Organic matter in small mesopores in sediments and soils

The three-way correlation among organic matter concentrations, specific surface area and small mesopores observed for many soils and sediments led to the hypothesis that enclosure within the pores might explain the apparent protection of organic matter by minerals. We test this hypothesis by examining whether the bulk of organic matter resides within small mesopores. Pore volumes as a function of pore width were measured before and after organic matter removal, and the volume differences ascribed to organic matter filling of pores. Minor changes in small mesopore size distributions upon treatments such as centrifugation and muffling indicate the robustness of the mineral matrices that form these pores. We developed an additional method to assess organic matter densities using high-resolution pycnometry, and used these densities to convert pore volumes to organic matter contents. Although smaller mesopores are shown to have sufficient volumes to contain significant fractions of the total organic matter, only small fractions of total organic matter were found to reside in them. These results are consistent with preferential association between organic matter and aluminous clay particle edges, rather than the largely siliceous clay faces that contribute most surface area and form pore walls. While simple enclosure within smaller mesopores cannot, therefore, explain protection, network effects working at larger size scales may account for exclusion of digestive agents and hence organic matter protection.     

U–Pb ages of Neoarchean granitoids from the Black Hills, South Dakota, USA: implications for crustal evolution in the Archean Wyoming province

Zircons in basement rocks from the eastern Wyoming province (Black Hills, South Dakota, USA) have been analyzed by ion microprobe (SHRIMP) in order to determine precise ages of Archean tectonomagmatic events. In the northern Black Hills (NBH) near Nemo, Phanerozoic and Proterozoic (meta)sedimentary rocks are nonconformably underlain by Archean biotite–feldspar gneiss (BFG) and Little Elk gneissic granite (LEG), both of which intrude older schists. The Archean granitoid gneisses exhibit a pervasive NW–SE-trending fabric, whereas an earlier NE–SW-trending fabric occurs sporadically only in the BFG, which is intruded by the somewhat younger LEG. Zircon crystals obtained from the LEG and BFG exhibit double terminations, oscillatory zoning, and Th/U ratios of 0.6±0.3—thereby confirming a magmatic origin for both lithologies. In situ analysis of the most U–Pb concordant domains yields equivalent ²⁰⁷Pb/²⁰⁶Pb ages (upper intercept, U–Pb concordia) of 2559±6 and 2563±6 Ma (both ±2σ) for the LEG and BFG, respectively, which constrains a late Neoarchean age for sequential pulses of magmatism in the NBH. Unzoned (in BSE) patches of 2560 Ma zircon commonly truncate coeval zonation in the same crystals with no change in Th/U ratio, suggesting that deuteric, fluid-assisted recrystallization accompanied post-magmatic cooling. A xenocrystic core of magmatic zircon observed in one LEG zircon yields a concordant age of 2894±6 Ma (±2σ). This xenocryst represents the oldest crustal material reported thus far in the Black Hills. Whether this older zircon originated as unmelted residue of 2900 Ma crust that potentially underlies the Black Hills or as detritus derived from 2900 Ma crustal sources in the Wyoming province cannot be discerned. In the southern Black Hills (SBH), the peraluminous granite at Bear Mountain (BMG) of previously unknown age intrudes biotite–plagioclase schist. Zircon crystals from the BMG are highly metamict and altered, but locally preserve small domains suitable for in situ analysis. A U–Pb concordia upper intercept age of 2596±11 Ma (±2σ) obtained for zircon confirms both the late Neoarchean magmatic age of the BMG and a minimum age for the schist it intrudes. Taken together, these data indicate that the Neoarchean basement granitoids were emplaced at 2590–2600 Ma (SBH) and 2560 Ma (NBH), most likely in response to subduction associated with plate convergence (final assembly of supercontinent Kenorland?). In contrast, thin rims present on some LEG–BFG zircons exhibit strong U–Pb discordance, high common Pb, and low Th/U ratios—suggesting growth or modification under hydrothermal conditions, as previously suggested for similar zircons from SE Wyoming. The LEG–BFG zircon rims yield a nominal upper intercept date of 1940–2180 Ma, which may represent a composite of multiple rifting events known to have affected the Nemo area between 2480 and 1960 Ma. Together, these observations confirm the existence of a Paleoproterozoic rift margin along the easternmost Wyoming craton. Moreover, the 2480–1960 Ma time frame inferred for rifting in the Black Hills (Nemo area) corresponds closely to a 2450–2100 Ma time frame previously inferred for the fragmentation of supercontinent Kenorland.     

Characterizing and classifying urban watersheds with compositional and structural attributes

Current land-use classifications used to assess urbanization effects on stream water quality date back to the 1980s when limited information was available to characterize watershed attributes that mediate non-point source pollution. With high resolution remote sensing and widely used GIS tools, there has been a vast increase in the availability and precision of geospatial data of built environments. In this study, we leverage geospatial data to expand the characterization of developed landscapes and create a typology that allows us to better understand the impact of complex developed landscapes across the rural to urban gradient. We assess the ability of the developed landscape typology to reveal patterns in stream water chemistry previously undetected by traditional land-cover based classification. We examine the distribution of land-cover, infrastructure, topography and geology across 3876 National Hydrography Dataset Plus catchments in the Piedmont region of North Carolina, USA. From this dataset, we generate metrics to evaluate the abundance, density and position of landscape features relative to streams, catchment outlets and topographic wetness metrics. While impervious surfaces are a key distinguishing feature of the urban landscape, sanitary infrastructure, population density and geology are better predictors of baseflow stream water chemistry. Unsupervised clustering was used to generate a distinct developed landscape typology based on the expanded, high-resolution landscape feature information. Using stream chemistry data from 37 developed headwater catchments, we compared the baseflow water chemistry grouped by traditional land-cover based classes of urbanization (rural, low, medium and high density) to our composition and structure-based classification (a nine-class typology). The typology based on 22 metrics of developed landscape composition and structure explained over 50% of the variation in NO₃⁻-N, TDN, DOC, Cl⁻, and Br⁻ concentration, while the ISC-based classification only significantly explained 23% of the variation in TDN. These results demonstrate the importance of infrastructure, population and geology in defining developed landscapes and improving discrete classes for water management.     

Soil property variation mapping through data mining of soil category maps

Spatial information on soil properties is an important input to hydrological models. In current hydrological modelling practices, soil property information is often derived from soil category maps by the linking method in which a representative soil property value is linked to each soil polygon. Limited by the area‐class nature of soil category maps, the derived soil property variation is discontinuous and less detailed than high resolution digital terrain or remote sensing data. This research proposed dmSoil, a data‐mining‐based approach to derive continuous and spatially detailed soil property information from soil category maps. First, the soil–environment relationships are extracted through data mining of a soil map. The similarity of the soil at each location to different soil types in the soil map is then estimated using the mined relationships. Prediction of soil property values at each location is made by combining the similarities of the soil at that location to different soil types and the representative soil property values of these soil types. The new approach was applied in the Raffelson Watershed and Pleasant Valley in the Driftless Area of Wisconsin, United States to map soil A horizon texture (in both areas) and depth to soil C horizon (in Pleasant Valley). The property maps from the dmSoil approach capture the spatial gradation and details of soil properties better than those from the linking method. The new approach also shows consistent accuracy improvement at validation points. In addition to the improved performances, the inputs for the dmSoil approach are easy to prepare, and the approach itself is simple to deploy. It provides an effective way to derive better soil property information from soil category maps for hydrological modelling. Copyright © 2014 John Wiley & Sons, Ltd.     

Metal binding to dissolved organic matter and adsorption to ferrihydrite in shallow peat groundwaters: Application to diamond exploration in the James Bay Lowlands,Canada

The speciation and solubility of kimberlite pathfinder metals (Ni, Nd, Ba and K) in shallow peat groundwaters is investigated over the Yankee, Zulu and Golf kimberlites in the Attawapiskat region, James Bay Lowlands, Canada. The purpose of this study is to examine the relationship between dissolved organic matter (DOM) complexation with kimberlite pathfinder metals and determine the spatial distribution of those metals in shallow peat groundwaters along sampling transects over subcropping kimberlites. Nickel, Nd, Ba and K complexation with DOM and the adsorption of these metals onto ferrihydrite were calculated using Visual MINTEQ 3.0 and the NICA-Donnan database. Calculations predict almost 100% of soluble Nd, Ni and Ba form complexes with DOM at sampling sites with little to no contribution from upwelling groundwater (i.e., dissolved organic C (DOC) concentrations = 40–132 mg/L, pH = 3.9–5.5, and log ionic strength ??3). In only the most ombrotrophic peat groundwater conditions does a majority fraction of K bind to DOM. By contrast, under conditions with large contributions from upwelling groundwaters (i.e., DOC concentrations ?40 mg/L, pH = 5.5–6.5, and log ionic strength = ?3 to ?2), as little as 10% of Nd and Ni, and 0% K and Ba are predicted to complex with DOM. The modeling calculations suggest the dominant control on metal–DOM complexation, particularly with respect to Ni and Nd, is competitive effects for DOM binding sites due to elevated ionic strength where there is evidence of strong groundwater upwelling. Visual MINTEQ modeling of metal adsorption on ferrihydrite surfaces predicts that under strong upwelling conditions, Ni and Nd are scavenged from solution due to increased ferrihydrite precipitation and decreased fractions of metals complexed with DOM. Analytical geochemical data are consistent with model predictions of metal adsorption on ferrihydrite. Total dissolved Ni and Nd concentrations at sites of strong upwelling are up to five times lower than waters with little to no upwelling and log ferrihydrite saturation indices (logSI_ferr) indicate precipitation (values up to 5) at sites of strong groundwater upwelling. Where the majority of Ni and Nd complex with DOM and ferrihydrite is highly under saturated (logSI_ferr = ?18 to ?5), the concentrations of total Ni and Nd are elevated compared to other sites along sampling transects. Metal complexation with DOM effectively inhibits metal scavenging from solution via adsorption and/or from forming secondary mineral precipitates. Also, because alkaline earth metals do not compete strongly with Ni and Nd for adsorption sites on ferrihydrite surfaces, but do compete strongly for insoluble organic sites, Ni and Nd are more likely to adsorb onto ferrihydrite.     

Aspects of wave behaviour in the mid‐ and upper troposphere of the southern Hemisphere

Abstract

The zonal wavenumber spectra of the geopotential heights of the 300‐ and 500‐mb surfaces in the Southern Hemisphere were determined for each month between May 1972 and November 1979 using daily operational analyses produced by the Australian Bureau of Meteorology. During over one‐quarter of the “summer” months (November through March) there are very prominent peaks at zonal wavenumber five in the region of the mid‐latitude jet (～35–60°S). Frequently wavenumber five totally dominates the eddy fields in individual daily maps so that height contours in mid‐latitudes take on virtually pentagonal shapes. During periods when wavenumber 5 is prominent, it is observed to propagate eastward in a very regular manner with a period of about eleven days. All these findings are consistent with Salby's (1982) earlier results concerning the Southern Hemisphere height fields during the first few months of the FGGE experiment.

There is little evidence for a similar phenomenon in the winter circulation of the Southern Hemisphere.     

Fish Predation on Juvenile Penaeid Shrimp: Examining Relative Predator Impact and Size-Selective Predation

Predation is likely the primary source of mortality for juvenile penaeid shrimp and, therefore, a key factor driving their population dynamics. We sampled juvenile penaeids and their potential predators in a salt marsh from July to August 2012 to examine the impact of these predators and possible size-selective predation on the shrimp population. We quantified predator impact using the frequency of occurrence (FO) index and a relative predation index (RPI) that accounts for predator abundance and the number of shrimp consumed per individual predator. Size selectivity was assessed by comparing the size distribution of shrimp in the study area to the size distribution of shrimp removed from predator stomachs. Two penaeid species, white shrimp Litopenaeus setiferus and brown shrimp Farfantepenaeus aztecus, were collected, and most (86%) were juvenile white shrimp ≤?12 mm carapace length. Spotted seatrout Cynoscion nebulosus, which consumed relatively large shrimp, was the most important predator based on the FO index. Bay whiff Citharichthys spilopterus, which ate the smallest shrimp, was the most important predator based on the RPI. The size distribution of shrimp removed from predator stomachs differed from those collected in the study area; the smallest shrimp were disproportionally more abundant in predator stomachs. Using the RPI, we identified some potentially important predators (e.g., bay whiff) that may impact shrimp populations by consuming the smallest shrimp in estuarine nurseries. Our approach could be useful for examining predator impacts on other populations of juvenile penaeids and more generally for any prey consumed by fish predators.