Geophysical constraints on deep weathering and water storage potential in the Southern Sierra Critical Zone Observatory

The conversion of bedrock to regolith marks the inception of critical zone processes, but the factors that regulate it remain poorly understood. Although the thickness and degree of weathering of regolith are widely thought to be important regulators of the development of regolith and its water‐storage potential, the functional relationships between regolith properties and the processes that generate it remain poorly documented. This is due in part to the fact that regolith is difficult to characterize by direct observations over the broad scales needed for process‐based understanding of the critical zone. Here we use seismic refraction and resistivity imaging techniques to estimate variations in regolith thickness and porosity across a forested slope and swampy meadow in the Southern Sierra Critical Zone Observatory (SSCZO). Inferred seismic velocities and electrical resistivities image a weathering zone ranging in thickness from 10 to 35 m (average = 23 m) along one intensively studied transect. The inferred weathering zone consists of roughly equal thicknesses of saprolite (P‐velocity < 2 km s^?1) and moderately weathered bedrock (P‐velocity = 2–4 km s^?1). A minimum‐porosity model assuming dry pore space shows porosities as high as 50% near the surface, decreasing to near zero at the base of weathered rock. Physical properties of saprolite samples from hand augering and push cores are consistent with our rock physics model when variations in pore saturation are taken into account. Our results indicate that saprolite is a crucial reservoir of water, potentially storing an average of 3 m³ m^?2 of water along a forested slope in the headwaters of the SSCZO. When coupled with published erosion rates from cosmogenic nuclides, our geophysical estimates of weathering zone thickness imply regolith residence times on the order of 10⁵ years. Thus, soils at the surface today may integrate weathering over glacial–interglacial fluctuations in climate. Copyright © 2013 John Wiley & Sons, Ltd.     

Modeling of Stress Changes at Mayon Volcano,Philippines

In this paper, we analyze the stress change associated with the inverted volcanic source models at Mayon volcano, Philippines, where there are gravity changes without significant deformation after the 1993 eruption. We detail the applicable data and the associated inversion techniques and models prior to calculating the appropriate stress changes. It is determined that the stress change associated with the central magmatic source produces compressional stress changes at a secondary source to the northwest, prompting a change in the local water storage in the underlying fractured rock.     

Molecular indicators for palaeoenvironmental change in a Messinian evaporitic sequence (Vena del Gesso, Italy). II: High-resolution variations in abundances and 13C contents of free and sulphur-bound carbon skeletons in a single marl bed

The extractable organic matter of 10 immature samples from a marl bed of one evaporitic cycle of the Vena del Gesso sediments (Gessoso-solfifera Fm., Messinian, Italy) was analyzed quantitatively for free hydrocarbons and organic sulphur compounds. Nickel boride was used as a desulphurizing agent to recover sulphur-bound lipids from the polar and asphaltene fractions. Carbon isotopic compositions (delta vs PDB) of free hydrocarbons and of S-bound hydrocarbons were also measured. Relationships between these carbon skeletons, precursor biolipids, and the organisms producing them could then be examined. Concentrations of S-bound lipids and free hydrocarbons and their delta values were plotted vs depth in the marl bed and the profiles were interpreted in terms of variations in source organisms, 13 C contents of the carbon source, and environmentally induced changes in isotopic fractionation. The overall range of delta values measured was 24.7%, from -11.6% for a component derived from green sulphur bacteria (Chlorobiaceae) to -36.3% for a lipid derived from purple sulphur bacteria (Chromatiaceae). Deconvolution of mixtures of components deriving from multiple sources (green and purple sulphur bacteria, coccolithophorids, microalgae and higher plants) was sometimes possible because both quantitative and isotopic data were available and because either the free or S-bound pool sometimes appeared to contain material from a single source. Several free n-alkanes and S-bound lipids appeared to be specific products of upper-water-column primary producers (i.e. algae and cyanobacteria). Others derived from anaerobic photoautotrophs and from heterotrophic protozoa (ciliates), which apparently fed partly on Chlorobiaceae. Four groups of n-alkanes produced by algae or cyanobacteria were also recognized based on systematic variations of abundance and isotopic composition with depth. For hydrocarbons probably derived from microalgae, isotopic variations are well correlated with those of total organic carbon. A resistant aliphatic biomacromolecule produced by microalgae is, therefore, probably an important component of the kerogen. These variations reflect changes in the depositional environment and early diagenetic transformations. Changes in the concentrations of S-bound lipids induced by variations in conditions favourable for sulphurization were discriminated from those related to variations in primary producer assemblages. The water column of the lagoonal basin was stratified and photic zone anoxia occurred during the early and middle stages of marl deposition. During the last stage of the marl deposition the stratification collapsed due to a significant shallowing of the water column. Contributions from anaerobic photoautotrophs were apparently associated with variations in depth of the chemocline.     

Diploptene: an indicator of terrigenous organic carbon in Washington coastal sediments

The pentacyclic triterpene 17 beta(H),21 beta(H)-hop-22(29)-ene (diploptene) occurs in sediments throughout the Columbia River drainage basin and off the southern coast of Washington state in concentrations comparable to long-chain plantwax n-alkanes. The same relationship is evident for diploptene and long-chain n-alkanes in soils from the Willamette Valley. Microorganisms indigenous to soils and soil erosion are indicated as the biological source and physical process, respectively, for diploptene in coastal sediments. Similarity between the stable carbon isotopic composition (delta 13CPDB) of diploptene isolated from soil in the Willamette Valley (-31.2 +/- 0.3%) and from sediments deposited throughout the Washington coastal environment (-31.2 +/- 0.5%) supports this argument. Values of delta for diploptene in river sediments are variable and 8-17% lighter, indicating that an additional biological source such as methane-oxidizing bacteria makes a significant contribution to the diploptene record in river sediments. Selective biodegradation resulting from a difference in the physicochemical association within eroded particles can explain the absence of the more-13C-depleted form of diploptene in Washington coastal sediments, but this mechanism remains unproven.     

Stable carbon-isotopic compositions of lipids isolated from the ammonia-oxidizing chemoautotroph Nitrosomonas europaea

For the ammonia-oxidizing bacterium Nitrosomonas europaea, grown autotrophically using semicontinuous culturing, average biomass was depleted in ¹³C relative to CO₂ dissolved in the medium by ca. 20‰ and the total-lipid extract was depleted in ¹³C relative to biomass by 3.7‰. The n-alkyl lipids (weighted average of fatty acids) and isoprenoid lipids (weighted average of hopanoids) were both depleted in ¹³C relative to biomass by about 9‰. The large depletion in the isoprenoid lipids seems to indicate that isotopic fractionations associated with the biosynthesis of methylerythritol phosphate (MEP) affected at least two carbon positions in each isoprene unit. Among the fatty acids, trans-9-hexadecenoic acid was most depleted (13.0‰ relative to biomass), followed by cis-9- hexadecenoic acid (9.6‰) and hexadecanoic acid (6.9‰). Isotopic relationships between the three acids suggest that significant isotope effects were associated with the desaturation and cis to trans isomerization of fatty acids. Given these observations, hopanoids produced by ammonia-oxidizing bacteria growing in natural waters are likely to be depleted in ¹³C by 26–30‰ relative to dissolved CO₂. Since CO₂ at aquatic oxyclines is often depleted in ¹³C, the range of δ values expected for hopanoids is ca. −34‰ to −55‰. The δ values of geohopanoids observed in numerous studies and attributed to unspecified chemoautotrophs fall within this range.     

Diel variation of selenium and arsenic in a wetland of the Great Salt Lake, Utah

Diel (24-h) changes in Se and As concentrations in a freshwater wetland pond bordering the Great Salt Lake (GSL) were examined. Selenium concentrations (filtered and unfiltered) changed on a diel basis, i.e., were depleted during early morning and enriched during daytime over August 17-18. During the May 24-25, 2006 and September 29-30 diel studies, no significant 24-h trends were observed in Se concentrations compared to August, which showed daily maximums up to 59% greater than the daily minimum. Both filtered and unfiltered As concentrations also varied on a diel cycle, with increased concentrations during early morning and decreased concentrations during daytime. Filtered As concentrations increased 110% during the May 24-25, 2006 diel study. Selenium varied in phase with pH, dissolved O₂ (DO), and water temperature (T_w) whereas As varied opposite to Se, pH, DO and T_w. Changes in pH, DO and T_w showed a direct linear correlation (r = 0.74, 0.75, and 0.55, respectively) to filtered Se. Also pH, DO and T_w were inversely correlated to filtered As concentration (r = −0.88, −0.87, and −0.84, respectively). Equilibrium geochemical speciation and sorption models were used to examine the potential oxidation state changes in Se and As, and sorption and desorption reactions corresponding to the observed 24-h variations in pe and pH. In this wetland it was postulated that diel Se variation was driven by sorption and desorption due to photosynthesis-induced changes in pH and redox conditions. Diel variations of As were hypothesized to be linked to pH-driven sorption and desorption as well as co-precipitation and co-dissolution with mineral phases of Mn.     

Fractionation of carbon isotopes by phytoplankton and estimates of ancient CO2 levels

Reports of the 13C content of marine particulate organic carbon are compiled and on the basis of GEOSECS data and temperatures, concentrations, and isotopic compositions of dissolved CO2 in the waters in which the related phytoplankton grew are estimated. In this way, the fractionation of carbon isotopes during photosynthetic fixation of CO2 is found to be significantly correlated with concentrations of dissolved CO2. Because ancient carbon isotopic fractionations have been determined from analyses of sedimentary porphyrins [Popp et al., 1989], the relationship between isotopic fractionation and concentrations of dissolved CO2 developed here can be employed to estimate concentrations of CO2 dissolved in ancient oceans and, in turn, partial pressures of CO2 in ancient atmospheres. The calculations take into account the temperature dependence of chemical and isotopic equilibria in the dissolved-inorganic-carbon system and of air-sea equilibria. Paleoenvironmental temperatures for each sample are estimated from reconstructions of paleogeography, latitudinal temperature gradients, and secular changes in low-latitude sea surface temperature. It is estimated that atmospheric partial pressures of CO2 were over 1000 micro atm 160 - 100 Ma ago, then declined to values near 300 micro atm during the next 100 Ma. Analysis of a high-resolution record of carbon isotopic fractionation at the Cenomanian-Turonian boundary suggests that the partial pressure of CO2 in the atmosphere was drawn down from values near 840 micro atm to values near 700 micro atm during the anoxic event.