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M. S. Schulz

Publications and source records attributed to M. S. Schulz.

12 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↗
USGS2010

Variations in the fine-scale composition of a central Pacific ferromanganese crust: Paleoceanographic implications

A 47- to 60-mm-thick Fe-Mn crust from Horizon Guyot (water depth 1800–1780 m), central Pacific, was used to evaluate the potential of crusts as recorders of Neogene paleoceanographic and paleoclimatic conditions. The chemical composition was determined by microprobe for 16 elements from a polished thin section. Three analyses were made per millimeter and averaged to give the composition of each millimeter. The age of the crust was determined by measuring the strontium isotope composition of the crust and comparing it with the Tertiary seawater curve. The crust represents 18.5 m.y. of growth of Fe and Mn oxyhydroxides. The crust is composed of alternating botryoidal and laminated layers. The botryoidal layers formed during the same time intervals that widespread Neogene deep-sea hiatuses were forming in bottom sediments. The botryoidal layers represent growth during times of intensified deepwater flow, whereas the laminated intervals represent more quiescent conditions. The correspondence between the botryoidal layers and the Neogene hiatuses is so strong that we were able to choose a variable growth rate model over a constant growth rate model for the crust. Chemical changes in the crust take two forms. The first is represented by broad changes in the composition defined chiefly by fourth-order polynomial fits to the chemical profiles of each element with depth in the crust. The second is high-frequency changes in composition. The broader changes occurred primarily at about 15, 11.5, 7.4, 6.4, 5.2, and 4.6 Ma, which may correlate with major changes in paleoceanographic circulation and development of ice caps at the poles. The periods of the high-frequency changes may reflect climatic changes that resulted from orbital forcing. These high-frequency changes may correspond to the high-order eccentricity periods of 3.47, 2.04, and 1.31 m.y.

Paleoceanography and Paleoclimatology↗
USGS2010

Biologic origin of iron nodules in a marine terrace chronosequence, Santa Cruz, California

The distribution, chemistry, and morphology of Fe nodules were studied in a marine terrace soil chronosequence northwest of Santa Cruz, California. The Fe nodules are found at depths <1 m on all terraces. The nodules consisted of soil mineral grains cemented by Fe oxides. The nodules varied in size from 0.5 to 25 mm in diameter. Nodules did not occur in the underlying regolith. The Fe-oxide mineralogy of the nodules was typically goethite; however, a subset of nodules consisted of maghemite. There was a slight transformation to hematite with time. The abundance of soil Fe nodules increased with terrace age on the five terraces studied (aged 65,000-226,000 yr). Scanning electron microscopy (SEM) revealed Fe-oxide-containing fungal hyphae throughout the nodules, including organic structures incorporating fine-grained Fe oxides. The fine-grained nature of the Fe oxides was substantiated by M??ssbauer spectroscopy. Our microscopic observations led to the hypothesis that the nodules in the Santa Cruz terrace soils are precipitated by fungi, perhaps as a strategy to sequester primary mineral grains for nutrient extraction. The fungal structures are fixed by the seasonal wetting and dry cycles and rounded through bioturbation. The organic structures are compacted by the degradation of fungal C with time. ?? Soil Science Society of America. All rights reserved.

Soil Science Society of America Journal↗
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↗
USGS2008

Diffuse flow hydrothermal manganese mineralization along the active Mariana and southern Izu-Bonin arc system, western Pacific

Abundant ferromanganese oxides were collected along 1200 km of the active Izu-Bonin-Mariana arc system. Chemical compositions and mineralogy show that samples were collected from two deposit types: Fe-Mn crusts of mixed hydrogenetic/hydrothermal origin and hydrothermal Mn oxide deposits; this paper addresses only the second type. Mn oxides cement volcaniclastic and biogenic sandstone and breccia layers (Mn sandstone) and form discrete dense stratabound layers along bedding planes and within beds (stratabound Mn). The Mn oxide was deposited within coarse-grained sediments from diffuse flow systems where precipitation occurred below the seafloor. Deposits were exposed at the seabed by faulting, mass wasting, and erosion. Scanning electron microscopy and microprobe analyses indicate the presence of both amorphous and crystalline 10 ?? and 7 ?? manganate minerals, the fundamental chemical difference being high water contents in the amorphous Mn oxides. Alternation of amorphous and crystalline laminae occurs in many samples, which likely resulted from initial rapid precipitation of amorphous Mn oxides from waxing pulses of hydrothermal fluids followed by precipitation of slow forming crystallites during waning stages. The chemical composition is characteristic of a hydrothermal origin including strong fractionation between Fe (mean 0.9 wt %) and Mn (mean 48 wt %) for the stratabound Mn, generally low trace metal contents, and very low rare earth element and platinum group element contents. However, Mo, Cd, Zn, Cu, Ni, and Co occur in high concentrations in some samples and may be good indicator elements for proximity to the heat source or to massive sulfide deposits. For the Mn sandstones, Fe (mean-8.4%) and Mn (12.4%) are not significantly fractionated because of high Fe contents in the volcaniclastic material. However, the proportion of hydrothermal Fe (nondetrital Fe) to total Fe is remarkably constant (49-58%) for all the sample groups, regardless of the degree of Mn mineralization. Factor analyses indicate various mixtures of two dominant components: hydrothermal Mn oxide for the stratabound Mn and detrital aluminosilicate for the Mn-cemented sandstone; and two minor components, hydrothermal Fe oxyhydroxide and biocarbonate/biosilica. Our conceptual model shows that Mn mineralization was produced by hydrothermal convection cells within arc volcanoes and sedimentary prisms that occur along, the flanks and within calderas. The main source of hydrothermal fluid was seawater that penetrated through fractures, faults, and permeable volcanic edifices. The fluids were heated by magma, enriched in metals by leaching of basement rocks and sediments, and mixed with magmatic fluids and gases. Dikes and sills may have been another source of heat that drove small-scale circulation within sedimentary prisms. Copyright 2008 by the American Geophysical Union.

Journal of Geophysical Research B: Solid Earth↗
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↗
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↗
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↗
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↗
USGS1990

Insular and submarine ferromanganese mineralization of the Tonga-Lau region

Ferromanganese oxides in the Tonga-Lau region are divided into crusts and stratabound deposits. Crusts were collected from the Tonga and Lau Ridges and have Fe/Mn ratios greater than 1, and an average Co content of 0.25%. The crusts average less than 10 mm thick with a maximum of 50 mm, and growth rates of tens of millimeters per million years. The thickest crust is probably less than a million years old. Crusts formed by both hydrogenetic and hydrothermal precipitation, with the hydrothermal input averaging 76%. Stratabound deposits are divided into three types. The source rocks through which the circulating fluids passed controlled the dominant minor element compositions of the stratabound deposits from each area: Valu Fa Ridge, Mo; Tonga Ridge Ti; Tonumea, Sr and Eua, V. -from Authors

Marine Mining↗