible nutrient gradients, reflecting biological cycling in the shallower soils, from downward chemical weathering gradients in the deeper soils. The A/B interface is pedologically defined by argillic clay horizons centered at soil depths of about one meter which intensify with soil age. Below these horizons, elevated solute Na/Ca, Mg/Ca and Sr/Ca ratios reflect plagioclase and smectite weathering along pore water flow paths. Above the A/B interface, lower cation ratios denote temporal variability due to seasonal plant nutrient uptake and litter leaching. Potassium and Ca exhibit no seasonal variability beneath the A/B interface, indicating closed nutrient cycling within the root zone, whereas Mg variability below the A/B interface denotes downward leakage resulting from higher inputs of marine aerosols and lower plant nutrient requirements. The fraction of a mineral nutrient annually cycled through the plants, compared to that lost from pore water discharge, is defined their respective fluxes F j,plants = q j,plants /( q j,plants + q j,discharge ) with average values for K and Ca ( F K,plants = 0.99; F Ca,plants = 0.93) much higher than for Mg and Na ( F Mg,plants 0.64; F Na,plants = 0.28). The discrimination against Rb and Sr by plants is described by fractionation factors ( K Sr/Ca = 0.86; K Rb/K = 0.83) which are used in Rayleigh fractionation-mixing calculations to fit seasonal patterns in solute K and Ca cycling. K Rb/K and K 24 Mg / 22 Mg "> K24Mg/22Mg values (derived from isotope data in the literature) fall within fractionation envelopes bounded by inputs from rainfall and mineral weathering. K Sr/Ca and K 44 Ca / 40 Ca "> K44Ca/40Ca fractionation factors fall outside these envelopes indicating that Ca nutrient cycling is closed to these external inputs. Small net positive K and Ca fluxes (6–14 mol m −2 yr −1 ), based on annual mass balances, indicate that the soils are accumulating mineral nutrients, probably as a result of long-term environmental disequilibrium.

California↗
USGS2009

Chemical weathering of a marine terrace chronosequence, Santa Cruz, California. Part II: Solute profiles, gradients and the comparisons of contemporary and long-term weathering rates

The spatial and temporal changes in hydrology and pore water elemental and 87 Sr/ 86 Sr compositions are used to determine contemporary weathering rates in a 65- to 226-kyr-old soil chronosequence formed from granitic sediments deposited on marine terraces along coastal California. Soil moisture, tension and saturation exhibit large seasonal variations in shallow soils in response to a Mediterranean climate. These climate effects are dampened in underlying argillic horizons that progressively developed in older soils, and reached steady-state conditions in unsaturated horizons extending to depths in excess of 15 m. Hydraulic fluxes (q h ), based on Cl mass balances, vary from 0.06 to 0.22 m yr -1 , resulting in fluid residence times in the terraces of 10-24 yrs. As expected for a coastal environment, the order of cation abundances in soil pore waters is comparable to sea water, i.e., Na > Mg > Ca > K > Sr, while the anion sequence Cl > NO 3 > HCO 3 > SO 4 reflects modifying effects of nutrient cycling in the grassland vegetation. Net Cl-corrected solute Na, K and Si increase with depth, denoting inputs from feldspar weathering. Solute 87 Sr/ 86 Sr ratios exhibit progressive mixing of sea water-dominated precipitation with inputs from less radiogenic plagioclase. While net Sr and Ca concentrations are anomalously high in shallow soils due to biological cycling, they decline with depth to low and/or negative net concentrations. Ca/Mg, Sr/Mg and 87 Sr/ 86 Sr solute and exchange ratios are similar in all the terraces, denoting active exchange equilibration with selectivities close to unity for both detrital smectite and secondary kaolinite. Large differences in the magnitudes of the pore waters and exchange reservoirs result in short-term buffering of the solute Ca, Sr, and Mg. Such buffering over geologic time scales can not be sustained due to declining inputs from residual plagioclase and smectite, implying periodic resetting of the exchange reservoir such as by past vegetational changes and/or climate. Pore waters approach thermodynamic saturation with respect to albite at depth in the younger terraces, indicating that weathering rates ultimately become transport-limited and dependent on hydrologic flux. Contemporary rates R solute are estimated from linear Na and Si pore weathering gradients b solute such that R solute = frac(q h , b solute ?? S v ) where S v is the volumetric surface area and ?? is the stoichiometric coefficient. Plagioclase weathering rates (0.38-2.8 ?? 10 -15 mol m -2 s -1 ) are comparable to those based on 87 Sr/ 86 Sr mass balances and solid-state Na and Ca gradients using analogous gradient approximations. In addition, contemporary solute gradients, under transport-limited conditions, approximate long-term solid-state gradients when normalized against the mass of protolith plagioclase and its corresponding aqueous solubility. The multi-faceted weathering analysis presented in this paper is perhaps the most comprehensive yet applied to a single field study. Within uncertainties of the methods used, present day weathering rates, based on solute characterizations, are comparable to average long-term past rates as evidenced by soil profiles.

Geochimica et Cosmochimica Acta↗
USGS2005

The ubiquitous nature of accessory calcite in granitoid rocks: Implications for weathering, solute evolution, and petrogenesis

Calcite is frequently cited as a source of excess Ca, Sr and alkalinity in solutes discharging from silicate terrains yet, no previous effort has been made to assess systematically the overall abundance, composition and petrogenesis of accessory calcite in granitoid rocks. This study addresses this issue by analyzing a worldwide distribution of more than 100 granitoid rocks. Calcite is found to be universally present in a concentration range between 0.028 to 18.8 g kg −1 (mean = 2.52 g kg −1 ). Calcite occurrences include small to large isolated anhedral grains, fracture and cavity infillings, and sericitized cores of plagioclase. No correlation exists between the amount of calcite present and major rock oxide compositions, including CaO. Ion microprobe analyses of in situ calcite grains indicate relatively low Sr (120 to 660 ppm), negligible Rb and 87 Sr/ 86 Sr ratios equal to or higher than those of coexisting plagioclase. Solutes, including Ca and alkalinity produced by batch leaching of the granitoid rocks (5% CO 2 in DI water for 75 d at 25°C), are dominated by the dissolution of calcite relative to silicate minerals. The correlation of these parameters with higher calcite concentrations decreases as leachates approach thermodynamic saturation. In longer term column experiments (1.5 yr), reactive calcite becomes exhausted, solute Ca and Sr become controlled by feldspar dissolution and 87 Sr/ 86 Sr by biotite oxidation. Some accessory calcite in granitoid rocks is related to intrusion into carbonate wall rock or produced by later hydrothermal alteration. However, the ubiquitous occurrence of calcite also suggests formation during late stage (subsolidus) magmatic processes. This conclusion is supported by petrographic observations and 87 Sr/ 86 Sr analyses. A review of thermodynamic data indicates that at moderate pressures and reasonable CO 2 fugacities, calcite is a stable phase at temperatures of 400 to 700°C.

Geochimica et Cosmochimica Acta↗
USGS1999

The role of disseminated calcite in the chemical weathering of granitoid rocks

Accessory calcite, present at concentrations between 300 and 3000 mg kg-1, occurs in fresh granitoid rocks sampled from the Merced watershed in Yosemite National Park, CA, USA; Loch Vale in Rocky Mountain National Park CO USA; the Panola watershed, GA USA; and the Rio Icacos, Puerto Rico. Calcite occurs as fillings in microfractures, as disseminated grains within the silicate matrix, and as replacement of calcic cores in plagioclase. Flow-through column experiments, using de-ionized water saturated with 0.05 atm. CO2, produced effluents from the fresh granitoid rocks that were dominated by Ca and bicarbonate and thermodynamically saturated with calcite. During reactions up to 1.7 yr, calcite dissolution progressively decreased and was superceded by steady state dissolution of silicates, principally biotite. Mass balance calculations indicate that most calcite had been removed during this time and accounted for 57-98% of the total Ca released from these rocks. Experimental effluents from surfically weathered granitoids from the same watersheds were consistently dominated by silicate dissolution. The lack of excess Ca and alkalinity indicated that calcite had been previously removed by natural weathering. The extent of Ca enrichment in watershed discharge fluxes corresponds to the amounts of calcite exposed in granitoid rocks. High Ca/Na ratios relative to plagioclase stoichiometries indicate excess Ca in the Yosemite, Loch Vale, and other alpine watersheds in the Sierra Nevada and Rocky Mountains of the western United States. This Ca enrichment correlates with strong preferential weathering of calcite relative to plagioclase in exfoliated granitoids in glaciated terrains. In contrast, Ca/Na flux ratios are comparable to or less than the Ca/Na ratios for plagioclase in the subtropical Panola and tropical Rio Icacos watersheds, in which deeply weathered regoliths exhibit concurrent losses of calcite and much larger masses of plagioclase during transport-limited weathering. These results indicate that the weathering of accessory calcite may strongly influence Ca and alkalinity fluxes from silicate rocks during and following periods of glaciation and tectonism but is much less important for older stable geomorphic surfaces.

Geochimica et Cosmochimica Acta↗
USGS1999

The effect of temperature on experimental and natural chemical weathering rates of granitoid rocks

The effects of climatic temperature variations (5-35??C) on chemical weathering are investigated both experimentally using flow-through columns containing fresh and weathered granitoid rocks and for natural granitoid weathering in watersheds based on annual solute discharge. Although experimental Na and Si effluent concentrations are significantly higher in the fresh relative to the weathered granitoids, the proportional increases in concentration with increasing temperature are similar. Si and Na exhibit comparable average apparent activation energies (E(a)) of 56 and 61 kJ/mol, respectively, which are similar to those reported for experimental feldspar dissolution measured over larger temperature ranges. A coupled temperature-precipitation model, using an expanded database for solute discharge fluxes from a global distribution of 86 granitoid watersheds, produces an apparent activation energy for Si (51 kJ/mol), which is also comparable to those derived from the experimental study. This correlation reinforces evidence that temperature does significantly impact natural silicate weathering rates. Effluent K concentrations in the column study are elevated with respect to other cations compared to watershed discharge due to the rapid oxidation/dissolution of biotite. K concentrations are less sensitive to temperature, resulting in a lower average E(a) value (27 kJ/mol) indicative of K loss from lower energy interlayer sites in biotite. At lower temperatures, initial cation release from biotite is significantly faster than cation release from plagioclase. This agrees with reported higher K/Na ratios in cold glacial watersheds relative to warmer temperate environments. Increased release of less radiogenic Sr from plagioclase relative to biotite at increasing temperature produces corresponding decreases in 87Sr/86Sr ratios in the column effluents. A simple mixing calculation using effluent K/Na ratios, Sr concentrations and 87Sr/86Sr ratios for biotite and plagioclase approximates stoichiometric cation ratios from biotite/plagioclase dissolution at warmer temperatures (35??C), but progressively overestimates the relative proportion of biotite with decreasing temperature. Ca, Mg, and Sr concentrations closely correlate, exhibit no consistent trends with temperature, and are controlled by trace amounts of calcite or exchange within weathered biotite. The inability of the watershed model to differentiate a climate signal for such species correlates with the lower temperature dependence observed in the experimental studies.

Geochimica et Cosmochimica Acta↗
USGS1998

Chemical weathering in a tropical watershed, Luquillo Mountains, Puerto Rico: I. Long-term versus short-term weathering fluxes

The pristine Rio Icacos watershed in the Luquillo Mountains in eastern Puerto Rico has the fastest documented weathering rate of silicate rocks on the Earth's surface. A regolith propagation rate of 58 m Ma-1 calculated from iso-volumetric saprolite formation from quartz diorite, is comparable to the estimated denudation rate (25-50 Ma-1) but is an order of magnitude faster than the global average weathering rate (6 Ma-1). Weathering occurs in two distinct environments; plagioclase and hornblende react at the saprock interface and biotite and quartz weather in the overlying thick saprolitic regolith. These environments produce distinctly different water chemistries, with K, Mg, and Si increasing linearly with depth in saprolite porewaters and with stream waters dominated by Ca, Na, and Si. Such differences are atypical of less intense weathering in temperate watersheds. Porewater chemistry in the shallow regolith is controlled by closed-system recycling of inorganic nutrients such as K. Long-term elemental fluxes through the regolith (e.g., Si = 1.7 ?? 10-8 moles m-2 s-1) are calculated from mass losses based on changes in porosity and chemistry between the regolith and bedrock and from the age of the regolith surface (200 Ma). Mass losses attributed to solute fluxes are determined using a step-wise infiltration model which calculates mineral inputs to the shallow and deep saprolite porewaters and to stream water. Pressure heads decrease with depth in the shallow regolith (-2.03 m H2O m-1), indicating that both increasing capillary tension and graviometric potential control porewater infiltration. Interpolation of experimental hydraulic conductivities produces an infiltration rate of 1 m yr-1 at average field moisture saturation which is comparable with LiBr tracer tests and with base discharge from the watershed. Short term weathering fluxes calculated from solute chemistries and infiltration rates (e.g., Si = 1.4 ?? 10-8 moles m-2 s-1) are compared to watershed flux rates (e.g., Si = 2.7 ?? 10-8 moles m-2 s-1). Consistency between three independently determined sets of weathering fluxes imply that possible changes in precipitation, temperature, and vegetation over the last several hundred thousand years have not significantly impacted weathering rates in the Luquillo Mountains of Puerto Rico. This has important ramifications for tropical environments and global climate change. Copyright ?? 1998 Elsevier Science Ltd.

Geochimica et Cosmochimica Acta↗
USGS1985

Selected methods for dissolved iron (II, III) and dissolved sulfide (-II) determinations in geothermal waters

Dissolved sulfide (-II) and dissolved iron (II, III) were determined in geothermal well water samples collected at Cerro Prieto, Mexico. Most samples consisted of liquid and gas (two phases) at the instant of collection; and a subset of samples, referred to as ' flashed ' samples, consisted of pressurized steam samples which were allowed to condense. Sulfide was determined by sulfide specific ion electrode; Fe(II) and Fe(III) plus Fe(II) were determined spectrophotometrically. The precision and accuracy of the methods were evaluated for these high-silica waters with replicate analyses, spike recoveries, and an alternate method. Direct current (d.c.) argon plasma emission spectrometry was the alternate method used for Fe(III)-plus-Fe(II) analyses. Mean dissolved iron concentrations ranged from 20.2 to 834 micrograms/L (ug/L) as Fe(II) and 26.8 to 904 ug/L as Fe(III) plus Fe(II). Mean sulfide concentrations ranged from about 0.01 to 5.3 mg/L (S-II) Generally, higher S(-II) values and larger Fe(II)/Fe(III) ratios were found in the two-phase samples. These findings suggest that the ' flashed ' samples are at a less reduced state than the two-phase samples. (Author 's abstract)

Water-Resources Investigations Report↗
USGS1984

Specific-lon electrode determinations of sulfide preconcentrated from San Francisco Bay waters

Measurements of low-level dissolved-sulfide concentrations in estuarine water from San Francisco Bay have been made using the sulfide-specific electrode after preservation, separation, and preconcentration of the sulfide species. The separation and preconcentration were acheived by coprecipitation of ZnS with Zn(OH)2 followed by collection and dissolution of the precipitate, giving concentration factors up to 160-fold Preconcentration provided sulfide solutions that were adequately measurable within the practical working range of the specific-ion electrode The sulfide detection limit with the preconcentration step is 0 02 ??g/l Spike recoveries in the range of 81 to 10 1% have been achieved for laboratory-prepared samples having S2- concentrations as low as 0 6 ??g/l and 84 to 100% for an estuarine sample spiked in the field with 2 ??g/l (S(-II) Positive correlations have been found between dissolved S(-II) concentrations and concentrations of dissolved Cd, Cu, and Ni, negative correlations have been found between bisulfide (HS-) activity and activities of Cd2+, Cu2+, and Ag+ species ?? 1984 Springer-Verlag New York Inc.

Environmental Geology and Water Sciences↗