The effect of humic acids on the sequential extraction of metals in soils and sediments using ICP-AES and chemometric analysis

The effect of humic acids on the sequential extraction of metals from various soils and sediments has been studied. A new multi-element extraction method optimised via experimental design has been employed. The method uses centrifugation to pass the extractant solution, at varying pH, through the sediment sample. The sequential leaches were collected and analysed by ICP-AES. Chemometric data processing was utilised to identify the composition of the physico-chemical components in order to characterise the sample. A sediment sample collected from Carnon River (Cornwall, UK) and a reference material (NIST 2711 agricultural soil) were spiked with humic acids and the sequential extraction scheme was used to monitor the changes in metal distribution. The method has proved a quick and reliable way to evaluate different sediment samples, and has potential as a new tool for environmental geochemistry analysis.     

Dioxins and polychlorinated biphenyls (PCDD/Fs and PCBs) in food from farms close to foot and mouth disease animal pyres

To control the outbreak of foot and mouth disease, which occurred in the UK in early 2001, a large number of farm animals were slaughtered. Where it was not possible to render or landfill the carcasses, they were destroyed by burning on open pyres, with wood, coal and other materials. Uncontrolled combustion such as this is known to produce small quantities of dioxins and an investigation was made into whether, as a result of the burning, there was an elevation in the concentrations of these compounds in food produced in the areas close to the pyres. With few exceptions, concentrations of PCDD/Fs and PCBs were within the expected ranges as predicted by reference data. No accumulation over time was evident from a repeat milk sampling exercise. Where elevated concentrations of PCDD/Fs and PCBs were found in chickens and eggs, they were in samples not destined for the food chain. Elevated levels in some samples of milk from Dumfries and Galloway were not found in earlier or later samples and may have been found as a result of a temporary feeding regime. Elevated concentrations in lamb from Carmarthenshire were from very young animals which would not have entered the food chain. There was no evidence of any significant increase in dietary exposure to PCDD/Fs and PCBs as a result of the FMD pyres.     

A cation exchange model to describe Cs+ sorption at high ionic strength in subsurface sediments at Hanford site, USA

A theoretical and experimental study of cation exchange in high ionic strength electrolytes was performed using pristine subsurface sediments from the U.S. Department of Energy Hanford site. These sediments are representative of the site contaminated sediments impacted by release of high level waste (HLW) solutions containing 137Cs+ in NaNO3 brine. The binary exchange behavior of Cs+-Na+, Cs+-K+, and Na+-K+ was measured over a range in electrolyte concentration. Vanselow selectivity coefficients (Kv) that were calculated from the experimental data using Pitzer model ion activity corrections for aqueous species showed monotonic increases with increasing electrolyte concentrations. The influence of electrolyte concentration was greater on the exchange of Na+-Cs+ than K+-Cs+, an observation consistent with the differences in ion hydration energy of the exchanging cations. A previously developed two-site ion exchange model [Geochimica et Cosmochimica Acta 66 (2002) 193] was modified to include solvent (water) activity changes in the exchanger phase through application of the Gibbs-Duhem equation. This water activity-corrected model well described the ionic strength effect on binary Cs+ exchange, and was extended to the ternary exchange system of Cs+-Na+-K+ on the pristine sediment. The model was also used to predict 137Cs+ distribution between sediment and aqueous phase (Kd) beneath a leaked HLW tank in Hanfordd's S-SX tank using the analytical aqueous data from the field and the binary ion exchange coefficients for the pristine sediment. The Kd predictions closely followed the trend in the field data and were improved by consideration of water activity effects that were considerable in certain regions of the vadose zone plume.     

THE IMPACT OF RUNOFF GENERATION MECHANISMS ON THE LOCATION OF CRITICAL SOURCE AREAS1

ABSTRACT: Identifying phosphorus (P) source areas and transport pathways is a key step in decreasing P loading to natural water systems. This study compared the effects of two modeled runoff generation processes ‐ saturation excess and infiltration excess ‐ on total phosphorus (TP) and soluble reactive phosphorus (SRP) concentrations in 10 catchment streams of a Catskill mountain watershed in southeastern New York. The spatial distribution of runoff from forested land and agricultural land was generated for both runoff processes; results of both distributions were consistent with Soil Conservation Service‐Curve Number (SCS‐CN) theory. These spatial runoff distributions were then used to simulate stream concentrations of TP and SRP through a simple equation derived from an observed relation between P concentration and land use; empirical results indicate that TP and SRP concentrations increased with increasing percentage of agricultural land. Simulated TP and SRP stream concentrations predicted for the 10 catchments were strongly affected by the assumed runoff mechanism. The modeled TP and SRP concentrations produced by saturation excess distribution averaged 31 percent higher and 42 percent higher, respectively, than those produced by the infiltration excess distribution. Misrepresenting the primary runoff mechanism could not only produce erroneous concentrations, it could fail to correctly locate critical source areas for implementation of best management practices. Thus, identification of the primary runoff mechanism is critical in selection of appropriate models in the mitigation of nonpoint source pollution. Correct representation of runoff processes is also critical in the future development of biogeochemical transport models, especially those that address nutrient fluxes.     

STEP WISE,MULTIPLE OBJECTIVE CALIBRATION OF A HYDROLOGIC MODEL FOR A SNOWMELT DOMINATED BASIN1

ABSTRACT: The ability to apply a hydrologic model to large numbers of basins for forecasting purposes requires a quick and effective calibration strategy. This paper presents a step wise, multiple objective, automated procedure for hydrologic model calibration. This procedure includes the sequential calibration of a model's simulation of solar radiation (SR), potential evapotranspiration (PET), water balance, and daily runoff. The procedure uses the Shuffled Complex Evolution global search algorithm to calibrate the U.S. Geological Survey's Precipitation Runoff Modeling System in the Yampa River basin of Colorado. This process assures that intermediate states of the model (SR and PET on a monthly mean basis), as well as the water balance and components of the daily hydrograph are simulated consistently with measured values.     

Distribution and speciation of metals in annual rings of black willow

Information on the spatial distribution and speciation of metals in nonhyperaccumulator plants is lacking. This study used synchrotron X-ray fluorescence (SXRF) compositional imaging to investigate the spatial distribution of Ni, Mn, Cu, Zn, and Fe in annual rings of black willow (Salix nigra L.) collected from a metal-contaminated area, and used X-ray absorption spectroscopy (XAS) to investigate Ni and Mn speciation in regions of the annual rings with elevated Ni concentrations. Annual rings were recollected in early 2003 from an individual known to be enriched with Ni from previous studies. Compositional imaging showed Ni and associated co-contaminants conservatively located in an annual ring. When compared with a corresponding photomicrograph, SXRF compositional images showed that metals were sharply constrained by the boundaries of the annual ring, indicating a sudden onset and cessation of uptake, and a lack of post-growth mobility of the metals. There was a particularly strong correlation between Ni and Mn in the metal-enriched annual ring (r = 0.8822), which suggested similar transport and binding behavior of these elements. X-ray absorption spectroscopy showed Ni and Mn to be present in the 2+ oxidation state. X-ray absorption near edge structure spectroscopy (XANES) fingerprinting of localized, highly Ni-enriched regions within the lumen of willow xylem vessels found similarities with Ni-pectic acid complexes, Ni-histidine, and NiSO4.     

SERENDIPITY: CAPTURING A DESIGN LEVEL PRECIPITATION EVENT1

ABSTRACT: On February 23–24, 1998, a frontal system moved across the U.S. Department of Energy's 3,500 km² Nevada Test Site (NTS) and resulted in significant depths of precipitation at all recording gages on the NTS. A preliminary analysis suggested that this precipitation event was of the magnitude and duration for which many flood mitigation structures have been designed. Given the data and field observations available and the potential implications of the event on the methodologies used to size flood mitigation structures throughout the West, a detailed analysis of this event was undertaken. The goals of this study were to compare this event with the regulatory design precipitation event, compare the estimated peak flow rates from the rainfall/runoff model used to size the flood mitigation structures at a radioactive waste management site with the estimated peak flows from the precipitation event, and examine if modification of the standard source of the design depths of precipitation is warranted.     

Public-private partnerships: spreading the three Rs

The privatization of government services is a complex, long-term endeavor with significant contractual, financial, operational and political considerations. This article addresses the very different perspectives of government and business toward privatization and identifies areas for negotiation based on examples in the water, solid waste, housing, energy and telecommunications sectors. The article also addresses the fundamentals of privatization—risks, responsibilities and rewards—and the ways in which business and government assess and allocate (or spread) these elements. The article then stresses that each entity must move beyond these basic assessments to better appreciate the legitimate perspectives of their counterparts at the negotiating table. Only then may a critical blending of goals and expectations begin to emerge and form the foundation for a successful privatization programme.     

Reside0ntial solar water heating as a potential Clean Development Mechanism project: A South African case study

A community-based Clean Development Mechanism (CDM) project – asolar water heating project in a low-income community in South Africa –is analysed to illustrate the methodological and policy challenges that faceimplementation of the Kyoto Protocol to the United Nations FrameworkConvention on Climate Change. We evaluate four baseline options, andthree potential CDM interventions. The emissions reductions range from –670 to +5 929 Mg CO₂ per year, with all option but oneshowing positive emission reductions. Using metered solar water heatingwith liquefied petroleum gas back-up as the CDM intervention, and electricstorage geysers as the baseline, the annual emissions reductions are 5686 Mg CO₂. The cost-effectiveness from the national perspective,which is the incremental life cycle costs divided by the lifetime emissionsreductions, is –$18 per Mg CO₂ From the perspective of theCDM investor, however, the cost-effectiveness is $5.2 per mgCO₂, assuming that the investor receives all of the carbon credits forproviding the incremental capital investment. From our analysis, weconclude that using the current technology (kerosene stoves) as a baselineis probably not appropriate because it does not reflect likely future trendsand also penalises the community for their poverty and current lack ofinfrastructure. We also highlight the importance of credit sharing, and howit affects the cost-effectiveness of the project from the CDM investor'sperspective. The lessons from this analysis are important for the currentinternational policy debate on how to preferentially treat small-scale CDMprojects.