Brantley S.L.

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

Buss, Heather L., Ryan Mathur, Arthur F. White, and Susan L. Brantley. 2010. Phosphorus and iron cycling in deep saprolite, luquillo mountains, puerto rico. Chemical Geology 269 (1-2) (JAN 15): 52-61.

Abstract: 
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 δ56Fe=0 to −0.1‰ throughout the saprolite except at the surface and at 5 m depth where δ56Fe=−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.

Long‐term patterns and short‐term dynamics of stream solutes and suspended sediment in a rapidly weathering tropical watershed

Shanley, J. B., W. H. McDowell, and R. F. Stallard (2011), Long‐term patterns and short‐term dynamics of stream
solutes and suspended sediment in a rapidly weathering tropical watershed, Water Resour. Res., 47, W07515,
doi:10.1029/2010WR009788

Abstract: 
The 326 ha Río Icacos watershed in the tropical wet forest of the Luquillo Mountains, northeastern Puerto Rico, is underlain by granodiorite bedrock with weathering rates among the highest in the world. We pooled stream chemistry and total suspended sediment (TSS) data sets from three discrete periods: 1983–1987, 1991–1997, and 2000–2008. During this period three major hurricanes crossed the site: Hugo in 1989, Hortense in 1996, and Georges in 1998. Stream chemistry reflects sea salt inputs (Na, Cl, and SO4), and high weathering rates of the granodiorite (Ca, Mg, Si, and alkalinity). During rainfall, stream composition shifts toward that of precipitation, diluting 90% or more in the largest storms, but maintains a biogeochemical watershed signal marked by elevated K and dissolved organic carbon (DOC) concentration. DOC exhibits an unusual “boomerang” pattern, initially increasing with flow but then decreasing at the highest flows as it becomes depleted and/or vigorous overland flow minimizes contact with watershed surfaces. TSS increased markedly with discharge (power function slope 1.54), reflecting the erosive power of large storms in a landslide‐prone landscape. The relations of TSS and most solute concentrations with stream discharge were stable through time, suggesting minimal long‐term effects from repeated hurricane disturbance. Nitrate concentration, however, increased about threefold in response to hurricanes then returned to baseline over several years following a pseudo first‐order decay pattern. The combined data sets provide insight about important hydrologic pathways, a long‐term perspective to assess response to hurricanes, and a framework to evaluate future climate change in tropical ecosystems.

Iron and phosphorus cycling in deep saprolite, Luquillo Mountains, Puerto Rico

Buss H.L., Mathur R., White A.F., and Brantley S.L. 2010. Iron and phosphorus cycling in deep saprolite, Luquillo Mountains, Puerto Rico. Chem. Geol., 269, 52-61.

Abstract: 
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 δ56Fe = 0 to − 0.1‰ throughout the saprolite except at the surface and at 5 m depth where δ56Fe = − 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. Keywords: Phosphorus; Iron isotopes; Saprolite; Apatite weathering rate; Fe(II)-oxidizing bacteria

Twelve testable hypotheses on the Geobiology of weathering

Brantley S.L., Megonigal J.P., Scatena F.N. et al 2010. Twelve testable hypotheses on the Geobiology of weathering. Geobiology. DOI: 10.1111/j.1472-4669.2010.00264.x

Abstract: 
Critical Zone (CZ) research investigates the chemical, physical, and biological processes that modulate the Earth’s surface. Here, we advance 12 hypotheses that must be tested to improve our understanding of the CZ: (1) Solar-to-chemical conversion of energy by plants regulates flows of carbon, water, and nutrients through plant-microbe soil networks, thereby controlling the location and extent of biological weathering. (2) Biological stoichiometry drives changes in mineral stoichiometry and distribution through weathering. (3) On landscapes experiencing little erosion, biology drives weathering during initial succession, whereas weathering drives biology over the long term.(4) In eroding landscapes, weathering-front advance at depth is coupled to surface denudation via biotic processes.(5) Biology shapes the topography of the Critical Zone.(6) The impact of climate forcing on denudation rates in natural systems can be predicted from models incorporating biogeochemical reaction rates and geomorphological transport laws.(7) Rising global temperatures will increase carbon losses from the Critical Zone.(8) Rising atmospheric PCO2 will increase rates and extents of mineral weathering in soils.(9) Riverine solute fluxes will respond to changes in climate primarily due to changes in water fluxes and secondarily through changes in biologically mediated weathering.(10) Land use change will impact Critical Zone processes and exports more than climate change. (11) In many severely altered settings, restoration of hydrological processes is possible in decades or less, whereas restoration of biodiversity and biogeochemical processes requires longer timescales.(12) Biogeochemical properties impart thresholds or tipping points beyond which rapid and irreversible losses of ecosystem health, function, and services can occur.

A spheroidal weathering model coupling porewater chemistry to soil thicknesses during steady-state denudation

Fletcher, R.C., Buss, H.L., Brantley, S.L., 2006.Aspheroidal weathering
model coupling porewater chemistry to soil thicknesses during
steady-state denudation. Earth Planet. Sci. Lett. 244, 444–457.

Abstract: 
Spheroidal weathering, a common mechanism that initiates the transformation of bedrock to saprolite, creates concentric fractures demarcating relatively unaltered corestones and progressively more altered rindlets. In the spheroidally weathering Rio Blanco quartz diorite (Puerto Rico), diffusion of oxygen into corestones initiates oxidation of ferrous minerals and precipitation of ferric oxides. A positive ΔV of reaction results in the build-up of elastic strain energy in the rock. Formation of each fracture is postulated to occur when the strain energy in a layer equals the fracture surface energy. The rate of spheroidal weathering is thus a function of the concentration of reactants, the reaction rate, the rate of transport, and the mechanical properties of the rock. Substitution of reasonable values for the parameters involved in the model produces results consistent with the observed thickness of rindlets in the Rio Icacos bedrock (≈2–3cm) and a time interval between fractures (≈200–300 a) based on an assumption of steady-state denudation at the measured rate of 0.01cm/a. Averaged over times longer than this interval, the rate of advance of the bedrock–saprolite interface during spheroidal weathering (the weathering advance rate) is constant with time. Assuming that the oxygen concentration at the bedrock–saprolite interface varies with the thickness of soil/saprolite yields predictive equations for how weathering advance rate and steady-state saprolite/soil thickness depend upon atmospheric oxygen levels and upon denudation rate. The denudation and weathering advance rates at steady state are therefore related through a condition on the concentration of porewater oxygen at the base of the saprolite. In our model for spheroidal weathering of the Rio Blanco quartz diorite, fractures occur every ∼250yr, ferric oxide is fully depleted over a four rindlet set in ∼1000yr, and saprolitization is completed in ∼5000yr in the zone containing ∼20 rindlets. Spheroidal weathering thus allows weathering to keep up with the high rate of denudation by enhancing access of bedrock to reactants by fracturing. Coupling of denudation and weathering advance rates can also occur for the case that weathering occurs without spheroidal fractures, but for the same kinetics and transport parameters, the maximum rate of saprolitization achieved would be far smaller than the rate of denudation for the Rio Blanco system. The spheroidal weathering model provides a quantitative picture of how physical and chemical processes can be coupled explicitly during bedrock alteration to soil to explain weathering advance rates that are constant in time.

Weathering of the Rio Blanco quartz diorite, Luquillo Mountains, Puerto Rico: Coupling oxidation, dissolution, and fracturing

Buss HL, Sak PB, Webb SM, Brantley SL. 2008. Weathering of the Rio
Blanco quartz diorite, Luquillo Mountains, Puerto Rico: coupling
oxidation, dissolution, and fracturing. Geochimica et Cosmochimica
Acta 72: 4488–4507.

Abstract: 
In the mountainous Rio Icacos watershed in northeastern Puerto Rico, quartz diorite bedrock weathers spheroidally, producing a 0.2–2 m thick zone of partially weathered rock layers (2.5 cm thickness each) called rindlets, which form concentric layers around corestones. Spheroidal fracturing has been modeled to occur when a weathering reaction with a positive DV of reaction builds up elastic strain energy. The rates of spheroidal fracturing and saprolite formation are therefore controlled by the rate of the weathering reaction. Chemical, petrographic, and spectroscopic evidence demonstrates that biotite oxidation is the most likely fractureinducing reaction. This reaction occurs with an expansion in d (001) from 10.0 to 10.5A ˚ , forming ‘‘altered biotite”. Progressive biotite oxidation across the rindlet zone was inferred from thin sections and gradients in K and Fe(II). Using the gradient in Fe(II) and constraints based on cosmogenic age dates, we calculated a biotite oxidation reaction rate of 8.2  1014 mol biotite m2 s1. Biotite oxidation was documented within the bedrock corestone by synchrotron X-ray microprobe fluorescence imaging and XANES. X-ray microprobe images of Fe(II) and Fe(III) at 2 lm resolution revealed that oxidized zones within individual biotite crystals are the first evidence of alteration of the otherwise unaltered corestone. Fluids entering along fractures lead to the dissolution of plagioclase within the rindlet zone. Within 7 cm surrounding the rindlet–saprolite interface, hornblende dissolves to completion at a rate of 6.3  1013 mol hornblende m2 s1: the fastest reported rate of hornblende weathering in the field. This rate is consistent with laboratory-derived hornblende dissolution rates. By revealing the coupling of these mineral weathering reactions to fracturing and porosity formation we are able to describe the process by which the quartz diorite bedrock disaggregates and forms saprolite. In the corestone, biotite oxidation induces spheroidal fracturing, facilitating the influx of fluids that react with other minerals, dissolving plagioclase and chlorite, creating additional porosity, and eventually dissolving hornblende and precipitating secondary minerals. The thickness of the resultant saprolite is maintained at steady state by a positive feedback between the denudation rate and the weathering advance rate driven by the concentration of pore water O2 at the bedrock–saprolite interface.

A spheroidal weathering model coupling porewater chemistry to soil thicknesses during steady-state denudation

Fletcher, R.C., Buss, H.L., Brantley, S.L., 2006.Aspheroidal weathering
model coupling porewater chemistry to soil thicknesses during
steady-state denudation. Earth Planet. Sci. Lett. 244, 444–457.

Abstract: 
Spheroidal weathering, a common mechanism that initiates the transformation of bedrock to saprolite, creates concentric fractures demarcating relatively unaltered corestones and progressively more altered rindlets. In the spheroidally weathering Rio Blanco quartz diorite (Puerto Rico), diffusion of oxygen into corestones initiates oxidation of ferrous minerals and precipitation of ferric oxides. A positive ΔV of reaction results in the build-up of elastic strain energy in the rock. Formation of each fracture is postulated to occur when the strain energy in a layer equals the fracture surface energy. The rate of spheroidal weathering is thus a function of the concentration of reactants, the reaction rate, the rate of transport, and the mechanical properties of the rock. Substitution of reasonable values for the parameters involved in the model produces results consistent with the observed thickness of rindlets in the Rio Icacos bedrock (≈2–3cm) and a time interval between fractures (≈200–300 a) based on an assumption of steady-state denudation at the measured rate of 0.01cm/a. Averaged over times longer than this interval, the rate of advance of the bedrock–saprolite interface during spheroidal weathering (the weathering advance rate) is constant with time. Assuming that the oxygen concentration at the bedrock–saprolite interface varies with the thickness of soil/saprolite yields predictive equations for how weathering advance rate and steady-state saprolite/soil thickness depend upon atmospheric oxygen levels and upon denudation rate. The denudation and weathering advance rates at steady state are therefore related through a condition on the concentration of porewater oxygen at the base of the saprolite. In our model for spheroidal weathering of the Rio Blanco quartz diorite, fractures occur every ∼250yr, ferric oxide is fully depleted over a four rindlet set in ∼1000yr, and saprolitization is completed in ∼5000yr in the zone containing ∼20 rindlets. Spheroidal weathering thus allows weathering to keep up with the high rate of denudation by enhancing access of bedrock to reactants by fracturing. Coupling of denudation and weathering advance rates can also occur for the case that weathering occurs without spheroidal fractures, but for the same kinetics and transport parameters, the maximum rate of saprolitization achieved would be far smaller than the rate of denudation for the Rio Blanco system. The spheroidal weathering model provides a quantitative picture of how physical and chemical processes can be coupled explicitly during bedrock alteration to soil to explain weathering advance rates that are constant in time.

REDUCTION OF BEDROCK BLOCKS AS CORESTONES IN THE WEATHERING PROFILE: OBSERVATIONS AND MODEL

Fletcher RC, Brantley SL. 2010. Reduction of bedrock blocks as corestones in the weathering profile: observations
and model. Am. J. Sci. 310:131–64

Abstract: 
the Espiritu Santo and Mameyes rivers within the Luquillo Experimental Forest (Puerto Rico) are interpreted as corestones, reduced from initial joint-bounded bedrock blocks by subsurface weathering. Maximum corestone size, expressed as the geometric mean of the three dimensions, S 3 abc, shows a smooth envelope when plotted against elevation. We postulate that, for each catchment, they represent in situ corestones within a stratified weathering profile, many tens of meters in thickness, that has been subsequently exhumed by younger erosion. We formulate a simplified one-dimensional model for reduction in corestone size within a steady-state weathering profile that incorporates: (i) vertical fluid transport of the reactant and the soluble products of chemical weathering; (ii) linear kinetics of corestone reduction; and, subsequently, (iii) erosion. The rate of advance of a steady-state weathering profile is a statement of the mass balance between entering reactants and weathering components, here idealized as H and albite. The mathematical relations, tie the laboratory-determined rate constant for dissolution of albite (k) to a generalized kinetic constant for the rate of decrease (K) in corestone diameter to the advance rate of the weathering profile (V ). The last parentheses contain an effective roughness at the scale of the weathering profile, where S0 is the maximum size of initial bedrock blocks, inferred to be set by initial bedrock fracture spacing, and 3L* is the profile thickness. The laboratory scale roughness value, , is the ratio of the surface area accessed by BET analysis to that of the corestone grain scale. In the model, erosion is not coupled with weathering, although the presence of corestones of finite size, SE>0, exiting at the erosional surface may be postulated to affect the erosional flux. The thickness of the corestone weathering profile derived for the model for the distance between bedrock and a corestone-free saprolite cap is approximately This expression is the product of the effective pH buffering-adjusted input reactant flux per unit area times a stoichiometeric factor linking this to net albite dissolution, divided by the rate of corestone size reduction at the input concentration of protons. Further, the profile thickness scales with the input “particle” size, S0. The model fit, which yields the ratio is consistent with a rate constant for albite dissolution that lies between laboratorymeasured and field-estimated values. Sensitivity to the reaction order of albite dissolution with respect to H, N, is small, except near the base of the profile. This model yields insights into the relationship between fracture spacing and the evolution of particle size and chemistry in weathering profiles.

Twelve testable hypotheses on the geobiology of weathering

Abstract: 
Critical Zone (CZ) research investigates the chemical, physical, and biological processes that modulate the Earth's surface. Here, we advance 12 hypotheses that must be tested to improve our understanding of the CZ: (1) Solar-to-chemical conversion of energy by plants regulates flows of carbon, water, and nutrients through plant-microbe soil networks, thereby controlling the location and extent of biological weathering. (2) Biological stoichiometry drives changes in mineral stoichiometry and distribution through weathering. (3) On landscapes experiencing little erosion, biology drives weathering during initial succession, whereas weathering drives biology over the long term. (4) In eroding landscapes, weathering-front advance at depth is coupled to surface denudation via biotic processes. (5) Biology shapes the topography of the Critical Zone. (6) The impact of climate forcing on denudation rates in natural systems can be predicted from models incorporating biogeochemical reaction rates and geomorphological transport laws. (7) Rising global temperatures will increase carbon losses from the Critical Zone. (8) Rising atmospheric P(CO2) will increase rates and extents of mineral weathering in soils. (9) Riverine solute fluxes will respond to changes in climate primarily due to changes in water fluxes and secondarily through changes in biologically mediated weathering. (10) Land use change will impact Critical Zone processes and exports more than climate change. (11) In many severely altered settings, restoration of hydrological processes is possible in decades or less, whereas restoration of biodiversity and biogeochemical processes requires longer timescales. (12) Biogeochemical properties impart thresholds or tipping points beyond which rapid and irreversible losses of ecosystem health, function, and services can occur.
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