How temperature-dependent silicate weathering acts as Earth's geological thermostat.

Earth's climate may be stabilized over millennia by solubilization of atmospheric carbon dioxide (CO2) as minerals weather, but the temperature sensitivity of this thermostat is poorly understood. We discovered that the temperature dependence of weathering expressed as an activation energy increases from laboratory to watershed as transport, clay precipitation, disaggregation, and fracturing increasingly couple to dissolution. A simple upscaling to the global system indicates that the temperature dependence decreases to ~22 kilojoules per mole because (i) the lack of runoff limits weathering and retains base metal cations on half the land surface and (ii) other landscapes are regolith-shielded and show little weathering response to temperature. By comparing weathering from laboratory to globe, we reconcile some aspects of kinetic and thermodynamic controls on CO2 drawdown by natural or enhanced weathering.

Impact of shale gas development on regional water quality.

Unconventional natural gas resources offer an opportunity to access a relatively clean fossil fuel that could potentially lead to energy independence for some countries. Horizontal drilling and hydraulic fracturing make the extraction of tightly bound natural gas from shale formations economically feasible. These technologies are not free from environmental risks, however, especially those related to regional water quality, such as gas migration, contaminant transport through induced and natural fractures, wastewater discharge, and accidental spills. We review the current understanding of environmental issues associated with unconventional gas extraction. Improved understanding of the fate and transport of contaminants of concern and increased long-term monitoring and data dissemination will help manage these water-quality risks today and in the future.

Twelve testable hypotheses on the geobiology of weathering.

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.

Molybdenum isotope fractionation by cyanobacterial assimilation during nitrate utilization and N2 fixation.

We measured the δ98Mo of cells and media from molybdenum (Mo) assimilation experiments with the freshwater cyanobacterium Anabaena variabilis, grown with nitrate as a nitrogen (N) source or fixing atmospheric N2. This organism uses a Mo-based nitrate reductase during nitrate utilization and a Mo-based dinitrogenase during N2 fixation under culture conditions here. We also demonstrate that it has a high-affinity Mo uptake system (ModABC) similar to other cyanobacteria, including marine N2-fixing strains. Anabaena variabilis preferentially assimilated light isotopes of Mo in all experiments, resulting in fractionations of -0.2‰ to -1.0‰ ± 0.2‰ between cells and media (ε(cells-media)), extending the range of biological Mo fractionations previously reported. The fractionations were internally consistent within experiments, but varied with the N source utilized and for different growth phases sampled. During growth on nitrate, A. variabilis consistently produced fractionations of -0.3 ± 0.1‰ (mean ± standard deviation between experiments). When fixing N2, A. variabilis produced fractionations of -0.9 ± 0.1‰ during exponential growth, and -0.5 ± 0.1‰ during stationary phase. This pattern is inconsistent with a simple kinetic isotope effect associated with Mo transport, because Mo is likely transported through the ModABC uptake system under all conditions studied. We present a reaction network model for Mo isotope fractionation that demonstrates how Mo transport and storage, coordination changes during enzymatic incorporation, and the distribution of Mo inside the cell could all contribute to the total biological fractionations. Additionally, we discuss the potential importance of biologically incorporated Mo to organic matter-bound Mo in marine sediments.

Short- and long-term olivine weathering in Svalbard: implications for Mars.

Liquid water is essential to life as we know it on Earth; therefore, the search for water on Mars is a critical component of the search for life. Olivine, a mineral identified as present on Mars, has been proposed as an indicator of the duration and characteristics of water because it dissolves quickly, particularly under low-pH conditions. The duration of olivine persistence relative to glass under conditions of aqueous alteration reflects the pH and temperature of the reacting fluids. In this paper, we investigate the utility of 3 methodologies to detect silicate weathering in a Mars analog environment (Sverrefjell volcano, Svalbard). CheMin, a miniature X-ray diffraction instrument developed for flight on NASA's upcoming Mars Science Laboratory, was deployed on Svalbard and was successful in detecting olivine and weathering products. The persistence of olivine and glass in Svalbard rocks was also investigated via laboratory observations of weathered hand samples as well as an in situ burial experiment. Observations of hand samples are consistent with the inference that olivine persists longer than glass at near-zero temperatures in the presence of solutions at pH approximately 7-9 on Svalbard, whereas in hydrothermally altered zones, glass has persisted longer than olivine in the presence of fluids at similar pH at approximately 50 degrees C. Analysis of the surfaces of olivine and glass samples, which were buried on Sverrefjell for 1 year and then retrieved, documented only minor incipient weathering, though these results suggest the importance of biological impacts. The 3 types of observations (CheMin, laboratory observations of hand samples, burial experiments) of weathering of olivine and glass at Svalbard show promise for interpretation of weathering on Mars. Furthermore, the weathering relationships observed on Svalbard are consistent with laboratory-measured dissolution rates, which suggests that relative mineral dissolution rates in the laboratory, in concert with field observations, can be used to yield valuable information regarding the pH and temperature of reacting martian fluids.