Three-dimensional nickel ion transport through porous media using magnetic resonance imaging

The transport of Ni2+ ions in a column, filled with porous media, was observed in three dimensions and time by magnetic resonance imaging (MRI) in a clinical scanner. For porous media we used glass beads or quartz sand in a saturated continuous flow mode. The magnetic moment of Ni2+ decreased the T1 relaxation time of 1H in aqueous solution. This concentration-dependent effect was used by a fast low angle shot (FLASH) MRI sequence for imaging the concentration of the dissolved ions. Since Ni2+ behaves as a conservative tracer under the chosen conditions, the tracer motion was representative for the water flow in the porous medium. Currently, we can achieve an isotropic spatial resolution of 1.5 mm and a temporal resolution of 170 s. The transport observation gives direct access to hydraulic flow properties of the porous media. The fluid flow velocity field was calculated by a fronttracking method and the statistical properties of the velocities were investigated. We also compared the experimental data with the three-dimensional particle tracking model PARTRACE, which uses the experimental flow field as input.     

Ion cycling in hemlock-northern hardwood forests of the southern Lake Superior region: a preliminary study

Upland forests of the southern Lake Superior region are diverse and contain a shifting mosaic of eastern hemlock [Tsuga canadensis (L.) Carr.] and northern hardwood forests dominated by sugar maple (Acer saccharum Marsh.). In this study, we survey the relative effects of management practice (old growth vs. managed), forest cover type (hemlock vs. northern hardwood), and soil great group (Entic Haplorthod vs. Alfic Oxyaquic Fragiorthod) on ion cycling as a precursor to a longer-term, more detailed study. Bulk precipitation, throughfall, and soil leachates at three depths were collected for two growing seasons in eight stands on the Ottawa National Forest in the Upper Peninsula of Michigan. A total of 1210 solutions were analyzed for pH, Na, K, Mg, Ca, Cl, NO3, and SO4. Losses of base cations (Ca, Mg, K) and SO4 from the bottom of the rooting zone generally were greater in old-growth than in managed northern hardwoods on both fragic and nonfragic soils. Leaching losses of base cations and NO3 usually were greater beneath old-growth northern hardwoods than beneath old-growth hemlock on both soil types and for both forest cover types and management practices on fragic than nonfragic soils. Management practice, forest cover type, and soil type all appear to affect ion cycling within these forests. All of the stands featured striking losses of base cations that probably are influenced strongly by NO3 and SO4 in atmospheric deposition.     

Relationships between bacterial tolerance levels and forms of copper and zinc in soils

The effects of various fractions of copper (Cu) and zinc (Zn) on soil bacteria were evaluated by the heavy metal tolerance level of the bacterial community (IC50) in soil samples collected near a mine. The IC50 values had no relationship with the total concentrations of Zn and Cu in the soils, but were weakly correlated with the 0.05 M CaCl2-extractable form of each metal in the soils (Cu: R2 = 0.670, p < 0.01; Zn: R2 = 0.453, p < 0.05). It was found that the IC50 correlated strongly with the total concentration of each metal in the extracts from water-saturated soil samples, described below as "soil solution" (Cu: R2 = 0.789, p < 0.01; Zn: R2 = 0.617, p < 0.01). The speciation of these metals in the soil solutions was estimated using an equilibrium thermodynamic computer model, SOILCHEM. Simulated free Cu ion ranged from 18 to 98% of total Cu, and organic complexes of Cu ranged from < 1 to 56%. In all samples, Zn existing as the free ion was estimated to be more than 80% of total Zn in the soil solutions. The IC50 values were also correlated with the estimated free metal ion activities, but with slightly lower correlation coefficients than found for total concentration in the soil solutions (Cu: R2 = 0.735, p < 0.01; Zn: R2 = 0.610, p < 0.01). The results suggest that not only high metal ion activities, but also total dissolved metal concentrations in soil solutions may affect the bacterial community.     

Enzymatic transformation and binding of labeled 2,4,6-trinitrotoluene to humic substances during an anaerobic/aerobic incubation

Organic pollutants are degraded in soil and simultaneously nonextractable residues are formed. However, proof is lacking that this fixation has a detoxifying effect. We investigated the transformation and binding of 2,4,6-trinitrotoluene (TNT) with catechol or soil humic acid as cosubstrates. Carbon-14-labeled TNT and its reaction products were quantified by radiocounting; extractable compounds were identified by high performance liquid chromatography (HPLC). Bound and extractable residues of 15N-labeled TNT and metabolites were studied by 15N nuclear magnetic resonance spectroscopy (15N NMR). Since TNT is not easily transformed under oxidizing conditions an anaerobic/aerobic treatment was used. Anaerobic microorganisms from cow manure were used to reduce TNT during the anaerobic phase and subsequently, a laccase from Trametes villosa was used in the aerobic phase to oxidatively couple the metabolites to humic matter. Seventy-four percent of TNT was immobilized with catechol as cosubstrate, but only 25% with humic acid. With catechol the main extractable component was TNT, while with humic acid it was mostly the metabolite 4-aminodinitrotoluene. For both co-substrates, the spectra of immobilized metabolites obtained by solid-state 15N-cross polarization magic angle spinning (CPMAS) NMR spectroscopy showed signals in the chemical shift region for protonated aromatic amino compounds. However, in the presence of catechol, an additional signal from nonextractable nitro groups was found, which could represent sequestered TNT. The partially reduced metabolites of TNT that formed nonextractable residues in humic acid are not likely to be remobilized easily and are thus regarded as detoxified.     

Natural uranium and thorium distributions in podzolized soils and native blueberry

Plant uptake of radionuclides is one of many vectors for introduction of contaminants into the human food chain. Thus, it is critical to understand soil-plant relationships that control nuclide bioavailability. Our objectives in this study were to (i) determine the extent of U and Th uptake and cycling by blueberry (Vaccinium pallidum Aiton) in native habitat and (ii) identify the soil properties and processes that contribute most to U and Th bioavailability in this system. We collected composite samples of plant leaves and stems, and samples from surface (AE) horizons and from the upper part of the Bs horizon at two sites. Concentration ratios (CRs) for U and Th were calculated for all plant tissues, using both the AE and Bs horizons as the base. Soil concentrations of U ranged from 16 to 25 microg g(-1), with a mean of 21.1 microg g(-1). Soil concentrations of Th ranged from 14 to 97 microg g(-1), with a mean of 41.8 microg g(-1). Mean U concentrations were 8.65 x 10(-3) microg g(-1) in leaf tissue, and 7.95 x 10(-3) microg g(-1) in stem tissue. Mean Th concentrations were 1.59 x 10(-1) microg g(-1) in leaf tissue, and 9.10 x 10(-2) microg g(-1) in stem tissue. Blueberry plants are cycling both U and Th in this system, with Th cycling occurring to a greater extent than U. In addition, Th was translocated preferentially to plant leaves while U concentrations showed little preferential translocation. Uranium uptake, however, seemed more sensitive than Th uptake to soil properties.     

Influence of water treatment residuals on phosphorus solubility and leaching

Laboratory and greenhouse studies compared the ability of water treatment residuals (WTRs) to alter P solubility and leaching in Immokalee sandy soil (sandy, siliceous, hyperthermic Arenic Alaquod) amended with biosolids and triple superphosphate (TSP). Aluminum sulfate (Al-WTR) and ferric sulfate (Fe-WTR) coagulation residuals, a lime softening residual (Ca-WTR) produced during hardness removal, and pure hematite were examined. In equilibration studies, the ability to reduce soluble P followed the order Al-WTR > Ca-WTR = Fe-WTR > hematite. Differences in the P-fixing capacity of the sesquioxide-dominated materials (Al-WTR, Fe-WTR, hematite) were attributed to their varying reactive Fe- and Al-hydrous oxide contents as measured by oxalate extraction. Leachate P was monitored from greenhouse columns where bahiagrass (Paspalum notatum Flugge) was grown on Immokalee soil amended with biosolids or TSP at an equivalent rate of 224 kg P ha(-1) and WTRs at 2.5% (56 Mg ha(-1)). In the absence of WTRs, 21% of TSP and 11% of Largo cake biosolids total phosphorus (PT) leached over 4 mo. With co-applied WTRs, losses from TSP columns were reduced to 3.5% (Fe-WTR), 2.5% (Ca-WTR), and <1% (Al-WTR) of applied P. For the Largo biosolids treatments all WTRs retarded downward P flux such that leachate P was not statistically different than for control (soil only) columns. The phosphorus saturation index (PSI = [Pox]/ [Al(ox) + Fe(ox)], where Pox, Al, and Fe(ox) are oxalate-extractable P, Al, and Fe, respectively) based on a simple oxalate extraction of the WTR and biosolids is potentially useful for determining WTR application rates for controlled reduction of P in drainage when biosolids are applied to low P-sorbing soils.     

Coupled abiotic-biotic mineralization of 2,4,6-trinitrotoluene (TNT)

Munitions wastes such as TNT are widespread contaminants in soils and ground waters. We investigated a coupled abiotic-biotic treatment scheme for remediation of aqueous solutions of TNT. Mineralization of aqueous TNT (0.22 mM) was initially optimized with minimum reactant use (Fe3+ and H2O2) in light-assisted and dark, modified Fenton reactions at acidic and neutral pH. Complete TNT degradation occurred under all reaction conditions within 24 h. Using the optimum reactant concentrations, coupled abiotic-biotic reactions showed an increase in TNT mineralization, from 47 to 80%, after biomass addition to the acidic, dark Fenton-like reaction. Comparable increases of TNT mineralization were observed under neutral pH with similar reaction conditions. In light-assisted Fenton-like reactions at neutral pH, no increase in cumulative TNT mineralization (66%) was seen in coupled abiotic-biotic reactions. Abiotic photo-Fenton-like reactions alone, at acidic pH, produced complete TNT mineralization and required no biotic assistance. While light-enhanced Fenton reactions alone can provide high levels of TNT mineralization, the dark abiotic-biotic reaction scheme has perhaps a wider use due to a similar extent of TNT mineralization in the absence of light, leading to possible applications in soil slurry and in situ processes in the subsurface.     

Phosphorus leaching from biosolids-amended sandy soils

Increasing emphasis on phosphorus (P)-based nutrient management underscores the need to understand P behavior in soils amended with biosolids and manures. Laboratory and greenhouse column studies characterized P forms and leachability of eight biosolids products, chicken manure (CM), and commercial fertilizer (triple superphosphate, TSP). Bahiagrass (Paspalum notatum Flugge) was grown for 4 mo on two acid, P-deficient Florida sands, representing both moderate (Candler series: hyperthermic, uncoated Typic Quartzipsamments) and very low (Immokalee series: sandy, siliceous, hyperthermic Arenic Alaquods) P-sorbing capacities. Amendments were applied at 56 and 224 kg P(T) ha(-1), simulating P-based and N-based nutrient loadings, respectively. Column leachate P was dominantly inorganic and lower for biosolids P sources than TSP. For Candler soil, only TSP at the high P rate exhibited P leaching statistically greater (alpha = 0.05) than control (soil-only) columns. For the high P rate and low P-sorbing Immokalee soil, TSP and CM leached 21 and 3.0% of applied P, respectively. Leachate P for six biosolids was <1.0% of applied P and not statistically different from controls. Largo biosolids, generated from a biological P removal process, exhibited significantly greater leachate P in both cake and pelletized forms (11 and 2.5% of applied P, respectively) than other biosolids. Biosolids P leaching was correlated to the phosphorus saturation index (PSI = [Pox]/[Al(ox) + Fe(ox)]) based on oxalate extraction of the pre-applied biosolids. For hiosolids with PSI < or = approximately 1.1, no appreciable leaching occurred. Only Largo cake (PSI = 1.4) and pellets (PSI = 1.3) exhibited P leaching losses statistically greater than controls. The biosolids PSI appears useful for identifying biosolids with potential to enrich drainage P when applied to low P-sorbing soils.     

Modeling the fate of benzo[a]pyrene in the wastewater-irrigated areas of Tianjin with a fugacity model

A Level III fugacity model was applied to characterize the transfer processes and environmental fate of benzo[a]pyrene in wastewater-irrigated areas of Tianjin, China. The physical-chemical properties and transfer parameters of benzo[a]pyrene were used in the model and the concentration distribution of benzo[a]pyrene in sediment, soil, water, air, fish, and crop compartments, as well as transfer fluxes across the compartments, were then derived under steady-state assumptions. The calculated results were compared with monitoring data for air, soil, water, and sediment collected from the literature. The results indicate that there was generally good agreement and the differences were within an order of magnitude for air, soil, and sediment. The concentration of benzo[a]pyrene in the ambient air in the area was very low with a majority present sorbed to aerosol. In the water compartment, approximately 70% of benzo[a]pyrene dissolved in water phase. Relatively high concentrations of the compound were found in the soil and sediment, with the soil serving as the dominant sink in the area. Benzo[a]pyrene, with a slow metabolic rate, was found to accumulate in fish in the area.     

Bioavailability of calcium from sweetpotato and soy flour supplemented diets in hamsters

The bioavailability of calcium from two varieties of sweetpotatoes and supplementation of sweetpotatoes with soy flour was investigated in hamsters using plasma calcium concentration and femur calcium content as indicators. Five different diets were fed to five groups of animals for 28 days. There was no significant difference in plasma calcium concentrations of hamsters in all the diet groups. However, the femur calcium content of hamsters with transgenic sweetpotato flour (TSPF) and parent nontransgenic (from which transgenic was produced) sweetpotato flour (NTSPF) diets was significantly higher than that of the transgenic sweetotato flour supplemented with soy flour (TSPF + SF) and parent nontransgenic sweetpotato flour supplemented with soy flour (NTSPF + SF) diets. The relative bioavailability of calcium from the control (100%), TSPF+SF (30%), NTSPF+SF (23%), TSPF (57%) and NTSPF (46%) indicated that sweetpotatoes could be the better source of calcium, however, supplementation with soy flour might reduce the bioavailability of calcium.