The synergistic effect of calcium on organic carbon sequestration to ferrihydrite

Sequestration of organic carbon (OC) in environmental systems is critical to mitigating climate change. Organo-mineral associations, especially those with iron (Fe) oxides, drive the chemistry of OC sequestration and stability in soils. Short-range-ordered Fe oxides, such as ferrihydrite, demonstrate a high affinity for OC in binary systems. Calcium commonly co-associates with OC and Fe oxides in soils, though the bonding mechanism (e.g., cation bridging) and implications of the co-association for OC sequestration remain unresolved. We explored the effect of calcium (Ca²⁺) on the sorption of dissolved OC to 2-line ferrihydrite. Sorption experiments were conducted between leaf litter-extractable OC and ferrihydrite at pH 4 to 9 with different initial C/Fe molar ratios and Ca²⁺ concentrations. The extent of OC sorption to ferrihydrite in the presence of Ca²⁺ increased across all tested pH values, especially at pH ≥ 7. Sorbed OC concentration at pH 9 increased from 8.72 ± 0.16 to 13.3 ± 0.20 mmol OC g^?1 ferrihydrite between treatments of no added Ca²⁺ and 30 mM Ca²⁺ addition. Batch experiments were paired with spectroscopic studies to probe the speciation of sorbed OC and elucidate the sorption mechanism. ATR-FTIR spectroscopy analysis revealed that carboxylic functional moieties were the primary sorbed OC species that were preferentially bound to ferrihydrite and suggested an increase in Fe-carboxylate ligand exchange in the presence of Ca at pH 9. Results from batch to spectroscopic experiments provide significant evidence for the enhancement of dissolved OC sequestration to 2-line ferrihydrite and suggest the formation of Fe–Ca-OC ternary complexes. Findings of this research will inform modeling of environmental C cycling and have the potential to influence strategies for managing land to minimize OM stabilization.     

The Emergence of Standardized,Idealized, and Placeless Landscapes in Midwestern Main Street Postcards

Although Main Streets line small towns from Florida to Alaska, Main Street is more than just a street name; it is a place imbued with local pride, regional identity, and national virtues. This symbolic connection derives from the Midwestern Main Streets of the first half of the twentieth century, a time that coincides with the golden age of the picture postcard. This article explores how the connotative and denotative symbols from this golden age overlap. A sample of 140 postcards from small towns in Kansas and Nebraska with a viable Main Street from 1900 to 1945 was selected from books, personal collections, and Internet auction sites. Our discovery of a disconnect between picture postcard and reality was not surprising, but there was a shift from the significance of basic denotative signs and the particularities of individual Main Streets in the early part of the twentieth century to an increased importance of connotative signs unifying a homogeneous Main Street ideal. Three distinct eras of postcard manipulation emerged from the data: A slightly manipulated 1900–1911 era, a 1912–1930 era emphasizing a corridor of progress, and a 1931–1945 era that displayed a growing detachment from reality and moved from the unique characteristics of a particular town toward a homogenized and idealized “Main Street view.” This article offers empirical evidence for the theoretical propositions of humanist and critical geographers that the representations of the American landscape are becoming increasingly homogenized, contrived, and placeless.     

Experimental studies relating to microfracture in sandstone

A fundamental understanding of the relation between stress concentrations at grain contacts and microfractures in granular aggregates is obtained through two-dimensional photomechanical model studies and is tested through observational studies of experimentally deformed sandstone discs, glass beads, and quartz sand.In uncemented aggregates, the state of stress in each grain is controlled by the manner in which the applied load is transmitted across grain contacts. The angles between lines connecting pairs of contacts and the axis of the principal load acting at the boundaries of the aggregate determine which of all contacts will be most highly stressed or “critical”. Microfractures follow that maximum principal stress trajectory which connects critical contacts, and they propagate through those points where the magnitude of the local maximum stress difference is the greatest. Microfractures, therefore, are extension fractures. It then follows that both the locations and orientations of fractures can be predicted if the state of stress in the grains is known.Positioning of critical contacts depends primarily on sorting, packing, grain shapes, and the boundary load conditions applied to the aggregate. Some critical contacts and, therefore, microfractures tend to join together in a series or “chain”. Orientations of chains are most strongly influenced by the direction of the maximum compressive load at the boundary of the aggregate. A hydrostatic load applied on the boundaries of an aggregate can cause microfracturing within grains. Orientations for microfractures and contact lines are random in poorly sorted aggregates, but they are influenced by packing in well sorted aggregates.Grains of cemented aggregates are more highly stressed at their centers than at contacts. By analogy, microfracture orientations depend strongly on the position of the greatest load axis and only slightly on the low-magnitude stress concentrations at contacts. These microfractures parallel the greatest principal stress trajectory in regions where the magnitude of the maximum stress difference is greatest. These observations lead to the conclusion that fractures in grains of cemented aggregates are also extension fractures and should exhibit a higher degree of preferred orientation than in uncemented counterparts.These conclusions hold when cementing materials have about the same elastic moduli as the grains. Cements may be so weak that the aggregate behaves as if it were uncemented in terms of microfracture fabric, or so stiff that the major part of the load is transmitted by the cement, and the composite is no longer an aggregate in the mechanical sense.     

Climate change, water resources, and the politics of adaptation in the Middle East and North Africa

Through an examination of global climate change models combined with hydrological data on deteriorating water quality in the Middle East and North Africa (MENA), we elucidate the ways in which the MENA countries are vulnerable to climate-induced impacts on water resources. Adaptive governance strategies, however, remain a low priority for political leaderships in the MENA region. To date, most MENA governments have concentrated the bulk of their resources on large-scale supply side projects such as desalination, dam construction, inter-basin water transfers, tapping fossil groundwater aquifers, and importing virtual water. Because managing water demand, improving the efficiency of water use, and promoting conservation will be key ingredients in responding to climate-induced impacts on the water sector, we analyze the political, economic, and institutional drivers that have shaped governance responses. While the scholarly literature emphasizes the importance of social capital to adaptive governance, we find that many political leaders and water experts in the MENA rarely engage societal actors in considering water risks. We conclude that the key capacities for adaptive governance to water scarcity in MENA are underdeveloped.     

Correction and protection in limestone terrane

Structural features that are hazards to building foundations include pinnacles, slots, and chimney-like openings in rock, alternate strata of hard rock and soft clay, dome-like cavities in soil, caves in rock, weak and compressible soils in cone-shaped depressions over collapsed domes and cavities, and open sinkholes from soil or rock collapse and soil erosion Design to overcome them includes avoiding areas of concentrated hazards, correcting the hazards by filling them or collapsing them, bridging over small hazards, reinforcing the rock, bypassing shallow hazards with deeper foundations, and minimizing activation of the hazard-forming processes.     

A Paleoecological History of the Late Precolonial and Postcolonial Mesohaline Chesapeake Bay Food Web

Geochemical (total nitrogen, total organic carbon, total phosphorus, total sulfur, and carbon and nitrogen stable isotopes) and selected biotic (diatom, foraminifera, polychaete) indicators preserved in two estuarine sediment cores from the mesohaline Chesapeake Bay provide a history of alterations in the food web associated with land-use change. One core from the mouth of the Chester River (CR) (collected in 2000) represents a 1,000-year record. The second core (collected in 1999), from the Chesapeake Bay’s main stem opposite the Choptank River (MD), represents a 500-year record. As European settlers converted a primarily forested landscape to agriculture, sedimentation rates increased, water clarity decreased, salinity decreased in some areas, and the estuarine food web changed into a predominantly planktonic system. Representatives of the benthic macrofaunal community (foraminifera and the polychaetes Nereis spp.) were affected by local changes before there were widespread landscape alterations. Nitrogen stable isotope records indicated that land-use changes affected nitrogen cycling beginning in the early 1700s. Extreme changes were evident in the mid-nineteenth century following widespread deforestation and since the mid-twentieth century reflecting heightened eutrophication as development increased in the Chesapeake Bay watershed. Results also demonstrate how paleoecological records vary due to the degree of terrestrial inputs of freshwater runoff and nutrients at core locations within the Chesapeake Bay.     

Distinguishing sources of ground water recharge by using delta2H and delta18O

Stable isotope values of hydrogen and oxygen from precipitation and ground water samples were compared by using a volumetrically based mixing equation and stable isotope gradient to estimate the season and location of recharge in four basins. Stable isotopes were sampled at 11 precipitation sites of differing elevation during a 2-year period to quantify seasonal stable isotope contributions as a function of elevation. Supplemental stable isotope data collected by the International Atomic Energy Association during a 14-year period were used to reduce annual variability of the mean seasonal stable isotope data. The stable isotope elevation relationships and local precipitation elevation relationships were combined by using a digital elevation model to calculate the total volumetric contribution of water and stable isotope values as a function of elevation within the basins. The results of these precipitation calculations were compared to measured ground water stable isotope values at the major discharge points near the terminus of the basins. Volumetric precipitation contributions to recharge were adjusted to isolate contributing elevations. This procedure provides an improved representation of recharge contributions within the basins over conventional stable isotope methods. Stable isotope values from wells and springs at the terminus of each basin were used to infer the elevations of precipitation important for recharge of the regional ground water flow system. Ancillary climatic, geologic, and stable isotope values were used to further constrain the location where precipitation is entering the ground water flow system.     

Fraction of young water as an indicator of aquifer vulnerability along two regional flow paths in the Mississippi embayment aquifer system,southeastern USA

Wells along two regional flow paths were sampled to characterize changes in water quality and the vulnerability to contamination of the Memphis aquifer across a range of hydrologic and land-use conditions in the southeastern United States. The flow paths begin in the aquifer outcrop area and end at public supply wells in the confined parts of the aquifer at Memphis, Tennessee. Age-date tracer (e.g. SF₆, ³H, ¹⁴C) data indicate that a component of young water is present in the aquifer at most locations along both flow paths, which is consistent with previous studies at Memphis that documented leakage of shallow water into the Memphis aquifer locally where the overlying confining unit is thin or absent. Mixtures of young and old water were most prevalent where long-term pumping for public supply has lowered groundwater levels and induced downward movement of young water. The occurrence of nitrate, chloride and synthetic organic compounds was correlated to the fraction of young water along the flow paths. Oxic conditions persisted for 10 km or more down dip of the confining unit, and the presence of young water in confined parts of the aquifer suggest that contaminants such as nitrate-N have the potential for transport. Long-term monitoring data for one of the flow-path wells screened in the confined part of the aquifer suggest that the vulnerability of the aquifer as indicated by the fraction of young water is increasing over time.     

Relationship between climate and vegetation and the stable carbon isotope chemistry of soils in the eastern Mojave Desert, Nevada

The relationship between the stable C-isotope composition of the soil environment and modern climate and vegetation was determined empirically along a present-day climatic transect in the eastern Mojave Desert. The δ¹³C of the soil CO₂ and carbonates decreased with increasing elevation and plant density, even though plant assemblages at all elevations were isotopically similar. Several factors, including differences in the ratios of pedogenic of limestone calcite and differences in past vegetation, were considered as explanations of this trend, However, it appears that in the sparsely vegetated Mojave Desert, the δ¹³C of pedogenic carbonate is controlled by differences in plant density and biological activity. This relationship may provide a tool for assessing past vegetational densities, as long as the vegetation is isotopically homogeneous.