Trace element speciation in poultry litter

Trace elements are added to poultry feed for disease prevention and enhanced feed efficiency. High concentrations are found in poultry litter (PL), which raises concerns regarding trace element loading of soils. Trace metal cation solubility from PL may be enhanced by complexation with dissolved organic carbon (DOC). Mineralization of organo-As compounds may result in more toxic species such as As(III) and As(V). Speciation of these elements in PL leachates should assist in predicting their fate in soil. Elemental concentrations of 40 PL samples from the southeastern USA were determined. Water-soluble extractions (WSE) were fractionated into hydrophobic, anionic, and cationic species with solid-phase extraction columns. Arsenic speciation of seven As species, including the main As poultry feed additives, roxarsone (ROX; 3-nitro-4-hydroxyphenylarsonic acid) and p-arsanilic acid (p-ASA; 4-aminophenylarsonic acid), was performed by ion chromatography-inductively coupled plasma-mass spectrometry (IC-ICP-MS). Total As concentrations in the litter varied from 1 to 39 mg kg(-1), averaging 16 mg kg(-1). Mean total Cu, Ni, and Zn concentrations were 479, 11, and 373 mg kg(-1), respectively. Copper and Ni were relatively soluble (49 and 41% respectively) while only 6% of Zn was soluble. Arsenic was highly soluble with an average of 71% WSE. Roxarsone was the major As species in 50% of PL samples. However, the presence of As(V) as the major species in 50% of the PL samples indicates that mineralization of ROX had occurred. The high solubility of As from litter and its apparent ready mineralization to inorganic forms coupled with the large quantity of litter that is annually land-applied in the USA suggests a potential detrimental effect on soil and water quality in the long term.     

Major and trace elements of selected pedons in the USA

Few studies of soil geochemistry over large geographic areas exist, especially studies encompassing data from major pedogenic horizons that evaluate both native concentrations of elements and anthropogenically contaminated soils. In this study, pedons (n = 486) were analyzed for trace (Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Zn) and major (Al, Ca, Fe, K, Mg, Na, P, Si, Ti, Zr) elements, as well as other soil properties. The objectives were to (i) determine the concentration range of selected elements in a variety of U.S. soils with and without known anthropogenic additions, (ii) illustrate the association of elemental source and content by assessing trace elemental content for several selected pedons, and (iii) evaluate relationships among and between elements and other soil properties. Trace element concentrations in the non-anthropogenic dataset (NAD) were in the order Mn > (Zn, Cr, Ni, Cu) > (Pb, Co) > (Cd, Hg), with greatest mean total concentrations for the Andisol order. Geometric means by horizon indicate that trace elements are concentrated in surface and/or B horizons over C horizons. Median values for trace elements are significantly higher in surface horizons of the anthropogenic dataset (AD) over the NAD. Total Al, Fe, cation exchange capacity (CEC), organic C, pH, and clay exhibit significant correlations (0.56, 0.74, 0.50, 0.31, 0.16, and 0.30, respectively) with total trace element concentrations of all horizons of the NAD. Manganese shows the best inter-element correlation (0.33) with these associated total concentrations. Total Fe has one of the strongest relationships, explaining 55 and 30% of the variation in total trace element concentrations for all horizons in the NAD and AD, respectively.     

METHODOLOGIES FOR CALIBRATION AND PREDICTIVE ANALYSIS OF A WATERSHED MODEL1

ABSTRACT: The use of a fitted parameter watershed model to address water quantity and quality management issues requires that it be calibrated under a wide range of hydrologic conditions. However, rarely does model calibration result in a unique parameter set. Parameter nonuniqueness can lead to predictive nonuniqueness. The extent of model predictive uncertainty should be investigated if management decisions are to be based on model projections. Using models built for four neighboring watersheds in the Neuse River Basin of North Carolina, the application of the automated parameter optimization software PEST in conjunction with the Hydrologic Simulation Program Fortran (HSPF) is demonstrated. Parameter nonuniqueness is illustrated, and a method is presented for calculating many different sets of parameters, all of which acceptably calibrate a watershed model. A regularization methodology is discussed in which models for similar watersheds can be calibrated simultaneously. Using this method, parameter differences between watershed models can be minimized while maintaining fit between model outputs and field observations. In recognition of the fact that parameter nonuniqueness and predictive uncertainty are inherent to the modeling process, PEST's nonlinear predictive analysis functionality is then used to explore the extent of model predictive uncertainty.     

An environmental threshold for degree of phosphorus saturation in sandy soils

There is critical need for a practical indicator to assess the potential for phosphorus (P) movement from a given site to surface waters, either via surface runoff or subsurface drainage. The degree of phosphorus saturation (DPS), which relates a measure of P already adsorbed by a soil to its P adsorption capacity, could be a good indicator of that soil's P release capability. Our primary objective was to find a suitable analytical protocol for determining DPS and to examine the possibility of defining a threshold DPS value for Florida's sandy soils. Four farmer-owned dairy sprayfields were selected within the Suwannee River basin and soil profiles were randomly obtained from each site, as well as from adjacent unimpacted sites. The soil samples were divided either by horizon or depth, and DPS was determined for each soil sample using ammonium-oxalate (DPS(Ox)), Mehlich-1 (DPS(M1)), and Mehlich-3 (DPS(M3)) extracts. All methods of DPS calculations were linearly related to one another (r2 > 0.94). Relationships between water-soluble P and DPS indicate that the respective change points are: DPS(Ox) = 20%, DPS(M1) = 20%, and DPS(M3) = 16%. These relationships include samples from Ap, E, and Bt horizons, and various combinations thereof, suggesting that DPS values can be used as predictors of P loss from a soil irrespective of the depth of the soil within a profile. Taking into consideration the change points, confidence intervals, agronomic soil test values, and DPS values from other studies, we suggest replacing Mehlich-1 P values in the Florida P Index with the three DPS categories (DPS(M1) = <30, 30-60, and >60%) to assign different P loss ratings in the P Index.     

Importance of Sediment–Water Interactions in Coeur d’Alene Lake,Idaho, USA: Management Implications

A field study at Coeur dAlene Lake, Idaho, USA, was conducted between October 1998 and August 2001 to examine the potential importance of sediment–water interactions on contaminant transport and to provide the first direct measurements of the benthic flux of dissolved solutes of environmental concern in this lake. Because of potential ecological effects, dissolved zinc and orthophosphate were the solutes of primary interest. Results from deployments of an in situ flux chamber indicated that benthic fluxes of dissolved Zn and orthophosphate were comparable in magnitude to riverine inputs. Tracer analyses and benthic-community metrics provided evidence that solute benthic flux were diffusion-controlled at the flux-chamber deployment sites. That is, effects of biomixing (or bioturbation) and ground-water interactions did not strongly influence benthic flux. Remediation efforts in the river might not produce desired water-quality effects in the lake because imposed shifts in concentration gradients near the sediment–water interface would generate a benthic feedback response. Therefore, development of water-quality models to justify remediation strategies requires consideration of contaminant flux between the water column and underlying sediment in basins that have been affected by long-term (decadal) anthropogenic activities.     

Agricultural drainage ditches mitigate phosphorus loads as a function of hydrological variability

Phosphorus (P) loading from nonpoint sources, such as agricultural landscapes, contributes to downstream aquatic ecosystem degradation. Specifically, within the Mississippi watershed, enriched runoff contributions have far-reaching consequences for coastal water eutrophication and Gulf of Mexico hypoxia. Through storm events, the P mitigation capacity of agricultural drainage ditches under no-till cotton was determined for natural and variable rainfall conditions in north Mississippi. Over 2 yr, two experimental ditches were sampled monthly for total inorganic P concentrations in baseflow and on an event-driven basis for stormflows. Phosphorus concentrations, Manning's equations with a range of roughness coefficients for changes in vegetative densities within the ditches, and discharge volumes from Natural Resources Conservation Service dimensionless hydrographs combined to determine ranges in maximum and outflow storm P loads from the farms. Baseflow regressions and percentage reductions with P concentrations illustrated that the ditches alternated between being a sink and source for dissolved inorganic P and particulate P concentrations throughout the year. Storm event loads resulted in 5.5% of the annual applied fertilizer to be transported into the drainage ditches. The ditches annually reduced 43.92 +/- 3.12% of the maximum inorganic effluent P load before receiving waters. Agricultural drainage ditches exhibited a fair potential for P mitigation and thus warrant future work on controlled drainage to improve mitigation capacity.     

Decreased Runoff Response to Precipitation,Little Missouri River Basin,Northern Great Plains,USA

High variability in precipitation and streamflow in the semiarid northern Great Plains causes large uncertainty in water availability. This uncertainty is compounded by potential effects of future climate change. We examined historical variability in annual and growing season precipitation, temperature, and streamflow within the Little Missouri River Basin and identified differences in the runoff response to precipitation for the period 1976‐2012 compared to 1939‐1975 (n = 37 years in both cases). Computed mean values for the second half of the record showed little change (<5%) in annual or growing season precipitation, but average annual runoff at the basin outlet decreased by 22%, with 66% of the reduction in flow occurring during the growing season. Our results show a statistically significant (p < 0.10) 27% decrease in the annual runoff response to precipitation (runoff ratio). Surface‐water withdrawals for various uses appear to account for <12% of the reduction in average annual flow volume, and we found no published or reported evidence of substantial flow reduction caused by groundwater pumping in this basin. Results of our analysis suggest that increases in monthly average maximum and minimum temperatures, including >1°C increases in January through March, are the dominant driver of the observed decrease in runoff response to precipitation in the Little Missouri River Basin.     

Elimination of Methanol and Ethanol by Biofiltration: An Experimental Study

This study presents the experimental results obtained during long-term operation of two biofilters treating two alcohols: methanol and ethanol. The biofilters used for this purpose were previously packed with a compost material made from tobacco processing residues. The alcohols concentrations tested lay between 0.40 and 3.20 g/m³ for methanol, and 0.55 and 5.05 g/m³ for ethanol. The empty bed residence time in each biofilter was 60 s. Biofilter inlet loads of less than 190 and 300 g/m³/h for the methanol and ethanol additions respectively, were thereafter evaluated. In addition, the concentrations of nutrient nitrogen were also varied, from 0.1 to 2.0 g-N/l and from 0.3 to 11.3 g-N/l for the ethanol and the methanol, respectively. The results thus obtained have made it possible to select the optimal nitrogen concentrations which, for the cases examined, turn out to be 0.3 g-N/l and between 2 and 3.8 g-N/l for the ethanol and methanol substrates, respectively. The maximum elimination capacities obtained in this study were 82 and 150 g/m³/h, respectively for the methanol and ethanol cases. It was therefore concluded that, for a readily biodegradable compound such as ethanol, the nitrogen requirement is substantially lower than that needed for the methanol degradation, the latter appearing to be more difficult to degrade biologically under similar operating conditions. The production rate of the co-product carbon dioxide during methanol and ethanol biofiltration was also investigated. Also, a good correlation was found to exist between the temperature and the conversion achieved in the biofilter.     

Performance of a low cost MBT prior to landfilling: study of the biological treatment of size reduced MSW without mechanical sorting

In France, the interest in Mechanical Biological Treatment (MBT) prior to landfilling is actually growing. In the absence of acceptance criteria for the waste to be landfilled, an alternative to the intensive, high-technology MBT can only find its place in the French context if it shows substantial benefits from an environmental, economic or operational point of view. This paper presents an experiment of low-cost MBT of size reduced MSW without material splitting. The performance of an experimental, pilot-scale mechanical and biological treatment process has been studied on 37.5 Mg of raw municipal solid waste. The mechanical process has been kept simple with only coarse shredding and no material recovery. The biological treatment, which was a low-cost forced aeration process, was monitored for 25 weeks. The biogas production potential of the waste was reduced by 90% to 19 NL kgDM(-1). The initial AT4 index of 82.9 mg O2 gDM(-1) decreased to 16.0 mg O2 gDM(-1). After 25 weeks of aerobic treatment, the dry mass loss reached 37%, while the mass of waste going to landfill was reduced by 28%. The average performances of the process were explained by the biological process itself, which was not optimal, and also by the characteristics of the input waste. The high particle size of the treated waste and the high content of slowly biodegradable matter (such as paper and cardboard) may both be significant drawbacks for the biological stabilisation of waste.