micro-XANES and micro-XRF investigations of metal binding mechanisms in biosolids

Micro-X-ray fluorescence (micro-XRF) microprobe analysis and micro-X-ray absorption near-edge structure (micro-XANES) spectroscopy were employed to identify Fe and Mn phases and their association with selected metals in two biosolids (limed composted [LC] and Nu-Earth) before and after treatment to remove organic carbon (OC). Spatial correlations derived from elemental mapping of XRF images showed strong correlations between Fe and Cd, Cr, Pb, or Zn (r2= 0.65-0.92) before and after removal of most of the OC. The strong correlation between Fe and Cu that was present in intact samples disappeared after OC removal, suggesting that Cu was associated with OC coatings that may have been present on Fe compounds. Except for Fe and Cr, the spatial correlations of metals with Mn were improved after treatment to remove OC, indicating that the treatment may have altered more than the OC in the system. The Fe micro-XANES spectra of the intact biosolids sample showed that every point had varying mixtures of Fe(II and III) species and no two points were identical. The lack of uniformity in Fe species in the biosolids sample illustrates the complexity of the materials and the difficulty of studying biosolids using conventional analytical tools or chemical extraction techniques. Still, these microscopic observations provide independent information supporting the previous laboratory and field hypothesis that Fe compounds play a major role in retention of environmentally important trace elements in biosolids. This could be due to co-precipitation of the metals with Fe, adsorption of metals by Fe compounds, or a combination of both mechanisms.     

Nitrogen and phosphorus status of soils and trophic state of lakes associated with forage-based beef cattle operations in Florida

Forage-based livestock systems have been implicated as major contributors to deteriorating water quality, particularly for phosphorus (P) from commercial fertilizers and manures affecting surface and ground water quality. Little information exists regarding possible magnitudes of nutrient losses from pastures that are managed for both grazing and hay production and how these might impact adjacent bodies of water. We examined the changes that have occurred in soil fertility levels of rhizoma peanut (Arachis glabrata Benth.)-based beef cattle pastures (n = 4) in Florida from 1988 to 2002. These pastures were managed for grazing in spring followed by haying in late summer and were fertilized annually with P (39 kg P2O5 ha(-1)) and K (68 kg K2O ha(-1)). Additionally, we investigated trends in water quality parameters and trophic state index (TSI) of lakes (n = 3) associated with beef cattle operations from 1993 to 2002. Overall, there was no spatial or temporal buildup of soil P and other crop nutrients despite the annual application of fertilizers and daily in-field loading of animal waste. In fact, soil fertility levels showed a declining trend for crop nutrient levels, especially soil P (y = 146.57 - 8.14 x year; r2= 0.75), even though the fields had a history of P fertilization and the cattle were rotated into the legume fields. Our results indicate that when nutrients are not applied in excess, cow-calf systems are slight exporters of P, K, Ca, and Mg through removal of cut hay. Water quality in lakes associated with cattle production was "good" (30-46 TSI) based on the Florida Water Quality Standard. These findings indicate that properly managed livestock operations may not be major contributors to excess loads of nutrients (especially P) in surface water.     

Greenhouse gas emissions from conventional, agri-environmental scheme, and organic Irish suckler-beef units

The problems of overproduction within the European Union countries and the environmental impact of agriculture have lead to the introduction of schemes that aim to reduce both. Beef (Bos taurus) production forms a large component of the Irish agricultural industry and accounts for more than one quarter of agricultural economic output. Recently, the European CAP (Common Agricultural Policy) has been re-evaluated to include supplementary measures that encompass the environmental role of agriculture rather than just the production role. A life cycle assessment (LCA) method was adopted to estimate emissions per kilogram of CO2 equivalent per kilogram of live weight (LW) leaving the farm gate per annum (kg CO2 kg(-1) LW yr(-1)) and per hectare (kg CO2 ha(-1) yr(-1)). Fifteen units engaged in suckler-beef production (five conventional, five in an Irish agri-environmental scheme, and five organic units) were evaluated for emissions per unit product and area. The average emissions from the conventional units were 13.0 kg CO2 kg(-1) LW yr(-1), from the agri-environmental scheme units 12.2 kg CO2 kg(-1) LW yr(-1), and from the organic units 11.1 kg CO2 kg LW yr(-1). The average emissions per unit area from the conventional units was 5346 kg CO2 ha(-1) yr(-1), from the agri-environmental scheme units 4372 kg CO2 ha(-1) yr(-1), and from the organic units 2302 kg CO2 ha(-1) yr(-1). Results indicated that moving toward extensive production could reduce emissions per unit product and area but live weight production per hectare would be reduced.     

Influence of soil properties and aging on the toxicity of copper on compost worm and barley

Influence of soil properties and aging on Cu partitioning and toxicity was assessed on 10 artificial soils constituted using a statistical design considering pH (5.5 and 7.5), organic matter (1-30% [w/w]), and clay content (5-35% [w/w]). Total Cu as well as water-, CaCl2-, and diethylene triamine pentaacetic acid (DTPA)-extracted Cu fractions were determined for each soil mixture. Ecotoxic effect was assessed by determining growth inhibition of barley (Hordeum vulgare L.) and compost worm (Eisenia fetida) mortality. Analyses were repeated after a 16-wk aging period of the soils at pH 7.5 (8 x 2-wk wetting and drying cycle). Results indicated that pH was the main factor controlling Cu partitioning, ahead of organic matter and clay content. Calcium chloride (0.5 M)-extracted Cu fractions showed the best correlation with toxic responses (r = 0.55-0.66; p < 0.05), while total and DTPA-extracted Cu concentrations could not explain differences in toxicity. Direct regressions between toxicity and soil properties (pH, organic matter, and clay content) provided better explanation of variance: r2= 0.50 (p = 0.00006) for compost worm mortality, r2= 0.77 (p < 0.00001) for barley shoot inhibition, and r2= 0.92 (p < 0.00001) for barley root inhibition. Copper toxicity was mainly influenced by pH and, to a lesser extent, by organic matter and clay content. Aging in organic soils revealed a slight reduction in ecotoxicity while an increase was observed in soils with low organic matter content. Further investigation using longer aging periods would be necessary to assess the significance of this observation.     

Phosphorus fractions in manure from growing pigs receiving diets containing micronized peas and supplemental enzymes

Different livestock feeds manipulations have been reported to reduce the total P concentration in manure. Information on the influence of these dietary manipulation strategies on the forms of P in manure is, however, limited. This study was, therefore, conducted to investigate the effect of diet manipulation through feed micronization and enzyme supplementation on the forms of P in swine manure. Eight growing pigs were fed four diets: barley-raw pea (BRP), barley-micronized pea (BMP), barley-raw pea with enzyme (BRPE), and barley-micronized pea with enzyme (BMPE) in a 4 x 4 Latin square design. Because we are interested in the effect of enzyme cocktail and pea micronization on manure P, we did not reduce the non-phytate P with enzyme addition in this study. The fecal material and urine were collected and analyzed for total P. Fecal material was fractionated to determine the total P in H2O-, NaHCO3-, NaOH-, and HCl-extractable fractions. The total P in the residual fractions was also determined. About 98% of the total P excreted by the pigs was found in the fecal material. Inclusion of micronized pea in pig diet did not have any significant effect (p > 0.1) on either the total P or the different P fractions in the manure. The labile P (the sum of H2O-P and NaHCO3-P) was significantly reduced (p < 0.05) by the addition of enzyme to swine diets. Pigs fed the BRPE and BMPE had 14 and 18% lower labile P, respectively, compared with pigs fed the BRP. Enzyme addition to pig diets reduced not only the total P in manure, but also the labile P fraction, which is of great environmental concern. Thus, the potential of P loss to runoff and the subsequent eutrophication can be reduced by enzyme addition to pig diets.     

Phosphorus and nitrogen in rainfall simulation runoff after fresh and composted beef cattle manure application

Fresh beef cattle (Bos taurus) manure has traditionally been applied to cropland in southern Alberta, but there has been an increase in application of composted manure to cropland in this region. However, the quality of runoff under fresh manure (FM) versus composted manure (CM) has not been investigated. Our objective was to compare runoff quality under increasing rates (0, 13, 42, 83 Mg ha(-1) dry wt.) of FM and CM applied for two consecutive years to a clay loam soil cropped to irrigated barley (Hordeum vulgare L.). We determined total phosphorus (TP), particulate phosphorus (PP), dissolved reactive phosphorus (DRP), total nitrogen (TN), NH4-N, and NO3-N concentrations and loads in runoff after one (1999) and two (2000) applications of FM and CM. We found significantly (P < or = 0.05) higher TP, DRP, and NH4-N concentrations, and higher DRP and TN loads under FM than CM after 2 yr of manure application. The TP loads were also higher under FM than CM at the 83 Mg ha(-1) rate in 2000, and DRP loads were higher for FM than CM at this high rate when averaged over both years. Application rate had a significant effect on TP and DRP concentrations in runoff. In addition, the slope values of the regressions between TP and DRP in runoff versus application rate were considerably higher for FM in 2000 than for FM in 1999, and CM in both 1999 and 2000. Significant positive relationships were found for TP and DRP in runoff versus soil Kelowna-extractable P and soil water-extractable P for FM and CM in 2000, indicating that interaction of runoff with the soil controlled the release of P. Total P and DRP were the variables most affected by the treatments. Overall, our study found that application of CM rather than FM to cropland may lower certain forms of P and N in surface runoff, but this is dependent on the interaction with year, application rate, or both.     

Mapping ground water vulnerability to pesticide leaching with a process-based metamodel of EuroPEARL

To support EU policy, indicators of pesticide leaching at the European level are required. For this reason, a metamodel of the spatially distributed European pesticide leaching model EuroPEARL was developed. EuroPEARL considers transient flow and solute transport and assumes Freundlich adsorption, first-order degradation and passive plant uptake of pesticides. Physical parameters are depth dependent while (bio)-chemical parameters are depth, temperature, and moisture dependent. The metamodel is based on an analytical expression that describes the mass fraction of pesticide leached. The metamodel ignores vertical parameter variations and assumes steady flow. The calibration dataset was generated with EuroPEARL and consisted of approximately 60,000 simulations done for 56 pesticides with different half-lives and partitioning coefficients. The target variable was the 80th percentile of the annual average leaching concentration at 1-m depth from a time series of 20 yr. The metamodel explains over 90% of the variation of the original model with only four independent spatial attributes. These parameters are available in European soil and climate databases, so that the calibrated metamodel could be applied to generate maps of the predicted leaching concentration in the European Union. Maps generated with the metamodel showed a good similarity with the maps obtained with EuroPEARL, which was confirmed by means of quantitative performance indicators.     

Application of two organic amendments on soil restoration: effects on the soil biological properties

One method for recovering degraded soils in semiarid regions is to add organic matter to improve soil characteristics, thereby enhancing biogeochemical nutrient cycling. In this paper, we studied the changes in soil biological properties as a result of adding a crushed cotton gin compost (CCGC) and a poultry manure (PM) for 4 yr to restore a Xerollic Calciorthid located near Seville (Guadalquivir Valley, Andalusia, Spain). Organic wastes were applied at rates of 5, 7.5, and 10 Mg organic matter ha(-1). One year after the assay began, spontaneous vegetation had appeared in the treated plots, particularly in that receiving a high PM and CCGC dose. After 4 yr, the plant cover in these treated plots was around 88 and 79%, respectively, compared with 5% for the control. The effects on soil microbial biomass and six soil enzymatic activities (dehydrogenase, urease, BBA-protease, beta-glucosidase, arylsulfatase, and alkaline phosphatase activities) were ascertained. Both added organic wastes had a positive effect on the biological properties of the soil, although at the end of the experimental period and at high dosage, soil microbial biomass and soil enzyme activities were generally higher in the PM-amended soils compared to the CCGC-amended soils. Enzyme activity from the PM-amended soil was 5, 15, 13, 19, 22, 30, and 6% greater than CCGC-amended soil for soil microbial biomass, urease, BBA-protease, beta-glucosidase, alkaline phosphatase, arylsulfatase, and dehydrogenase activities, respectively. After 4 yr, the percentage of plant cover was > 48% in all treated plots and 5% in the control.     

Synthesis of functionalized mesoporous material from rice husk ash and its application in the removal of the polycyclic aromatic hydrocarbons

Environmental Science and Pollution Research - The rice husk ash (RHA) was used as an alternative source of silica for the synthesis of the functionalized mesoporous material, which was used in the...     

An uptake and elimination kinetics approach to assess the bioavailability of chromium,copper, and arsenic to earthworms (Eisenia andrei) in contaminated field soils

The aim of this study was to determine the bioavailability of metals in field soils contaminated with chromated copper arsenate (CCA) mixtures. The uptake and elimination kinetics of chromium, copper, and arsenic were assessed in the earthworm Eisenia andrei exposed to soils from a gradient of CCA wood preservative contamination near Hartola, Finland. In soils contaminated with 1480–1590 mg Cr/kg dry soil, 642–791 mg Cu/kg dry soil, and 850–2810 mg Ag/kg dry soil, uptake and elimination kinetics patterns were similar for Cr and Cu. Both metals were rapidly taken up and rapidly excreted by Eisenia andrei with equilibrium reached within 1 day. The metalloid As, however, showed very slow uptake and elimination in the earthworms and body concentrations did not reach equilibrium within 21 days. Bioaccumulation factors (BAF) were low for Cu and Cr (< 0.1), but high for As at 0.54–1.8. The potential risk of CCA exposure for the terrestrial ecosystem therefore is mainly due to As.