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Arthur F. White

Publications and source records attributed to Arthur F. White.

At least 19 recordsLinked to original sources

Lithological influences on contemporary and long-term regolith weathering at the Luquillo Critical Zone Observatory

Lithologic differences give rise to the differential weatherability of the Earth’s surface and globally variable silicate weathering fluxes, which provide an important negative feedback on climate over geologic timescales. To isolate the influence of lithology on weathering rates and mechanisms, we compare two nearby catchments in the Luquillo Critical Zone Observatory in Puerto Rico, which have similar climate history, relief and vegetation, but differ in bedrock lithology. Regolith and pore water samples with depth were collected from two ridgetops and at three sites along a slope transect in the volcaniclastic Bisley catchment and compared to existing data from the granitic Río Icacos catchment. The depth variations of solid-state and pore water chemistry and quantitative mineralogy were used to calculate mass transfer (tau) and weathering solute profiles, which in turn were used to determine weathering mechanisms and to estimate weathering rates. Regolith formed on both lithologies is highly leached of most labile elements, although Mg and K are less depleted in the granitic than in the volcaniclastic profiles, reflecting residual biotite in the granitic regolith not present in the volcaniclastics. Profiles of both lithologies that terminate at bedrock corestones are less weathered at depth, near the rock-regolith interfaces. Mg fluxes in the volcaniclastics derive primarily from dissolution of chlorite near the rock-regolith interface and from dissolution of illite and secondary phases in the upper regolith, whereas in the granitic profile, Mg and K fluxes derive from biotite dissolution. Long-term mineral dissolution rates and weathering fluxes were determined by integrating mass losses over the thickness of solid-state weathering fronts, and are therefore averages over the timescale of regolith development. Resulting long-term dissolution rates for minerals in the volcaniclastic regolith include chlorite: 8.9 × 10 −14 mol m −2 s −1 , illite: 2.1 × 10 −14 mol m −2 s −1 and kaolinite: 4.0 × 10 −14 mol m −2 s −1 . Long-term weathering fluxes are several orders of magnitude lower in the granitic regolith than in the volcaniclastic, despite higher abundances of several elements in the granitic regolith. Contemporary weathering fluxes were determined from net (rain-corrected) solute profiles and thus represent rates over the residence time of water in the regolith. Contemporary weathering fluxes within the granitic regolith are similar to the long-term fluxes. In contrast, the long-term fluxes are faster than the contemporary fluxes in the volcaniclastic regolith. Contemporary fluxes in the granitic regolith are generally also slightly faster than in the volcaniclastic. The differences in weathering fluxes over space and time between these two watersheds indicate significant lithologic control of chemical weathering mechanisms and rates.

Bisley watersheds

Long-term flow-through column experiments and their relevance to natural granitoid weathering rates

Four pairs of fresh and partly-weathered granitoids, obtained from well-characterized watersheds—Merced River, CA, USA; Panola, GA, USA; Loch Vale, CO, USA, and Rio Icacos, Puerto Rico—were reacted in columns under ambient laboratory conditions for 13.8 yrs, the longest running experimental weathering study to date. Low total column mass losses (<1 wt. %), correlated with the absence of pitting or surface roughening of primary silicate grains. BET surface area (S BET ) increased, primarily due to Fe-oxyhydroxide precipitation. Surface areas returned to within factors of 2 to 3 of their original values after dithionite extraction. Miscible displacement experiments indicated homogeneous plug flow with negligible immobile water, commonly cited for column experiments. Fresh granitoid effluent solute concentrations initially declined rapidly, followed by much slower decreases over the next decade. Weathered granitoid effluent concentrations increased modestly over the same time period, indicating losses of natural Fe-oxide and/or clay coatings and the increased exposure of primary mineral surfaces. Corresponding (fresh and weathered) elemental effluent concentrations trended toward convergence during the last decade of reaction. NETPATH/PHREEQC code simulations indicated non-stoichiometric dissolution involving Ca release from disseminated calcite and excess K release from interlayer biotite. Effluent 87 Sr/ 85 Sr ratios reflected a progressive weathering sequence beginning and ending with 87 Sr/ 85 Sr values of plagioclase with an additional calcite input and a radiogenic biotite excursion proportional to the granitoid ages. Effluents became thermodynamically saturated with goethite and gibbsite, slightly under-saturated with kaolinite and strongly under-saturated with plagioclase, consistent with kinetically-limited weathering in which solutes such as Na varied with column flow rates. Effluent Na concentrations showed no clear trend with time during the last decade of reaction (fresh granitoids) or increased slowly with time (weathered granitoids). Analysis of cumulative Na release indicated that plagioclase dissolution achieved steady state in 3 of the 4 fresh granitoids during the last decade of reaction. Surface-area normalized plagioclase dissolution rates exhibited a narrow range (0.95 to 1.26 10 -13 moles m -2 s -1 ), in spite of significant stoichiometric differences (An 0.21 to An 0.50 ). Rates were an order of magnitude slower than previously reported in shorter duration experiments but generally 2 to 3 orders of magnitude faster than corresponding natural analogs. CrunchFlow simulations indicated that more than a hundredfold decrease in column flow rates would be required to produce near-saturation reaction affinities that would start to slow plagioclase weathering to real-world levels. Extending simulations to approximate long term weathering in naturally weathered profiles required additional decreases in the intrinsic plagioclase dissolution and kaolinite precipitation rates and relatively large decreases in the fluid flow rate, implying that exposure to reactive mineral surfaces is significantly limited in the natural environment compared to column experiments.

Geochimica et Cosmochimica Acta

Probing the deep critical zone beneath the Luquillo Experimental Forest, Puerto Rico

Recent work has suggested that weathering processes occurring in the subsurface produce the majority of silicate weathering products discharged to the world's oceans, thereby exerting a primary control on global temperature via the well-known positive feedback between silicate weathering and CO 2 . In addition, chemical and physical weathering processes deep within the critical zone create aquifers and control groundwater chemistry, watershed geometry and regolith formation rates. Despite this, most weathering studies are restricted to the shallow critical zone (e.g. soils, outcrops). Here we investigate the chemical weathering, fracturing and geomorphology of the deep critical zone in the Bisley watershed in the Luquillo Critical Zone Observatory, Puerto Rico, from two boreholes drilled to 37.2 and 27.0 m depth, from which continuous core samples were taken. Corestones exposed aboveground were also sampled. Weathered rinds developed on exposed corestones and along fracture surfaces on subsurface rocks slough off of exposed corestones once rinds attain a thickness up to ~1 cm, preventing the corestones from rounding due to diffusion limitation. Such corestones at the land surface are assumed to be what remains after exhumation of similar, fractured bedrock pieces that were observed in the drilled cores between thick layers of regolith. Some of these subsurface corestones are massive and others are highly fractured, whereas aboveground corestones are generally massive with little to no apparent fracturing. Subsurface corestones are larger and less fractured in the borehole drilled on a road where it crosses a ridge compared with the borehole drilled where the road crosses the stream channel. Both borehole profiles indicate that the weathering zone extends to well below the stream channel in this upland catchment; hence weathering depth is not controlled by the stream level within the catchment and not all of the water in the watershed is discharged to the stream

Earth Surface Processes and Landforms

Water quality and landscape processes of four watersheds in eastern Puerto Rico

Humid tropical regions occupy about a quarter of Earth's land surface, yet they contribute a substantially higher fraction of the water, solutes, and sediment discharged to the world's oceans. Nearly half of Earth's population lives in the tropics, and development stresses can potentially harm soil resources, water quality, and water supply and in addition increase landslide and flood hazards. Owing to Puerto Rico's steep topography, low water storage capacity, and dependence on trade-wind precipitation, the island's people, ecosystems, and water supply are vulnerable to extreme weather such as hurricanes, floods, and droughts. Eastern Puerto Rico offers a natural laboratory for separating geologic and land-cover influences from regional- and global-scale influences because of its various bedrock types and the changing land cover surrounding intact, mature forest of the Luquillo Experimental Forest. Accordingly, a multiyear assessment of hydrological and biogeochemical processes was designed to develop an understanding of the effects of these differences on local climate, streamflow, water quality, and ecosystems, and to form the basis for a long-term and event-based program of climate and hydrologic monitoring. Because infrequent, large storms play a major role in this landscape, we focused on high-runoff events, sampling 263 storms, including all major hurricanes from 1991 through 2005. The largest storms have profound geomorphic consequences, such as landslides, debris flows, deep gullying on deforested lands, excavation and suspension of sediment in stream channels, and delivery of a substantial fraction of annual stream sediment load. Large storms sometimes entrain ocean foam and spray causing high concentrations of seasalt-derived constituents in stream waters during the storm. Past deforestation and agricultural activities in the Cayagu&aacute;s and Can&oacute;vanas watersheds accelerated erosion and soil loss, and this material continues to be remobilized during large storms. Nearly 5,000 routine and event samples were analyzed for parameters that allow determination of denudation rates based on suspended and dissolved loads; 860 of these samples were analyzed for a comprehensive suite of chemical constituents. The rivers studied are generally similar in water-quality characteristics, and windward or leeward aspect appears to exert a stronger influence on water quality than geology or land cover. Of samples analyzed for comprehensive chemistry and for sediment, 543 were collected at runoff rates greater than 1 millimeter per hour, 256 at rates exceeding 10 millimeters per hour, and 3 at rates exceeding 90 millimeters per hour. Streams have rarely been sampled during events with such high runoff rates. Rates of physical and chemical weathering are especially high, and physical denudation rates, forested watersheds included, are considerably greater than is expected for a steady-state system. The elevated physical erosion drives an increased particulate organic carbon flux, one that is large, important to the carbon cycle, and sustainable, because soil-carbon regeneration is rapid. The 15-year Water, Energy, and Biogeochemical Budget dataset, which includes discharge, field parameters, suspended sediment, major cations and anions, and nutrients, is available from the U.S. Geological Survey's National Water Information System (http://waterdata.usgs.gov/nwis). The dataset provides a baseline for characterizing future environmental change and will improve our understanding of the interdependencies of land, water, and biological resources and their responses to changes in climate and land use. Because eastern Puerto Rico resembles many tropical regions in terms of geology and patterns of development, implications from this study are transferable to other tropical regions facing deforestation, rapid land-use change, and climate change.

Professional Paper

Proposed initiative would study Earth's weathering engine

At the Earth's surface, a complex suite of chemical, biological, and physical processes combines to create the engine that transforms bedrock into soil (Figure 1). Earth's weathering engine provides nutrients to nourish ecosystems and human society mediates the transport of toxic components within the biosphere, creates water flow paths that carve and weaken bedrock, and contributes to the evolution of landscapes at all temporal and spatial scales. At the longest time scales, the weathering engine sequesters CO 2 , thereby influencing long-term climate change. Despite the importance of soil, our knowledge of the rate of soil formation is limited because the weathering zone forms a complex, ever-changing interface, and because scientific approaches and funding paradigms have not promoted integrated research agendas to investigate such complex interactions. No national initiative has promoted a systems approach to investigation of weathering science across the broad array of geology, soil science, ecology and hydrology. Such a program is certainly needed, and this article describes a platform on which to build the initiative to answer the following question: How does the Earth weathering engine break down rock to nourish ecosystems, carve terrestrial landscapes, and control carbon dioxide in the global atmosphere?

Eos Science News

A model for assessing, quantifying, and correcting for index element mobility in weathering studies

Evidence shows that high field strength (HFS) elements commonly used to index chemical weathering are variably mobile. This mobility may be linked to redistribution of suspended solids. A mass-balance model is presented that can quantify such redistribution without assuming immobility for any single element. Two tropical weathering profiles on quartz diorite and basalt are examined and redistribution of the HFS elements Zr and Ti is documented, along with potential corrections for the resulting changes in measured concentrations.

Applied Geochemistry

Seasonal dynamics of CO2 profiles across a soil chronosequence, Santa Cruz, California

Concentrations of CO 2 in soil atmosphere and CO 2 efflux were measured across a marine terrace soil chronosequence near Santa Cruz, California. Soil development, specifically the formation of an argillic horizon, has created a two-tier soil gas profile in the older terrace soils. The soil above the argillic horizon has seasonal variations in soil CO 2 associated with plant respiration. The older soils with dense argillic horizons maintain a year round ∼1%CO 2 below the argillic horizon. The CO 2 efflux during the growing season is higher on the older terraces.

California

Strong climate and tectonic control on plagioclase weathering in granitic terrain

Investigations to understand linkages among climate, erosion and weathering are central to quantifying landscape evolution. We approach these linkages through synthesis of regolith data for granitic terrain compiled with respect to climate, geochemistry, and denudation rates for low sloping upland profiles. Focusing on Na as a proxy for plagioclase weathering, we quantified regolith Na depletion, Na mass loss, and the relative partitioning of denudation to physical and chemical contributions. The depth and magnitude of regolith Na depletion increased continuously with increasing water availability, except for locations with mean annual temperature < 5 °C that exhibited little Na depletion, and locations with physical erosion rates < 20 g m − 2 yr − 1 that exhibited deep and complete regolith Na depletion. Surface Na depletion also tended to decrease with increasing physical erosion. Depth-integrated Na mass loss and regolith depth were both three orders of magnitude greater in the fully depleted, low erosion rate sites relative to other locations. These locations exhibited strong erosion-limitation of Na chemical weathering rates based on correlation of Na chemical weathering rate to total Na denudation. Sodium weathering rates in cool locations with positive annual water balance were strongly correlated to total Na denudation and precipitation, and exhibited an average apparent activation energy ( Ea ) of 69 kJ mol − 1 Na. The remaining water-limited locations exhibited kinetic limitation of Na weathering rates with an Ea of 136 kJ mol − 1 Na, roughly equivalent to the sum of laboratory measures of Ea and dissolution reaction enthalpy for albite. Water availability is suggested as the dominant factor limiting rate kinetics in the water-limited systems. Together, these data demonstrate marked transitions and nonlinearity in how climate and tectonics correlate to plagioclase chemical weathering and Na mass loss.

Earth and Planetary Science Letters

Phosphorus and iron cycling in deep saprolite, Luquillo Mountains, Puerto Rico

Rapid weathering and erosion rates in mountainous tropical watersheds lead to highly variable soil and saprolite thicknesses which in turn impact nutrient fluxes and biological populations. In the Luquillo Mountains of Puerto Rico, a 5-m thick saprolite contains high microorganism densities at the surface and at depth overlying bedrock. We test the hypotheses that the organisms at depth are limited by the availability of two nutrients, P and Fe. Many tropical soils are P-limited, rather than N-limited, and dissolution of apatite is the dominant source of P. We document patterns of apatite weathering and of bioavailable Fe derived from the weathering of primary minerals hornblende and biotite in cores augered to 7.5 m on a ridgetop as compared to spheroidally weathering bedrock sampled in a nearby roadcut. Iron isotopic compositions of 0.5 N HCl extracts of soil and saprolite range from about δ 56 Fe = 0 to − 0.1‰ throughout the saprolite except at the surface and at 5 m depth where δ 56 Fe = − 0.26 to − 0.64‰. The enrichment of light isotopes in HCl-extractable Fe in the soil and at the saprolite–bedrock interface is consistent with active Fe cycling and consistent with the locations of high cell densities and Fe(II)-oxidizing bacteria, identified previously. To evaluate the potential P-limitation of Fe-cycling bacteria in the profile, solid-state concentrations of P were measured as a function of depth in the soil, saprolite, and weathering bedrock. Weathering apatite crystals were examined in thin sections and an apatite dissolution rate of 6.8 × 10 − 14 mol m − 2 s − 1 was calculated. While surface communities depend on recycled nutrients and atmospheric inputs, deep communities survive primarily on nutrients released by the weathering bedrock and thus are tightly coupled to processes related to saprolite formation including mineral weathering. While low available P may limit microbial activity within the middle saprolite, fluxes of P from apatite weathering should be sufficient to support robust growth of microorganisms in the deep saprolite.

Puerto Rico

Effects of temperature on silicate weathering: Solute fluxes and chemical weathering in a temperate rain forest watershed, Jamieson Creek, British Columbia

Chemical weathering of silicate minerals has long been known as a sink for atmospheric CO 2 , and feedbacks between weathering and climate are believed to affect global climate. While warmer temperatures are believed to increase rates of weathering, weathering in cool climates can be accelerated by increased mineral exposure due to mechanical weathering by ice. In this study, chemical weathering of silicate minerals is investigated in a small temperate watershed. The Jamieson Creek watershed is covered by mature coniferous forest and receives high annual precipitation (4000 mm), mostly in the form of rainfall, and is underlain by quartz diorite bedrock and glacial till. Analysis of pore water concentration gradients indicates that weathering in hydraulically unsaturated ablation till is dominated by dissolution of plagioclase and hornblende. However, a watershed scale solute mass balance indicates high relative fluxes of K and Ca, indicating preferential leaching of these solutes possibly from the relatively unweathered lodgement till. Weathering rates for plagioclase and hornblende calculated from a watershed scale solute mass balance are similar in magnitude to rates determined using pore water concentration gradients. When compared to the Rio Icacos basin in Puerto Rico, a pristine tropical watershed with similar annual precipitation and bedrock, but with dissimilar regolith properties, fluxes of weathering products in stream discharge from the warmer site are 1.8 to 16.2-fold higher, respectively, and regolith profile-averaged plagioclase weathering rates are 3.8 to 9.0-fold higher. This suggests that the Arrhenius effect, which predicts a 3.5- to 9-fold increase in the dissolution rate of plagioclase as temperature is increased from 3.4° to 22 °C, may explain the greater weathering fluxes and rates at the Rio Icacos site. However, more modest differences in K and Ca fluxes between the two sites are attributed to accelerated leaching of those solutes from glacial till at Jamieson Creek. Our findings suggest that under conditions of high rainfall and favorable topography, weathering rates of silicate minerals in warm tropical systems will tend to be higher than in cool temperate systems, even if the temperate system is has been perturbed by an episode of glaciation that deposits regolith high in fresh mineral surface area.

British Columbia

Mg isotope constraints on soil pore-fluid chemistry: Evidence from Santa Cruz, California

Mg isotope ratios ( 26 Mg/ 24 Mg) are reported in soil pore-fluids, rain and seawater, grass and smectite from a 90 kyr old soil, developed on an uplifted marine terrace from Santa Cruz, California. Rain water has an invariant 26 Mg/ 24 Mg ratio (expressed as δ26 Mg> δ26 Mg ) at −0.79 ± 0.05‰, identical to seawater δ26 Mg> δ26 Mg . Detrital smectite (from the base of the soil profile, and therefore unweathered) has a δ26Mg"> δ26Mg value of 0.11‰, potentially enriched in 26 Mg by up to 0.3‰ compared to the bulk silicate Earth Mg isotope composition (although within the range of all terrestrial silicates). The soil pore-waters show a continuous profile with depth for δ26 Mg> δ26 Mg , ranging from −0.99‰ near the surface to −0.43‰ at the base of the profile. Shallow pore-waters (<1 m) have δ26 Mg> δ26 Mg values that are similar to, or slightly lower than the rain waters. This implies that the degree of biological cycling of Mg in the pore-waters is relatively small and is quantified as <32%, calculated using the average Mg isotope enrichment factor between grass and rain ( δ26 Mggrass- δ26 Mgrain> δ26 Mggrass- δ26 Mgrain ) of 0.21‰. The deep pore-waters (1–15 m deep) have δ26 Mg> δ26 Mg values that are intermediate between the smectite and rain, ranging from −0.76‰ to −0.43‰, and show a similar trend with depth compared to Sr isotope ratios. The similarity between Sr and Mg isotope ratios confirms that the Mg in the pore-waters can be explained by a mixture between rain and smectite derived Mg, despite the fact that Mg and Sr concentrations may be buffered by the exchangeable reservoir. However, whilst Sr isotope ratios in the pore-waters span almost the complete range between mineral and rain inputs, Mg isotopes compositions are much closer to the rain inputs. If Mg and Sr isotope ratios are controlled uniquely by a mixture, the data can be used to estimate the mineral weathering inputs to the pore-waters, by correcting for the rain inputs. This isotopic correction is compared to the commonly used chloride correction for precipitation inputs. A consistent interpretation is only possible if Mg isotope ratios are fractionated either by the precipitation of a secondary Mg bearing phase, not detected by conventional methods, or selective leaching of 24 Mg from smectite. There is therefore dual control on the Mg isotopic composition of the pore-waters, mixing of two inputs with distinct isotopic compositions, modified by fractionation. The data provide (1) further evidence for Mg isotope fractionation at the surface of the Earth and (2) the first field evidence of Mg isotope fractionation during uptake by natural plants. The coherent behaviour of Mg isotope ratios in soil environments is encouraging for the development of Mg isotope ratios as a quantitative tracer of both weathering inputs of Mg to waters, and the physicochemical processes that cycle Mg, a major cation linked to the carbon cycle, during continental weathering.

California

Shifting microbial community structure across a marine terrace grassland chronosequence, Santa Cruz, California

Changes in the biomass and structure of soil microbial communities have the potential to impact ecosystems via interactions with plants and weathering minerals. Previous studies of forested long-term (1000s – 100,000s of years) chronosequences suggest that surface microbial communities change with soil age. However, significant gaps remain in our understanding of long-term soil microbial community dynamics, especially for non-forested ecosystems and in subsurface soil horizons. We investigated soil chemistry, aboveground plant productivity, and soil microbial communities across a grassland chronosequence (65,000–226,000 yrs old) located near Santa Cruz, CA. Aboveground net primary productivity (ANPP) initially increased to a maximum and then decreased for the older soils. We used polar lipid fatty acids (PLFA) to investigate microbial communities including both surface (<0.1 m) and subsurface (≥0.2 m) soil horizons. PLFAs characteristic of Gram-positive bacteria and actinobacteria increased as a fraction of the microbial community with depth while the fungal fraction decreased relative to the surface. Differences among microbial communities from each chronosequence soil were found primarily in the subsurface where older subsurface soils had smaller microbial community biomass, a higher proportion of fungi, and a different community structure than the younger subsurface soil. Subsurface microbial community shifts in biomass and community structure correlated with, and were likely driven by, decreasing soil P availability and Ca concentrations, respectively. Trends in soil chemistry as a function of soil age led to the separation of the biological (≤1 m depth) and geochemical (>1 m) cycles in the old, slowly eroding landscape we investigated, indicating that this separation, commonly observed in tropical and subtropical ecosystems, can also occur in temperate climates. This study is the first to investigate subsurface microbial communities in a long-term chronosequence. Our results highlight connections between soil chemistry and both the aboveground and belowground parts of an ecosystem.

California

Approaches to modeling weathered regolith

Sustainable soils are a requirement for maintaining human civilizations ( Carter and Dale 1974 ; Lal 1989 ). However, as the “most complicated biomaterial on the planet” ( Young and Crawford 2004 ), soils represent one of the most difficult systems to understand and model with respect to chemical, physical, and biological coupling over time (Fig. 1 ). Despite the complexity of these interactions, certain patterns in soil properties and development are universally observed and have been used in soil science as a means for classification. Elemental, mineralogical, or isotopic concentrations in soils plotted versus depth beneath the land surface comprise such patterns. Soil depth profiles are often reported for solid soil materials, and, less frequently, for solutes in soil pore waters. These profiles cross a large range in spatial scales that traditionally have been studied by different disciplines. For example, shallow, biologically active horizons are commonly defined as the soil zone in agronomic studies whereas the mobile layer of the regolith is referred to as soil in geomorphological studies. In contrast, many geochemical studies target chemical weathering to tens or even hundreds of meters in depth, sometimes extending the definition of “soils” to include the entire regolith down to parent bedrock or alluvium. Soil profiles also exhibit a large range in temporal scales ( Amundson 2004 ; Brantley 2008b ). Solid-state profiles document chemical and mineralogical changes integrated over the time scales of evolution of regolith from protolith. This “geologic time” can vary from tens to hundreds of years for weathered material developed on moraines deposited by active glaciers ( Anderson et al. 1997 ), to millions or possibly hundreds of millions of years of regolith evolution as documented in laterites and bauxites on stable cratons ( Nahon 1986 ). In contrast, solute profiles reflect much shorter time scales corresponding to the residence time of the soil water which commonly ranges from days to decades ( Stonestrom et al. 1998 ). Factors impacting soil minerals can therefore be related to geologically old processes while those impacting pore waters are related to contemporary processes. We first discuss a geochemical frame work for modeling soil profiles, including a simple scheme that depends on the extent of enrichment or depletion. Such profiles are comprised of reaction fronts affected by chemical, hydrologic, geologic and biologic processes that control soil evolution. We then present a hierarchy of models that have been used to interpret both solid state and solute compositions in regolith. The more simple approaches to model depletion in soils, using analytical models, are first described. The most elementary of these is a linear model that calculates rate constants from the slopes of either solid or solute weathering gradients: these rate constants represent lumped parameters that describe weathering in terms of an integrated reaction rate. Two other analytical models are then presented that have been used to fit solid state elemental profiles with exponential and sigmoidal functions. All of these analytical approaches are derived for models of soils as containing a limited number of components, phases, and species. At a more complex level, numerical models are then presented to elucidate how kinetic and transport parameters as well as chemical, hydrologic, and physical soil data can be incorporated. We consider two forms of these models, first relatively simple spreadsheet calculators and then more sophisticated multi-component, multi-phase reactive-transport numerical codes. Our treatment of reactive transport modeling is relatively cursory, in recognition of the treatment in the chapter by Steefel and Maher (2009 , this volume). Because these models incorporate more phases, components, and species than the other approaches and explicitly model the more fundamental reaction mechanisms involved, they generally have a greater need for parameterization. In our conclusion section, we discuss how this hierarchy of approaches can yield generalizations about soils that are often complementary.

Reviews in Mineralogy and Geochemistry

Preface

No abstract available.

Book chapter

Quantitative approaches to characterizing natural chemical weathering rates

Silicate minerals, constituting more than 90% of the rocks exposed at the earth’s surface, are commonly formed under temperature and pressure conditions that make them inherently unstable in surficial environments. Undoubtedly, the most significant aspect of chemical weathering resulting from this instability is the formation of soils which makes life possible on the surface of the earth. Many soil macronutrients in this “critical zone” are directly related to the rate at which primary minerals weather (Huntington, 1995; Chadwick et al., 2003). Chemical weathering also creates economically significant ore deposits, such as those for Al and U (Samma, 1986; Misra, 2000), as well as potentially releasing high concentrations of toxic trace elements such as Se and As (Frankenberger and Benson, 1994). Silicate weathering is a significant buffer to acidification caused by atmospheric deposition (Driscoll et al., 1989) and from land use practices (Farley and Werritty, 1989). Atmospheric CO 2 levels have been primarily controlled by the balance between silicate weathering and the rate of volcanic inputs from the Earth’s interior, a relationship which may explain long-term climate stability (Ruddiman, 1997)

Book chapter

Chemical weathering of a marine terrace chronosequence, Santa Cruz, California: Deciphering reaction rates from mineral depth profiles

A soil chronosequence developed on marine terraces along coastal California, exhibits deeper and more intensively weathered mineral profiles with increasing age (65 to 226 kyrs). Feldspar concentrations generally increase linearly with terrace depth. The slope or weathering gradient is defined by the ratio of the weathering rate and the velocity at which the profile penetrates into the regolith.A spread sheet calculator further refines profile geometries, demonstrating that the non-linear regions at low residual feldspar concentrations are dominated by exponential changes in mineral surface to volume and at high residual feldspar concentrations by the approach to thermodynamic saturation.These parameters, in addition to the kinetic rate constant, are of secondary importance to the fluid flux qh which controls the weathering velocity and solute fluxes from the profile. © 2007 Taylor & Francis Group, London.

California

The effect of time on the weathering of silicate minerals: Why do weathering rates differ in the laboratory and field?

The correlation between decreasing reaction rates of silicate minerals and increasing duration of chemical weathering was investigated for both experimental and field conditions. Column studies, using freshly prepared Panola Granite, produced ambient plagioclase weathering rates that decreased parabolically over 6 years to a final rate of 7.0×10 −14 mol m −2 s −1 . In contrast, the corresponding plagioclase reaction rate for partially kaolinized Panola Granite, after reaching steady-state weathering after 2 months of reactions, was significantly less (2.1×10 −15 mol m −2 s −1 ). Both rates were normalized to plagioclase content and BET surface area. Extrapolation of decreasing rates for the fresh plagioclase with time indicated that several thousand years of reaction would be required to replicate the rate of the naturally weathered plagioclase under identical experimental conditions. Both rates would remain orders of magnitude faster than field weathering rates previously measured for a weathering profile in the Panola Granite. Additional trends in weathering rates with time were established from a tabulation of previously reported experimental and field rates for plagioclase, K-feldspar, hornblende and biotite. Discrepancies in the literature, produced by normalization of weathering rates with respect to surface areas measured by gas absorption (BET) and geometric methods, were overcome by developing a time-dependent roughness factor. Regression curves through the corrected rates produced strong correlations with time that were similar for the four silicate minerals. The average silicate weathering rate R (mol m −2 s −1 ) was described by the power function R=3.1&#xD7;10 &#x2212;13 t &#x2212;0.61 "> R=3.1×10 -13 t -0.61 which was similar to the relationship describing the decrease in the fresh Panola plagioclase with time and suggesting control by transport-limited reaction. The time dependency of silicate weathering is discussed in terms of processes intrinsic to the silicate mineral and those extrinsic to the weathering environment. Intrinsic surface area, which increases with the duration of weathering, was shown to account for a third of the exponential decrease in the weathering rate shown by the above equation. Other factors, including progressive depletion of energetically reactive surfaces and accumulation of leached layers and secondary precipitates, must explain differences for fresh and weathered plagioclase reacting under identical experimental conditions. Extrinsic controls, including low permeability, high mineral/fluid ratios and increased solute concentrations, produce weathering reactions close to thermodynamic equilibrium under field conditions compared to highly unsaturated conditions during experimental reaction of fresh and weathered plagioclase. These differences explain the time-dependent difference in field and lab rates.

Chemical Geology