Lixin Jin

Twelve testable hypotheses on the geobiology of weathering

Critical Zone (CZ) research investigates the chemical, physical, and biological processes that modulate the Earths 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.

Evidence for carbon sequestration by agricultural liming

[i] Agricultural lime can be a source or a sink for CO 2 , depending on whether reaction occurs with strong acids or carbonic acid. Here we examine the impact of liming on global warming potential by comparing the sum of Ca 2+ and Mg 2+ to carbonate alkalinity in soil solutions beneath unmanaged vegetation versus limed row crops, and of streams and rivers in agricultural versus forested watersheds, mainly in southern Michigan. Soil solutions sampled by tension indicated that lime can act as either a source or a sink for CO 2 . However, infiltrating waters tended to indicate net CO 2 uptake, as did tile drainage waters and streams draining agricultural watersheds. As nitrate concentrations increased in infiltrating waters, lime switched from a net CO 2 sink to a source, implying nitrification as a major acidifying process. Dissolution of lime may sequester CO 2 equal to roughly 25-50% of its C content, in contrast to the prevailing assumption that all of the carbon in lime becomes CO 2 . The ∼30 Tg/yr of agricultural lime applied in the United States could thus sequester up to 1.9 Tg C/yr, about 15% of the annual change in the U.S. CO 2 emissions (12 Tg C/yr for 2002-2003). The implications of liming for atmospheric CO 2 stabilization should be considered in strategies to mitigate global climate change.

Characterization of deep weathering and nanoporosity development in shale - a neutron study

Abstract We used small-angle and ultra-small-angle neutron scattering (SANS/USANS) to characterize the evolution of nanoscale features in weathering Rose Hill shale within the Susquehanna/Shale Hills Observatory (SSHO). The SANS/USANS techniques, here referred to as neutron scattering (NS), characterize porosity comprised of features ranging from approximately 3 nm to several micrometers in dimension. NS was used to investigate shale chips sampled by gas-powered drilling (“saprock”) or by hand-augering (“regolith”) at ridgetop. At about 20 m depth, dissolution is inferred to have depleted the bedrock of ankerite and all the chips investigated with NS are from above the ankerite dissolution zone. NS documents that 5-6% of the total ankerite-free rock volume is comprised of isolated, intraparticle pores. At 5 m depth, an abrupt increase in porosity and surface area corresponds with onset of feldspar dissolution in the saprock and is attributed mainly to peri-glacial processes from 15 000 years ago. At tens of centimeters below the saprock-regolith interface, the porosity and surface area increase markedly as chlorite and illite begin to dissolve. These clay reactions contribute to the transformation of saprock to regolith. Throughout the regolith, intraparticle pores in chips connect to form larger interparticle pores and scattering changes from a mass fractal at depth to a surface fractal near the land surface. Pore geometry also changes from anisotropic at depth, perhaps related to pencil cleavage created in the rock by previous tectonic activity, to isotropic at the uppermost surface as clays weather. In the most weathered regolith, kaolinite and Fe-oxyhydroxides precipitate, blocking some connected pores. These precipitates, coupled with exposure of more quartz by clay weathering, contribute to the decreased mineral-pore interfacial area in the uppermost samples. These observations are consistent with conversion of bedrock to saprock to regolith at SSHO due to: (1) transport of reactants (e.g., water, O2) into primary pores and fractures created by tectonic events and peri-glacial effects; (2) mineral-water reactions and particle loss that increase porosity and the access of water into the rock. From deep to shallow, mineral-water reactions may change from largely transport-limited where porosity was set largely by ancient tectonic activity to kinetic-limited where porosity is changing due to climate-driven processes.

Soils reveal widespread manganese enrichment from industrial inputs

It is well-known that metals are emitted to the air by human activities and subsequently deposited to the land surface; however, we have not adequately evaluated the geographic extent and ecosystem impacts of industrial metal loading to soils. Here, we demonstrate that atmospheric inputs have widely contaminated soils with Mn in industrialized regions. Soils record elemental fluxes impacting the Earths surface and can be analyzed to quantify inputs and outputs during pedogenesis. We use a mass balance model to interpret details of Mn enrichment by examining soil, bedrock, precipitation, and porefluid chemistry in a first-order watershed in central Pennsylvania, USA. This reveals that ∼ 53% of Mn in ridge soils can be attributed to atmospheric deposition from anthropogenic sources. An analysis of published data sets indicates that over half of the soils surveyed in Pennsylvania (70%), North America (60%), and Europe (51%) are similarly enriched in Mn. We conclude that soil Mn enrichment due to industrial inputs is extensive, yet patchy in distribution due to source location, heterogeneity of lithology, vegetation, and other attributes of the land surface. These results indicate that atmospheric transport must be considered a potentially critical component of the global Mn cycle during the Anthropocene.

The carbonate system geochemistry of shallow groundwater–surface water systems in temperate glaciated watersheds (Michigan, USA): Significance of open-system dolomite weathering

We present here a field geochemical study of controls on carbonate weathering within rapidly circulating, shallow groundwater–surface water systems in the glaciated mid-continent region. Groundwaters and surface waters in three watersheds spanning the Upper to Lower Peninsulas of Michigan consist of Ca 2+ -Mg 2+ -HCO 3 − solutions derived from the open-system dissolution of calcite and dolomite in soils developed on mixed mineralogy glacial drift. The thermodynamic stabilities of calcite and dolomite both decrease with decreasing temperature, with dolomite more strongly affected. Thus, the low mean annual temperature of these temperate weathering environments maximizes the absolute solubility of dolomite as well as its solubility relative to calcite. Many groundwaters in the study area approach equilibrium with respect to the more soluble dolomite and are moderately supersaturated with respect to calcite. Groundwaters in each watershed have distinct and relatively narrow ranges of carbon dioxide partial pressure ( P CO 2 ) values, which increase significantly from north to south (log P CO 2 of −3.0 to −2.2 atm), suggesting that there are landscape-level differences in carbon transformation rates in soil weathering zones. Increases in weathering-zone P CO 2 values produce HCO 3 − concentrations that vary by a factor of five, but the Mg 2+ /Ca 2+ and Mg 2+ /HCO 3 − ratios of all groundwaters are similar, suggesting relatively constant weathering input ratios of calcite and dolomite. Although surface waters commonly are between 2 and 10 times supersaturated with respect to calcite, the Mg 2+ /HCO 3 − ratios of surface waters are very close to initial groundwater values, suggesting that back precipitation of calcite is not a significant process in these systems. The enhanced solubility of dolomite at low temperatures coupled with the landscape-level differences in carbon cycling suggest that temperate-zone weathering reactions in glaciated terrains are significant contributors to continent-scale fluxes of both Mg 2+ and HCO 3 − .

Importance of vegetation for manganese cycling in temperate forested watersheds

Many surface soils are enriched in metals due to anthropogenic atmospheric inputs. To predict the persistence of these contaminants in soils, factors that impact rates of metal removal from soils into streams must be understood. Experiments at containerized seedling (mesocosm), pedon, and catchment scales were used to investigate the influence of vegetation on manganese (Mn) transport at the Susquehanna/Shale Hills Critical Zone Observatory (SSHCZO) in Pennsylvania, USA, where past atmospheric inputs from industrial sources have enriched Mn in surface soils. Large quantities of Mn that were leached from soil components into solution were taken up by vegetation; as a result, only relatively small quantities of Mn were removed from soil into effluent and streams. Manganese uptake into vegetation exceeded Mn losses in soil leachate by 20–200X at all scales, and net Mn loss from soils decreased in the presence of vegetation due to uptake into plant tissues. The majority of Mn taken up by forest vegetation at SSHCZO each year was returned to the soil in leaf litter and consequently immobilized as Mn oxides that formed during litter decomposition. Thus, plant uptake of Mn combined with rapid oxidation of Mn during litter decomposition contribute to long-term retention. Current release rates of soluble Mn from SSHCZO soils were similar to release rates from the larger Susquehanna River Basin, indicating that the processes observed at SSHCZO may be widespread across the region. Indeed, although atmospheric deposition of Mn has declined, surface soils at SSHCZO and throughout the eastern United States remain enriched in Mn. If recycling through vegetation can attenuate the removal of Mn from soils, as observed in this study, then Mn concentrations in soils and river waters will likely decrease slowly over time following watershed contamination. Understanding the role of vegetation in regulating metal transport is important for evaluating the long-term effects of historical and ongoing metal loading to soils.

Evaluation of geochemical processes and nitrate pollution sources at the Ljubljansko polje aquifer (Slovenia): A stable isotope perspective

The Ljubljansko polje aquifer, which is the main supply of drinking water for the local population in Ljubljana, Slovenia is highly vulnerable to anthropogenic pollution. In this study, the geochemistry of major constituents including nitrate concentrations and the dual isotopes of nitrate were used to ascertain the spatial distribution of processes and nitrate sources in the groundwater from seven wells at three different water supplies: Kleče, Hrastje and Jarški prod. The groundwater is of the Ca2+-Mg2+-HCO3- type approaching equilibrium with respect to dolomite and are moderately supersaturated with calcite. The groundwater nitrate concentrations ranged from 5.32 to 50.1 mg L-1 and are well above the threshold value for anthropogenic activity (3 mg L-1). The δ15NNO3 values ranged from 1.4 to 9.7‰, while δ18ONO3 values were from 6.3 to 34.6‰. Based on isotope mixing model three sources of nitrate were identified: atmospheric deposition, fertilizers and soil nitrogen. At Kleče 8, Kleče 12 and Jarški prod 3 the low δ15NNO3 and high δ18ONO3 values result from pristine nitrate sources, while in Hrastje 3 and Kleče 11 equal amounts of nitrate derived from soils with mixed fertilization and sewage. The data also indicate that the main sources of high nitrate concentrations in groundwater are from fertilizers and sewage-manure (comprising up to 64%). Such levels occurred in the Hrastje and Kleče 11 wells where precipitation is the main source of groundwater. Nitrate derived from atmospheric deposition accounted for approximately 10% of the nitrate in the groundwater. The message from this study is that to reduce the nitrogen load and improve water quality will involve containment and the careful management of sources from urban and agriculture inputs such as sewage-manure and fertilizers.