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.

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.

Controls on major solutes within the drainage network of a rapidly 3 weathering tropical watershed

Bhatt, M. P., and W. H. McDowell (2007), Controls on major solutes within the drainage network of a rapidly weathering
27 tropical watershed, Water Resour. Res., 43, XXXXXX, doi:10.1029/2007WR005915.

Surface water chemistry in the main stem and source points of the Rio Icacos basin 7 (Luquillo Experimental Forest, Puerto Rico) was studied to investigate the factors 8 regulating spatial variability in major solutes in a rapidly weathering landscape. We 9 sampled along the main stem as well as at small source points at high elevation where 10 fresh bedrock is frequently exposed, and at low elevation in the floodplain/colluvial 11 plain of the main stem. Concentrations of silicon, alkalinity, and the sum of base 12 cations were lower at the source points than in the main stem, and were lowest in low- 13 elevation source points. Calcium and sodium were the dominant cations at all sampling 14 points after sea-salt correction, reflecting the weathering of plagioclase feldspar 15 throughout the basin. The partial pressure of carbon dioxide (pCO2) tended to be higher, 16 and HCO3  concentrations were lower, in the low-elevation source points than at other 17 positions in the landscape. When coupled with the relatively low concentrations of Si and 18 base cations, this suggests that the availability of primary reactive minerals, rather than 19 carbonic acid concentrations, limits weathering in these low-elevation sources. 20 Mechanical denudation appears to enhance chemical weathering rates not only by 21 refreshing reactive mineral surfaces but also by contributing carbon dioxide from the 22 decomposition of organic-rich material in landslides, which occur frequently. The spatial 23 variability of major solutes appears to depend primarily on the availability of fresh primary 24 reactive minerals, carbon dioxide concentrations, and hydrolysis conditions.
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