Experimental and theoretical studies on physico-chemical parameters affecting the solubility of phosphogypsum

Phosphogypsum is a waste by-product of the phosphate fertilizer industry, which is usually disposed in the environment because of its restricted use in industrial applications. Physico-chemical conditions existing in stack fluids and leachates are of major importance and determine solubility and redox stability of phosphogypsum, as well as radionuclide release from stacks to terrestrial environments. The aim of this study is to assess the effect of key parameters (e.g. ionic strength, temperature, pH) on the solubility of phosphogypsum. Phosphogypsum sampling and in-situ measurements were carried out at a coastal stack in Cyprus, solubility experiments were performed in simulated laboratory systems and thermodynamic calculations by means of MINTEQA2, an equilibrium speciation model. Generally, increasing ionic strength and temperature leads to increased phosphogypsum solubility, with the former being much more effective. The increased solubility of phosphogypsum in saline solutions is attributed solely to ionic strength effects on the activity of ionic species in solution and no solid phase transformations could be observed. The effect of pH on phosphogypsum solubility seems to be insignificant at least in a pH range between 4 and 8. Regarding uranium levels, there is a strong correlation between salinity and uranium concentration and linear correlation between phosphogypsum solubility and uranium levels in stack solutions, indicating the incorporation of uranium into the gypsum lattice and the formation of a solid solution.     

The Use of Carbon and Nitrogen Isotopes to Study Watershed Erosion Processes1

Abstract:  Tracer studies are needed to better understand watershed soil erosion and calibrate watershed erosion models. For the first time, stable nitrogen and carbon isotopes (δ¹⁵N and δ¹³C) and the carbon to nitrogen atomic ratio (C/N) natural tracers are used to investigate temporal and spatial variability of erosion processes within a sub‐watershed. Temporal variability was assessed by comparing δ¹⁵N, δ¹³C, and C/N of eroded‐soils from a non‐equilibrium erosion event immediately following freezing and thawing of surface soils with two erosion events characterized by equilibrium conditions with erosion downcutting. Spatial variability was assessed for the equilibrium events by using the δ¹⁵N and δ¹³C signatures of eroded‐soils to measure the fraction of eroded‐soil derived from rill/interrill erosion on upland hillslopes as compared to headcut erosion on floodplains. In order to perform this study, a number of tasks were carried out including: (1) sampling source‐soils from upland hillslopes and floodplains, (2) sampling eroded‐soils with an in situ trap in the stream of the sub‐watershed, (3) isotopic and elemental analysis of the samples using isotope ratio mass spectrometry, (4) fractioning eroded‐soil to its upland rill/interrill and floodplain headcut end‐members using an unmixing model within a Bayesian Markov Chain Monte Carlo framework, and (5) evaluating tracer unmixing model results by comparison with process‐based erosion prediction models for rill/interrill and headcut erosion processes. Results showed that finer soil particles eroded during the non‐equilibrium event were enriched in δ¹⁵N and δ¹³C tracers and depleted in C/N tracer relative to coarser soil particles eroded during the equilibrium events. Correlation of tracer signature with soil particle size was explainable based on known biogeochemical processes. δ¹⁵N and δ¹³C were also able to distinguish between upland rill/interrill erosion and floodplain headcut erosion, which was due to different plant cover at the erosion sources. Results from the tracer unmixing model highlighted future needs for coupling rill/interrill and headcut erosion prediction models.     

WATERSHED AND INSTREAM IMPACTS ON THE FISH POPULATION IN THE SOUTH FORK OF THE CLEARWATER RIVER,IDAHO1

ABSTRACT: This paper presents the results of a statistical analysis performed for the watershed and stream corridor in the South Fork of the Clearwater River (SFCR) basin, in north central Idaho. The analysis was performed for 61 six‐field hydrological unit codes (HUCs) of the SFCR basin using an extensive record (up to 100 years) for 50 watershed and in‐stream parameters, including hydrologic, flow, fish, anthropogenic, and natural activity data. The objective of this research was twofold: first, the development of quantitative relations that describe the Index of Fish Density (IFD) of particular fish species as a function of watershed and instream parameters; and second, to provide a robust confirmation for the effects of some of these parameters, previously recorded by the fisheries profession, by using well established statistical techniques. The uniqueness of this work is the compilation and statistical analysis of large data sets to quantitatively describe the impacts of watershed and instream parameters on the IFD of all salmonids and specific fish species. Factor analysis was employed to regroup parameters that are highly correlated to each other into a set of single factors and to relate the IFD to these factors. Using factor extraction, 12 factors were developed from the 50 watershed and instream parameters. Multiple regression diagnostic tests indicated that only 7 of the 12 factors are strong predictors offish indicators. The strongest predictors are longitude, latitude, elevation, watershed gradient, and water temperature. The analysis indicated that the present model has reasonable predictive power, considering the uncertainty involved in estimating the interdependence of IFD with watershed parameters.     

Redox chemistry of sulphate and uranium in a phosphogypsum tailings dump

The present study aims to assess the effect of redox conditions existing within the tailings dump on the stability of phosphogypsum (e.g. sulphate reduction) and uranium(VI). Phosphogypsum sampling and in-situ measurements were carried out at a coastal tailings dump in Vasiliko Cyprus, pH, E_H and solubility experiments were performed in simulated laboratory systems and thermodynamic calculations using MINTEQA2. Generally, in the open tailings dump oxidizing conditions predominate stabilizing sulphur and uranium in their hexavalent oxidation states. On the other hand, after the application of a soil/vegetative cover and in the presence of natural organic matter, anoxic conditions prevail (E_H < −70 mV) resulting in S(VI) and U(VI) reduction to S(−II) and U(IV), respectively. Although, the sulphide anion can form very insoluble compounds with heavy metal ions (e.g. Cd(II), Pb(II) etc.) and U(IV) oxide has very low solubility, partial reduction of sulphate to sulphide within gypsum may affect the stability of phosphogypsum resulting in enhanced erosion of the material by rain- and seawater and washing out of contaminants in particulate/colloidal form.     

Integrated Environmental and Hydraulic Design of Xerias River,Corinthos, Greece,Training Works

The modern design of flood protection and training works in cases of major natural streams and creeks, requires a fine balance between a sound engineering approach in all engineering aspects on one hand, and an environmentally acceptable solution on the other. Progress in integrating environmental and hydraulic design has been achieved over the years due to different factors, like proper collaboration of engineering disciplines, hydraulic modeling enhancement, development and use of suitable materials, amelioration of the construction methods, and proper restoration and use of the affected areas. In this paper, a synopsis of the experience that has been gained by our firm over the years in designing flood protection and river training works for urban and rural areas is presented, including the general design principles to be used as guidelines, and illustrated with the case study of river Xerias, Greece. The river Xerias is located in Peloponnese, Greece. It flows from south to north and has a catchment area of 170 km². For the last 1500 m before discharging into the Corinthian gulf, the river flows through the city of Corinthos. This is the reach, which overflowed and flooded the city during the January 1997 flood, causing a lot of damage and human life casualties.     

Levels of dioxins and dioxin-like PCBs in food samples on the Greek market

Food intake is the main source of exposure to dioxin-like compounds for humans. The results of a surveillance programme on polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and co-planar polychlorinated biphenyls (co-PCBs) in 77 food samples from the Greek market and producers are presented. The study included the analyses of milk and dairy products, meat and meat products, fish, vegetable oil, eggs, fruit, vegetable and rice collected between August and December 2002. After extraction, extracts were cleaned up on a series of carbon column chromatography, silica gel, alumina chromatography, and then analysed by high resolution gas chromatography/high resolution mass spectrometry. All samples had a dioxin content far below the EC Regulation (2375/2001/EC) limits.