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Geology topics

A. F. White

Publications and source records attributed to A. F. White.

At least 19 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

Geochemistry of water at Cajon Pass, California: Preliminary results

Samples of water and associated gases were collected from the Cajon Pass well using downhole samplers, and from the pipe stands at the completion of drill stem tests. The fluids were recovered from fracture systems in granitic rocks from two uncased test intervals located at 1,829 to 1,905 m and 1,829 to 2,115 m. Results of chemical analysis indicate major differences in the composition of water from different fracture systems. Water from one fracture system in the first test interval has a salinity of 2,150 mg/L dissolved solids and is relatively high in Cl, Ca and Fe, but low in HCO 3 and SO 4 ; water salinity from a second fracture system is only 950 mg/L and is dominated by Na, HCO 3 and SO 4 . Most of the water from the second interval likely originated from one fracture system; it is alkaline, low in HCO 3 , has a salinity of 1,150 mg/L, and is a NaSO 4 type water characteristic of pore water in the granitic rocks of the area. The differences in water composition indicate different evolutionary paths and isolation of water within relatively proximal fracture systems.

Geophysical Research Letters↗
USGS2012

Applications of mineral surface chemistry to environmental problems

Environmental surface chemistry involves processes that occur at the interface between the regolith, hydrosphere and atmosphere. The more limited scope of the present review addresses natural and anthropogenically-induced inorganic geochemical reactions between solutes in surface and ground waters and soil and aquifer substrates. Important surficial reactions include sorption, ion exchange, dissolution, precipitation and heterogeneous oxidation/reduction processes occurring at the solid/aqueous interface. Recent research advances in this field have addressed, both directly and indirectly, societal issues related to water quality, pollution, biogeochemical cycling, nutrient budgets and chemical weathering related to long term global climate change. This review will include recent advances in the fundamental and theoretical understanding of these surficial processes, breakthroughs in experimental and instrumental surface characterization, and development of methodologies for field applications.

Reviews of Geophysics↗
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

The reduction of aqueous metal species on the surfaces of Fe(II)-containing oxides: The role of surface passivation

The reduction of aqueous transition metal species at the surfaces of Fe(II)- containing oxides has important ramifications in predicting the transport behavior in ground water aquifers. Experimental studies using mineral suspensions and electrodes demonstrate that structural Fe(II) heterogeneously reduces aqueous ferric, cupric, vanadate and chromate ions on magnetite and ilmenite surfaces. The rates of metal reduction on natural oxides is strongly dependent on the extent of surface passivation and redox conditions in the weathering environment. Synchrotron studies show that surface oxidation of Fe(II)-containing oxide minerals decreases their capacity for Cr(VI) reduction at hazardous waste disposal sites.

ACS Symposium Series↗
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↗
USGS2009

The role of reaction affinity and secondary minerals in regulating chemical weathering rates at the Santa Cruz Soil Chronosequence, California

In order to explore the reasons for the apparent discrepancy between laboratory and field weathering rates and to determine the extent to which weathering rates are controlled by the approach to thermodynamic equilibrium, secondary mineral precipitation, and flow rates, a multicomponent reactive transport model (CrunchFlow) was used to interpret soil profile development and mineral precipitation and dissolution rates at the 226 ka Marine Terrace Chronosequence near Santa Cruz, CA. Aqueous compositions, fluid chemistry, transport, and mineral abundances are well characterized [White A. F., Schulz M. S., Vivit D. V., Blum A., Stonestrom D. A. and Anderson S. P. (2008) Chemical weathering of a Marine Terrace Chronosequence, Santa Cruz, California. I: interpreting the long-term controls on chemical weathering based on spatial and temporal element and mineral distributions. Geochim. Cosmochim. Acta 72 (1), 36-68] and were used to constrain the reaction rates for the weathering and precipitating minerals in the reactive transport modeling. When primary mineral weathering rates are calculated with either of two experimentally determined rate constants, the nonlinear, parallel rate law formulation of Hellmann and Tisserand [Hellmann R. and Tisserand D. (2006) Dissolution kinetics as a function of the Gibbs free energy of reaction: An experimental study based on albite feldspar. Geochim. Cosmochim. Acta 70 (2), 364-383] or the aluminum inhibition model proposed by Oelkers et al. [Oelkers E. H., Schott J. and Devidal J. L. (1994) The effect of aluminum, pH, and chemical affinity on the rates of aluminosilicate dissolution reactions. Geochim. Cosmochim. Acta 58 (9), 2011-2024], modeling results are consistent with field-scale observations when independently constrained clay precipitation rates are accounted for. Experimental and field rates, therefore, can be reconciled at the Santa Cruz site. Additionally, observed maximum clay abundances in the argillic horizons occur at the depth and time where the reaction fronts of the primary minerals overlap. The modeling indicates that the argillic horizon at Santa Cruz can be explained almost entirely by weathering of primary minerals and in situ clay precipitation accompanied by undersaturation of kaolinite at the top of the profile. The rate constant for kaolinite precipitation was also determined based on model simulations of mineral abundances and dissolved Al, SiO 2 (aq) and pH in pore waters. Changes in the rate of kaolinite precipitation or the flow rate do not affect the gradient of the primary mineral weathering profiles, but instead control the rate of propagation of the primary mineral weathering fronts and thus total mass removed from the weathering profile. Our analysis suggests that secondary clay precipitation is as important as aqueous transport in governing the amount of dissolution that occurs within a profile because clay minerals exert a strong control over the reaction affinity of the dissolving primary minerals. The modeling also indicates that the weathering advance rate and the total mass of mineral dissolved is controlled by the thermodynamic saturation of the primary dissolving phases plagioclase and K-feldspar, as is evident from the difference in propagation rates of the reaction fronts for the two minerals despite their very similar kinetic rate laws. ?? 2009 Elsevier Ltd.

Geochimica et Cosmochimica Acta↗
USGS2008

Chemical weathering of a marine terrace chronosequence, Santa Cruz, California I: Interpreting rates and controls based on soil concentration-depth profiles

The spatial and temporal changes in element and mineral concentrations in regolith profiles in a chronosequence developed on marine terraces along coastal California are interpreted in terms of chemical weathering rates and processes. In regoliths up to 15 m deep and 226 kyrs old, quartz-normalized mass transfer coefficients indicate non-stoichiometric preferential release of Sr > Ca > Na from plagioclase along with lesser amounts of K, Rb and Ba derived from K-feldspar. Smectite weathering results in the loss of Mg and concurrent incorporation of Al and Fe into secondary kaolinite and Fe-oxides in shallow argillic horizons. Elemental losses from weathering of the Santa Cruz terraces fall within the range of those for other marine terraces along the Pacific Coast of North America. Residual amounts of plagioclase and K-feldspar decrease with terrace depth and increasing age. The gradient of the weathering profile bs is defined by the ratio of the weathering rate, R to the velocity at which the profile penetrates into the protolith. A spreadsheet calculator further refines profile geometries, demonstrating that the non-linear regions at low residual feldspar concentrations at shallow depth are dominated by exponential changes in mineral surface-to-volume ratios and at high residual feldspar concentrations, at greater depth, by the approach to thermodynamic saturation. These parameters are of secondary importance to the fluid flux qh, which in thermodynamically saturated pore water, controls the weathering velocity and mineral losses from the profiles. Long-term fluid fluxes required to reproduce the feldspar weathering profiles are in agreement with contemporary values based on solute Cl balances (qh = 0.025-0.17 m yr-1). During saturation-controlled and solute-limited weathering, the greater loss of plagioclase relative to K-feldspar is dependent on the large difference in their respective solubilities instead of the small difference between their respective reaction kinetics. The steady-state weathering rate under such conditions is defined asR = fenced(qh ?? frac(msol, Mtotal)) ?? fenced(frac(1, Sv ?? bs)) ??. The product of qh and the ratio of solubilized to solid state feldspar (msat/Mtotal) define the weathering velocity. The weathering gradient bs reflects the kinetic rate of reaction where Sv is the volumetric surface area of the residual feldspar. Both this rate expression and the spreadsheet calculations produce similar plagioclase weathering rates (R = 5-14 ?? 10-16 mol m-2 s-1) which agree with those reported for other environments of comparable climate and age. Weathering-dependent concentration profiles are commonly described in literature. The present paper provides methods by which these data can yield a more fundamental understanding of the weathering processes involved.

Geochimica et Cosmochimica Acta↗
USGS2008

Modelling chemical depletion profiles in regolith

Chemical or mineralogical profiles in regolith display reaction fronts that document depletion of leachable elements or minerals. A generalized equation employing lumped parameters was derived to model such ubiquitously observed patterns:C = frac(C0, frac(C0 - Cx = 0, Cx = 0) exp (??ini ?? over(k, ??) ?? x) + 1)Here C, Cx = 0, and Co are the concentrations of an element at a given depth x, at the top of the reaction front, or in parent respectively. ??ini is the roughness of the dissolving mineral in the parent and k???? is a lumped kinetic parameter. This kinetic parameter is an inverse function of the porefluid advective velocity and a direct function of the dissolution rate constant times mineral surface area per unit volume regolith. This model equation fits profiles of concentration versus depth for albite in seven weathering systems and is consistent with the interpretation that the surface area (m2 mineral m- 3 bulk regolith) varies linearly with the concentration of the dissolving mineral across the front. Dissolution rate constants can be calculated from the lumped fit parameters for these profiles using observed values of weathering advance rate, the proton driving force, the geometric surface area per unit volume regolith and parent concentration of albite. These calculated values of the dissolution rate constant compare favorably to literature values. The model equation, useful for reaction fronts in both steady-state erosional and quasi-stationary non-erosional systems, incorporates the variation of reaction affinity using pH as a master variable. Use of this model equation to fit depletion fronts for soils highlights the importance of buffering of pH in the soil system. Furthermore, the equation should allow better understanding of the effects of important environmental variables on weathering rates. ?? 2008.

Geoderma↗
USGS2007

Physical and chemical controls on the critical zone

Geochemists have long recognized a correlation between rates of physical denudation and chemical weathering. What underlies this correlation? The Critical Zone can be considered as a feed-through reactor. Downward advance of the weathering front brings unweathered rock into the reactor. Fluids are supplied through precipitation. The reactor is stirred at the top by biological and physical processes. The balance between advance of the weathering front by mechanical and chemical processes and mass loss by denudation fixes the thickness of the Critical Zone reactor. The internal structure of this reactor is controlled by physical processes that create surface area, determine flow paths, and set the residence time of material in the Critical Zone. All of these impact chemical weathering flux.

Elements↗
USGS2006

Coupling chemical weathering with soil production across soil-mantled landscapes

Soil-covered upland landscapes constitute a critical part of the habitable world. Our understanding of how they evolve as a function of different climatic, tectonic and geological regimes is important across a wide range of disciplines and depends, in part, on understanding the links between chemical and physical weathering processes. Extensive previous work has shown that soil production rates decrease with increasing soil column thickness, but chemical weathering rates were not measured. Here we examine a granitic, soil-mantled hillslope at Point Reyes, California, where soil production rates were determined using in situ produced cosmogenic nuclides ( 10 Be and 26 Al), and we quantify the extent as well as the rates of chemical weathering of the saprolite from beneath soil from across the landscape. We collected saprolite samples from the base of soil pits and analysed them for abrasion pH as well as for major and trace elements by X-ray fluorescence spectroscopy, and for clay mineralogy by X-ray diffraction spectroscopy. Our results show for the first time that chemical weathering rates decrease with increasing soil thickness and account for 13 to 51 per cent of total denudation. We also show that spatial variation in chemical weathering appears to be topographically controlled: weathering rate decreases with slope across the divergent ridge and increases with upslope contributing area in the convergent swale. Furthermore, to determine the best measure for the extent of saprolite weathering, we compared four different chemical weathering indices – the Vogt ratio, the chemical index of alteration (CIA), Parker's index, and the silicon–aluminium ratio – with saprolite pH. Measurements of the CIA were the most closely correlated with saprolite pH, showing that weathering intensity decreases linearly with an increase in saprolite pH from 4·7 to almost 7. Data presented here are among the first to couple directly rates of soil production and chemical weathering with how topography is likely to control weathering at a hillslope scale.

Earth Surface Processes and Landforms↗
USGS2006

Controls on soil pore water solutes: An approach for distinguishing between biogenic and lithogenic processes

Spatial and temporal variations in pore water compositions are characterized for a deep regolith profile developed on a marine terrace chronosequence near Santa Cruz California. Variations are resolved in terms of the dominance of either a lithogenic process, i.e. chemical weathering, or a biogenic process, i.e. plant nutrient cycling. The concept of elemental fractionation is introduced describing the extent that specific elements are mobilized and cycled as a result of these processes.

Journal of Geochemical Exploration↗
USGS2005

Measurement and interpretation of low levels of dissolved oxygen in ground water

A Rhodazine-D colorimetric technique was adapted to measure low-level dissolved oxygen concentrations in ground water. Prepared samples containing between 0 and 8.0 μmoles · 1 -1 dissolved oxygen in equilibrium with known gas mixtures produced linear spectrophotometric absorbance with a lower detection limit of 0.2 μmoles · 1 -1 . Excellent reproducibility was found for solutions ranging in composition from deionized water to sea water with chemical interferences detected only for easily reduced metal species such as ferric ion, cupric ion, and hexavalent chromium. Such effects were correctable based on parallel reaction stoichiometries relative to oxygen. The technique, coupled with a downhole wire line tool, permitted low-level monitoring of dissolved oxygen in wells at the selenium-contaminated Kesterson Reservoir in California. Results indicated a close association between low but measurable dissolved oxygen concentrations and mobility of oxidized forms of selenium in the shallow aquifer which were in general electrochemical disequilibrium.

Groundwater↗
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↗
USGS2005

Chemical weathering rates of a soil chronosequence on granitic alluvium: III. Hydrochemical evolution and contemporary solute fluxes and rates

Although long-term changes in solid-state compositions of soil chronosequences have been extensively investigated, this study presents the first detailed description of the concurrent hydrochemical evolution and contemporary weathering rates in such sequences. The most direct linkage between weathering and hydrology over 3 million years of soil development in the Merced chronosequence in Central California relates decreasing permeability and increasing hydrologic heterogeneity to the development of secondary argillic horizons and silica duripans. In a highly permeable, younger soil (40 kyr old), pore water solutes reflect seasonal to decadal-scale variations in rainfall and evapotranspiration (ET). This climate signal is strongly damped in less permeable older soils (250 to 600 kyr old) where solutes increasingly reflect weathering inputs modified by heterogeneous flow. Elemental balances in the soils are described in terms of solid state, exchange and pore water reservoirs and input/output fluxes from precipitation, ET, biomass, solute discharge and weathering. Solute mineral nutrients are strongly dependent on biomass variations as evidenced by an apparent negative K weathering flux reflecting aggradation by grassland plants. The ratios of solute Na to other base cations progressively increase with soil age. Discharge fluxes of Na and Si, when integrated over geologic time, are comparable to solid-state mass losses in the soils, implying similar past weathering conditions. Similarities in solute and sorbed Ca/Mg ratios reflect short-term equilibrium with the exchange reservoir. Long-term consistency in solute ratios, when contrasted against progressive decreases in solid-state Ca/Mg, requires an additional Ca source, probably from dry deposition. Amorphous silica precipitates from thermodynamically-saturated pore waters during periods of high evapotranspiration and result in the formation of duripans in the oldest soils. The degree of feldspar and secondary gibbsite and kaolinite saturation varies both spatially and temporally due to the seasonality of plant-respired CO 2 and a decrease in organically complexed Al. In deeper pore waters, K-feldspar is in equilibrium and plagioclase is about an order of magnitude undersaturated. Hydrologic heterogeneity produces a range of weathering gradients that are constrained by solute distributions and matrix and macropore flow regimes. Plagioclase weathering rates, based on precipitation-corrected Na gradients, vary between 3 and 7 × 10 −16 mol m −2 s −1 . These rates are similar to previously determined solid-state rates but are several orders of magnitude slower than for experimental plagioclase dissolution indicating strong inhibitions to natural weathering, partly due to near-equilibrium weathering reactions.

Geochimica et Cosmochimica Acta↗
USGS2002

Determining mineral weathering rates based on solid and solute weathering gradients and velocities: Application to biotite weathering in saprolites

Chemical weathering gradients are defined by the changes in the measured elemental concentrations in solids and pore waters with depth in soils and regoliths. An increase in the mineral weathering rate increases the change in these concentrations with depth while increases in the weathering velocity decrease the change. The solid-state weathering velocity is the rate at which the weathering front propagates through the regolith and the solute weathering velocity is equivalent to the rate of pore water infiltration. These relationships provide a unifying approach to calculating both solid and solute weathering rates from the respective ratios of the weathering velocities and gradients. Contemporary weathering rates based on solute residence times can be directly compared to long-term past weathering based on changes in regolith composition. Both rates incorporate identical parameters describing mineral abundance, stoichiometry, and surface area. Weathering gradients were used to calculate biotite weathering rates in saprolitic regoliths in the Piedmont of Northern Georgia, USA and in Luquillo Mountains of Puerto Rico. Solid-state weathering gradients for Mg and K at Panola produced reaction rates of 3 to 6 x 10-17 mol m-2 s-1 for biotite. Faster weathering rates of 1.8 to 3.6 ?? 10-16 mol m-2 s-1 are calculated based on Mg and K pore water gradients in the Rio Icacos regolith. The relative rates are in agreement with a warmer and wetter tropical climate in Puerto Rico. Both natural rates are three to six orders of magnitude slower than reported experimental rates of biotite weathering. ?? 2002 Elsevier Science B.V. All rights reserved.

Chemical Geology↗
USGS2001

Differential rates of feldspar weathering in granitic regoliths

Differential rates of plagioclase and K-feldspar weathering commonly observed in bedrock and soil environments are examined in terms of chemical kinetic and solubility controls and hydrologic permeability. For the Panola regolith, in the Georgia Piedmont Province of southeastern United States, petrographic observations, coupled with elemental balances and 87Sr/86Sr ratios, indicate that plagioclase is being converted to kaolinite at depths > 6 m in the granitic bedrock. K-feldspar remains pristine in the bedrock but subsequently weathers to kaolinite at the overlying saprolite. In contrast, both plagioclase and K-feldspar remain stable in granitic bedrocks elsewhere in Piedmont Province, such as Davis Run, Virginia, where feldspars weather concurrently in an overlying thick saprolite sequence. Kinetic rate constants, mineral surface areas, and secondary hydraulic conductivities are fitted to feldspar losses with depth in the Panola and Davis Run regoliths using a time-depth computer spreadsheet model. The primary hydraulic conductivities, describing the rates of meteoric water penetration into the pristine granites, are assumed to be equal to the propagation rates of weathering fronts, which, based on cosmogenic isotope dating, are 7 m/106 yr for the Panola regolith and 4 m/106 yr for the Davis Run regolith. Best fits in the calculations indicate that the kinetic rate constants for plagioclase in both regoliths are factors of two to three times faster than K-feldspar, which is in agreement with experimental findings. However, the range for plagioclase and K-feldspar rates (kr = 1.5 x 10-17 to 2.8 x 10-16 mol m-2 s-1) is three to four orders of magnitude lower than for that for experimental feldspar dissolution rates and are among the slowest yet recorded for natural feldspar weathering. Such slow rates are attributed to the relatively old geomorphic ages of the Panola and Davis Run regoliths, implying that mineral surface reactivity decreases significantly with time. Differential feldspar weathering in the low-permeability Panola bedrock environment is more dependent on relative feldspar solubilities than on differences in kinetic reaction rates. Such weathering is very sensitive to primary and secondary hydraulic conductivities (qp and qs), which control both the fluid volumes passing through the regolith and the thermodynamic saturation of the feldspars. Bedrock permeability is primarily intragranular and is created by internal weathering of networks of interconnected plagioclase phenocrysts. Saprolite permeability is principally intergranular and is the result of dissolution of silicate phases during isovolumetric weathering. A secondary to primary hydraulic conductivity ratio of qs/qp = 150 in the Panola bedrock results in kinetically controlled plagioclase dissolution but thermodynamically inhibited K-feldspar reaction. This result is in accord with calculated chemical saturation states for groundwater sampled in the Panola Granite. In contrast, greater secondary conductivities in the Davis Run saprolite, qs/qp = 800, produces both kinetically controlled plagioclase and K-feldspar dissolution. Faster plagioclase reaction, leading to bedrock weathering in the Panola Granite but not at Davis Run, is attributed to a higher anorthite component of the plagioclase and a wetter and warmer climate. In addition, the Panola Granite has an abnormally high content of disseminated calcite, the dissolution of which precedes the plagioclase weathering front, thus creating additional secondary permeability. Copyright ?? 2001 Elsevier Science Ltd.

Geochimica et Cosmochimica Acta↗