Removal of selenate from water by zerovalent iron

Zerovalent iron (ZVI) has been widely used in the removal of environmental contaminants from water. In this study, ZVI was used to remove selenate [Se(VI)] at a level of 1000 microg L(-1) in the presence of varying concentrations of Cl-, SO(2-)4, NO(-)3, HCO(-)3, and PO(3-)4. Results showed that Se(VI) was rapidly removed during the corrosion of ZVI to iron oxyhydroxides (Fe(OH)). During the 16 h of the experiments, 100 and 56% of the added Se(VI) was removed in 10 mM Cl- and SO(2-)4 solutions under a closed contained system, respectively. Under an open condition, 100 and 93% of the added Se(VI) were removed in the Cl- and SO(2-)4 solutions, respectively. Analysis of Se species in ZVI-Fe(OH) revealed that selenite [Se(IV)] and nonextractable Se increased during the first 2 to 4 h of reaction, with a decrease of Se(VI) in the Cl- experiment and no detection of Se(VI) in the SO(2-)4 experiment. Two mechanisms can be attributed to the rapid removal of Se(VI) from the solutions. One is the reduction of Se(VI) to Se(IV), followed by rapid adsorption of Se(IV) to Fe(OH). The other is the adsorption of Se(VI) directly to Fe(OH), followed by its reduction to Se(IV). The results also show that there was little effect on Se(VI) removal in the presence of Cl- (5, 50, and 100 mM), NO(-)3 (1, 5, and 10 mM), SO(2-)4 (5 mM), HCO(-)3 (1 and 5 mM), or PO(3-)4 (1 mM) and only a slight effect in the presence of SO(2-)4 (50 and 100 mM), HCO(-)3 (10 mM), and PO(3-)4 (5 mM) during a 2-d experiment, whereas 10 mM PO(3-)4 significantly inhibited Se(VI) removal. This work suggests that ZVI may be an effective agent to remove Se from Se-contaminated agricultural drainage water.     

In situ ground water denitrification in stratified, permeable soils underlying riparian wetlands

The ground water denitrification capacity of riparian zones in deep soils, where substantial ground water can flow through low-gradient stratified sediments, may affect watershed nitrogen export. We hypothesized that the vertical pattern of ground water denitrification in riparian hydric soils varies with geomorphic setting and follows expected subsurface carbon distribution (i.e., abrupt decline with depth in glacial outwash vs. negligible decline with depth in alluvium). We measured in situ ground water denitrification rates at three depths (65, 150, and 300 cm) within hydric soils at four riparian sites (two per setting) using a 15N-enriched nitrate "push-pull" method. No significant difference was found in the pattern and magnitude of denitrification when grouping sites by setting. At three sites there was no significant difference in denitrification among depths. Correlations of site characteristics with denitrification varied with depth. At 65 cm, ground water denitrification correlated with variables associated with the surface ecosystem (temperature, dissolved organic carbon). At deeper depths, rates were significantly higher closer to the stream where the subsoil often contains organically enriched deposits that indicate fluvial geomorphic processes. Mean rates ranged from 30 to 120 microg N kg(-1) d(-1) within 10 m versus <1 to 40 microg N kg(-1) d(-1) at >30 m from the stream. High denitrification rates observed in hydric soils, down to 3 m within 10 m of the stream in both alluvial and glacial outwash settings, argue for the importance of both settings in evaluating the significance of riparian wetlands in catchment-scale N dynamics.     

Tillage erosion and its effect on soil properties and crop yield in Denmark

Tillage erosion had been identified as a major process of soil redistribution on sloping arable land. The objectives of our study were to investigate the extent of tillage erosion and its effect on soil quality and productivity under Danish conditions. Soil samples were collected to a 0.45-m depth on a regular grid from a 1.9-ha site and analyzed for 137Cs inventories, as a measure of soil redistribution, soil texture, soil organic carbon (SOC) contents, and phosphorus (P) contents. Grain yield was determined at the same sampling points. Substantial soil redistribution had occurred during the past decades, mainly due to tillage. Average tillage erosion rates of 2.7 kg m(-2) yr(-1) occurred on the shoulderslopes, while deposition amounted to 1.2 kg m(-2) yr(-1) on foot- and toeslopes. The pattern of soil redistribution could not be explained by water erosion. Soil organic carbon and P contents in soil profiles increased from the shoulder- toward the toeslopes. Tillage translocation rates were strongly correlated with SOC contents, A-horizon depth, and P contents. Thus, tillage erosion had led to truncated soils on shoulderslopes and deep, colluvial soils on the foot- and toeslopes, substantially affecting within-field variability of soil properties. We concluded that tillage erosion has important implications for SOC dynamics on hummocky land and increases the risk for nutrient losses by overland flow and leaching. Despite the occurrence of deep soils across the study area, evidence suggested that crop productivity was affected by tillage-induced soil redistribution. However, tillage erosion effects on crop yield were confounded by topography-yield relationships.     

Equilibrium and kinetic studies on biosorption of Hg(II), Cd(II) and Pb(II) ions onto microalgae Chlamydomonas reinhardtii

The microalgae Chlamydomonas reinhardtii was used for the biosorption of Hg(II), Cd(II) and Pb(II) ions. The maximum adsorption of Hg(II) and Cd(II) ions on Chlamydomonas reinhardtii biomass was observed at pH 6.0 and the corresponding value for Pb(II) ions was 5.0. The biosorption of Hg(II), Cd(II) and Pb(II) ions by microalgae biomass increased as the initial concentration of Hg(II), Cd(II) and Pb(II) ions increased in the biosorption medium. The maximum biosorption capacities of microalgae for Hg(II), Cd(II) and Pb(II) ions were 72.2+/-0.67, 42.6+/-0.54 and 96.3+/-0.86 mg/g dry biomass, respectively. The affinity order for algal biomass was Pb(II)>Hg(II)>Cd(II). FT-IR analysis of algal biomass revealed the presence of amino, carboxyl, hydroxyl and carbonyl groups, which were responsible for biosorption of metal ions. Biosorption equilibrium was established in about 60 min and the equilibrium was well described by the Freundlich biosorption isotherms. Temperature change in the range of 5-35 degrees C did not affect the biosorption capacity. The microalgae could be regenerated using 0.1 M HCl, with up to 98% recovery, which allowed the reuse of the biomass in six biosorption-desorption cycles without any considerable loss of biosorption capacity.     

A multi-objective optimisation approach to water management

The management of river basins is complex especially when decisions about environmental flows are considered in addition to those concerning urban and agricultural water demand. The solution to these complex decision problems requires the use of mathematical techniques that are formulated to take into account conflicting objectives. Many optimization models exist for water management systems but there is a knowledge gap in linking bio-economic objectives with the optimum use of all water resources under conflicting demands. The efficient operation and management of a network of nodes comprising storages, canals, river reaches and irrigation districts under environmental flow constraints is challenging. Minimization of risks associated with agricultural production requires accounting for uncertainty involved with climate, environmental policy and markets. Markets and economic criteria determine what crops farmers would like to grow with subsequent effect on water resources and the environment. Due to conflicts between multiple goal requirements and the competing water demands of different sectors, a multi-criteria decision-making (MCDM) framework was developed to analyze production targets under physical, biological, economic and environmental constraints. This approach is described by analyzing the conflicts that may arise between profitability, variable costs of production and pumping of groundwater for a hypothetical irrigation area.     

Spatial variability of soil phosphorus in relation to the topographic index and critical source areas: sampling for assessing risk to water quality

A measure of soil P status in agricultural soils is generally required for assisting with prediction of potential P loss from agricultural catchments and assessing risk for water quality. The objectives of this paper are twofold: (i) investigating the soil P status, distribution, and variability, both spatially and with soil depth, of two different first-order catchments; and (ii) determining variation in soil P concentration in relation to catchment topography (quantified as the "topographic index") and critical source areas (CSAs). The soil P measurements showed large spatial variability, not only between fields and land uses, but also within individual fields and in part was thought to be strongly influenced by areas where cattle tended to congregate and areas where manure was most commonly spread. Topographic index alone was not related to the distribution of soil P, and does not seem to provide an adequate indicator for CSAs in the study catchments. However, CSAs may be used in conjunction with soil P data for help in determining a more "effective" catchment soil P status. The difficulties in defining CSAs a priori, particularly for modeling and prediction purposes, however, suggest that other more "integrated" measures of catchment soil P status, such as baseflow P concentrations or streambed sediment P concentrations, might be more useful. Since observed soil P distribution is variable and is also difficult to relate to nationally available soil P data, any assessment of soil P status for determining risk of P loss is uncertain and problematic, given other catchment physicochemical characteristics and the sampling strategy employed.     

Evaluation of simplifying assumptions on pesticide degradation in soil

There is evidence that degradation of pesticides in simple laboratory systems may differ from that in the field, but it is not clear which of the simplifications inherent in laboratory studies present serious shortcomings. Laboratory experiments evaluated several simplifying assumptions for a clay loam soil and contrasting pesticides. Degradation of cyanazine [2-(4-chloro-6-ethylamino-1,3,5-triazin-2-ylamino)-2-methylpropiononitrile] and bentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide] at fluctuating temperature and moisture was predicted reasonably well based on parameters derived from degradation under constant conditions. There was a tendency for slower degradation of cyanazine and bentazone in soil aggregates of 3 to 5 mm in diameter (DT50 at 15 degrees C and 40% maximum water holding capacity of 25.1 and 58.2 d, where DT50 is the time for 50% decline of the initial pesticide concentration) than in soil sieved to <3 mm (DT50 of 19.1 and 37.6 d), but the differences were not significant for most datasets. Degradation of cyanazine, isoproturon [3-(4-isopropylphenyl)-1,1-dimethylurea], and chlorotoluron [3-(3-chloro-p-tolyl)-1,1-dimethylurea] was measured in soil amended with different amounts of lignin. The effect of lignin on degradation was small despite considerable differences in sorption. The DT50 values of cyanazine, isoproturon, and chlorotoluron were 16.2, 18.6, and 33.0 d, respectively, in soil without lignin and 19.0, 23.4, and 34.6 d, respectively, in soil amended with 2% lignin. Degradation of bentazone and cyanazine in repacked soil columns was similar under static and flow conditions with 50.1 and 47.2% of applied bentazone and 74.7 and 73.6% of applied cyanazine, respectively, degraded within 20 d of application. Thus, the assumptions underpinning laboratory to field extrapolation tested here were considered to hold for our experimental system. Additional work is required before general conclusions can be drawn.     

Quantifying the impact of regular cutting on vegetative buffer efficacy for nitrogen-15 sequestration

This study used the stable 15N isotope to quantitatively examine the effects of cutting on vegetative buffer uptake of NO3(-)-N based on the theory that regular cutting would increase N demand and sequestration by encouraging new plant growth. During the summer of 2002, 10 buffer plots were established within a flood-irrigated pasture. In 2003, 15N-labeled KNO3 was applied to the pasture area at a rate of 5 kg N ha(-1) and 99.7 atom % 15N. One-half of the buffer plots were trimmed monthly. In the buffers, the cutting effect was not significant in the first few weeks following 15N application, with both the cut and uncut buffers sequestering 15N. Over the irrigation season, however, cut buffers sequestered 2.3 times the 15N of uncut buffers, corresponding to an increase in aboveground biomass following cutting. Cutting and removing vegetation allowed the standing biomass to take advantage of soil 15N as it was released by microbial mineralization. In contrast, the uncut buffers showed very little change in 15N sequestration or biomass, suggesting senescence and a corresponding decrease in N demand. Overall, cutting significantly improved 15N attenuation from both surface and subsurface water. However, the effect was temporally related, and only became significant 21 to 42 d after 15N application. The dominant influence on runoff water quality from irrigated pasture remains irrigation rate, as reducing the rate by 75% relative to the typical rate resulted in a 50% decrease in total runoff losses and a sevenfold decrease in 15N concentration.     

Polycyclic aromatic hydrocarbons (PAHs) in soils of the Moscow Region--concentrations, temporal trends, and small-scale distribution

The knowledge of the environmental fate of polycyclic aromatic hydrocarbons (PAHs) is restricted to few climatic regions of the world almost excluding the Taiga. Our objectives were to (i) separate anthropogenic from background contributions to PAH concentrations and (ii) determine temporal trends in PAH concentrations during the last century including the change in distribution of PAHs in interior and exterior portions of aggregates in soils of the Moscow region. Along a southeast-bound transect from Moscow (windward in winter) and at a background location northeast of Moscow (leeward in winter), seven topsoil samples were collected in 1910-1954 and 35 in 1998-2003. We fractionated the soils in interior and exterior portions of aggregates > 10 mm and remaining soil without aggregates. The sum of 21 PAHs (sigma21PAHs) concentrations in recent bulk soil ranged from 59 to 1350 ng g(-1). The concentrations of all PAHs were lower outside than in Moscow. The range of the concentrations of the sigma21PAHs in archived soil samples (159-1280 ng g(-1)) was similar as in recent soils. In most recent and archived samples, naphthalene and phenanthrene, were most abundant. The concentrations of low-molecular-weight PAHs decreased during the last century at most sites; those of high-molecular-weight compounds increased. The sigma21PAHs concentrations were accumulated in the exterior of aggregates (109%) and depleted in the interior (95%) relative to the concentration in bulk soil (defined as 100%), which was similar to that in the soil without aggregates (99%). The differences between aggregate interior and exterior did not change during the last century. The dominance of naphthalene and phenanthrene is typical of remote regions. The urban influence on PAH concentrations in the last century was small.     

Uptake and transport of radioactive nickel and cadmium into three vegetables after wet aerial contamination

Knowledge of radionuclide or trace element retention and translocation to plants following an aerial contamination event, for example, sprinkling with contaminated water, is necessary for the evaluation of human exposure through consumption of contaminated vegetables. The fate of 63Ni and 109Cd in all plant parts of three different vegetables after wet deposition on leaves or on fruits was studied. Lettuce (Lactuca sativa L.), radish (Raphanus sativus L.), and bean (Phaseolus vulgaris L.) grown under controlled conditions in a growth chamber were contaminated with 63Ni and 109Cd either on leaves, by means of two different contamination methods (a single early contamination and a repetitive one), or on bean husks (third contamination method: a single contamination at a late stage). Spiked and nonspiked organs were harvested at maturity and radionuclide contents were measured. The fraction retained was on average 56% of the initially administered doses of 63Ni and 87% of 109Cd. The leaf-to-other organ translocation factor was considerably higher for 63Ni (on average 43% of retained radioactivity) than for 109Cd (8%). Nickel-63 migrated throughout the whole plant following foliar contamination, and mainly toward young leaves, seeds in formation, and sink organs, whereas 109Cd migrated to a much lesser extent and only to the organs that were closest to the spiked one, and not at all into fruit. After a fruit contamination event, both radionuclides were translocated into the seeds of spiked fruits. Radionuclide retention and translocation were not affected by plant species, but principally by the type of organ contaminated.