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.     

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.     

Stream buffer effectiveness in an agriculturally influenced area, southwestern Georgia: responses of water quality, macroinvertebrates, and amphibians

To determine useful metrics for assessing stream water quality in the Southeastern Coastal Plain, we examined differences among two buffered and three unbuffered streams in an agricultural landscape in southwestern Georgia. Potential indicators included amphibian diversity and abundance, aquatic macroinvertebrate populations, riparian vegetative structure, water quality, and stream physical parameters. Variability among sites and treatments (buffered vs. unbuffered) existed, with sites in the same treatment as most similar, and disturbances from a nearby eroding gully strongly affecting one unbuffered site. Of the invertebrate metrics examined, percentages of clingers, Ephemeroptera-Plecoptera-Trichoptera (EPT), Elmidae (Coleoptera), Crustacea (Decapoda and Amphipoda), and dipterans were found to be possible indicators of stream health for perennial streams within this region. Overall, buffered sites showed higher percentages of sensitive invertebrate groups and showed lower and more stable concentrations of nitrate N, suspended solids, and fecal coliforms (FCs). Percent canopy cover was similar among sites; however, riparian vegetative coverage and percent leaf litter were greatest at buffered sites. No differences in amphibian abundance, presence, and absence within the riparian area were apparent between sites; however, instream larval salamanders were more abundant at buffered streams. In this study, stream buffers appeared to decrease nutrient and sediment loads to adjacent streams, enhancing overall water quality. Selected benthic macroinvertebrate metrics and amphibian abundance also appeared sensitive to agricultural influences. Amphibians show potential as indicator candidates, however further information is needed on their responses and tolerances to disturbances from the microhabitat to landscape levels.     

Management of mine spoil for crop productivity with lignite fly ash and biological amendments

Long-term field trials using lignite fly ash (LFA) were carried out in rice crops during the period 1996-2000 at Mine I, Neyveli Lignite Corporation, Tamil Nadu. LFA, being alkaline and endowed with an excellent pozzolanic nature, silt loam texture, and plant nutrients, has the potential to improve the texture, fertility, and crop productivity of mine spoil. The rice crops were the first, third, fifth, and sixth crops in rotation. The other crops, such as green gram (second) and sun hemp (fourth), were grown as green manure. For experimental trials, LFA was applied at various dosages (0, 5, 10, 20, 50, 100, and 200 t/ha), with and without press mud (10 t/ha), before cultivation of the first crop. Repeat applications of LFA were made at the same dosages in treatments of up to 50 t/ha (with and without press mud) before cultivation of the third and fifth crops. Press mud, a lightweight organic waste product from the sugar industry, was used as an organic amendment and source of plant nutrients. Also, a recommended dosage of chemical fertilizer, along with gypsum, humic acid, and biofertilizer as supplementing agents, was applied in all the treatments, including control. With one-time and repeat applications of LFA, from 5 to 20 t/ha (with and without press mud), the crop yield (grain and straw) increased significantly (p < 0.05), in the range from 3.0 to 42.0% over the corresponding control. The maximum yield was obtained with repeat applications of 20 t/ha of LFA with press mud in the third crop. The press mud enhanced the yield in the range of 1.5-10.2% with various dosages of LFA. The optimum dosage of LFA was 20 t/ha for both one-time and repeat applications. Repeat applications of LFA at lower dosages of up to 20 t/ha were more effective in increasing the yield than the corresponding one-time applications of up to 20 t/ha and repeat applications at 50 t/ha. One-time and repeat applications of LFA of up to 20 t/ha (with and without press mud), apart from increasing the yield, evinced improvement in the texture and fertility of mine spoil and the nutrient content of crop produce. Furthermore, some increase in the content of trace and heavy metals and the level of gamma-emitters in the mine spoil and crop produce was observed, but well within the permissible limits. The residual effect of LFA on succeeding crops was also encouraging in terms of eco-friendliness. Beyond 20 t/ha of LFA, the crop yield decreased significantly (p < 0.05), as a result of the formation of hardpan in the mine spoil and possibly the higher concentration of soluble salts in the LFA. However, the adverse effects of soluble salts were annulled progressively during the cultivation of succeeding crops. A plausible mechanism for the improved fertility of mine spoil and the carryover or uptake of toxic trace and heavy metals and gamma-emitters in mine spoil and crop produce is also discussed.     

Managing disposal of water produced with petroleum in Kuwait

Disposal of water produced with petroleum has been of great interest in Kuwait for the last 20 years. The current problem arose when the Burgan oil field, which is the second largest field in the world, experienced successive increases in the water content of the produced oil. This study introduces a decision-making analysis of the considered alternatives for the disposal of the produced water. Four alternative solutions exist for the industry as practical solutions for the disposal of water produced in Kuwait. The first method utilizes a large number of pits to discharge water. The second alternative depends on discharging water into sealed pits. The third approach to dispose water is by injecting the water underground. The last method is similar to the previous one, but takes into consideration the recovery of reservoir pressure to maintain the rate of oil production. A questionnaire was distributed to 48 experts at the top management level of the petroleum companies and the governmental authority. The data collected considered cost, efficiency, and environmental parameters. Based on the data, a statistical analysis was conducted using the factor analysis method to reduce the number of investigated variables. The analysis concluded that the optimal solution is to use the effluent injection method to discharge water produced with oil in Burgan and similar fields in Kuwait.     

Visitor-induced changes in the chemical composition of soils in backcountry areas of Mt Robson Provincial Park, British Columbia, Canada

Balancing recreation and conservation is an important issue in Canada's parks and protected areas. Increased levels of visitation to parks, especially to backcountry areas, create undue pressure on natural resources, resulting in a variety of ecological impacts. This paper illustrates the issue of visitor-induced changes on the chemical composition of soils in Mt Robson Provincial Park, British Columbia. Soil samples were collected from dish wash stations and fire pits (disturbed sites) at seven campgrounds located along two popular backcountry trails, and were compared to samples obtained from adjacent undisturbed control sites. Analysis of soil samples suggest that the lower amounts of aluminum, potassium, magnesium and sodium in many of the 'disturbed' samples can be related to intense leaching in dish wash stations, and can be attributed to frequent disposal of waste water from washing and cooking activities. Soils in wash stations generally had higher phosphorus, copper and zinc contents as compared to controls. Soils in fire pits were elevated in copper, relative to controls. Results of this study support park regulations that waste water disposal and camp fires be restricted to designated areas. Informing the public of scientific studies helps them understand the consequences of their activities; this may help persuade them to observe park rules and regulations.     

Effects of calibration on L-THIA GIS runoff and pollutant estimation

Urbanization can result in alteration of a watershed's hydrologic response and water quality. To simulate hydrologic and water quality impacts of land use changes, the Long-Term Hydrologic Impact Assessment (L-THIA) system has been used. The L-THIA system estimates pollutant loading based on direct runoff quantity and land use based pollutant coefficients. The accurate estimation of direct runoff is important in assessing water quality impacts of land use changes. An automated program was developed to calibrate the L-THIA model using the millions of curve number (CN) combinations associated with land uses and hydrologic soil groups. L-THIA calibration for the Little Eagle Creek (LEC) watershed near Indianapolis, Indiana was performed using land use data for 1991 and daily rainfall data for six months of 1991 (January 1-June 30) to minimize errors associated with use of different temporal land use data and rainfall data. For the calibration period, the Nash-Sutcliffe coefficient was 0.60 for estimated and observed direct runoff. The calibrated CN values were used for validation of the model for the same year (July 1-December 31), and the Nash-Sutcliffe coefficient was 0.60 for estimated and observed direct runoff. The Nash-Sutcliffe coefficient was 0.52 for January 1, 1991 to December 31, 1991 using uncalibrated CN values. As shown in this study, the use of better input parameters for the L-THIA model can improve accuracy. The effects on direct runoff and pollutant estimation of the calibrated CN values in the L-THIA model were investigated for the LEC. Following calibration, the estimated average annual direct runoff for the LEC watershed increased by 34%, total nitrogen by 24%, total phosphorus by 22%, and total lead by 43%. This study demonstrates that the L-THIA model should be calibrated and validated prior to application in a particular watershed to more accurately assess the effects of land use changes on hydrology and water quality.     

Recycling of an industrial sludge and marine clay as light-weight aggregates

The geographical limitations of Singapore, its restricted natural resources and voluminous municipal and industrial waste streams, make environmental management a major challenge for the island state. In an attempt to find ways to reduce importation of raw materials and the waste sent to landfill, light weight aggregates were produced from marine clay and a CaF(2)-rich semiconductor industry sludge. Aggregates were produced in a bench-scale rotary kiln with three clay/sludge loadings (90/10, 70/30 and 50/50%). All three mixtures showed good bloating behavior during firing and the ceramic pellets (1-1.5cm diameter) had densities well below that required for light-weight aggregates. In the initial tests, the pore sizes of the aggregates were in general too large resulting in high water absorption. Comparisons between the composition of the two waste products and the aggregates showed a significant loss of fluorine (40-60%) during processing; a problem which may require flue gas treatment. Leach testing showed that the formed aggregates would not pose a human or environmental hazard in terms of fluorine mobilization.     

Modelling the Distribution and Quality of Sand and Gravel Resources in 3D: a Case Study in the Thames Basin,UK

Three-dimensional (3D) models are often utilised to assess the presence of sand and gravel deposits. Expanding these models to provide a better indication of the suitability of the deposit as aggregate for use in construction would be advantageous. This, however, leads to statistical challenges. To be effective, models must be able to reflect the interdependencies between different criteria (e.g. depth to deposit, thickness of deposit, ratio of mineral to waste, proportion of ‘fines’) as well as the inherent uncertainty introduced because models are derived from a limited set of boreholes in a study region. Using legacy borehole data collected during a systematic survey of sand and gravel deposits in the UK, we have developed a 3D model for a 2400 km² region close to Reading, southern England. In developing the model, we have reassessed the borehole grading data to reflect modern extraction criteria and explored the most suitable statistical modelling technique. The additive log-ratio transform and the linear model of coregionalization have been applied, techniques that have been previously used to map soil texture classes in two dimensions, to assess the quality of sand and gravel deposits in the area. The application of these statistical techniques leads to a model which can be used to generate thousands of plausible realisations of the deposit which fully reflect the extent of model uncertainty. The approach offers potential to improve regional-scale mineral planning by providing an enhanced understanding of sand and gravel deposits and the extent to which they meet current extraction criteria.

     

Ozone facilitated degradation of caffeine using Ce-TiO2 catalyst

The ozone initiated oxidation of 1,3,7-trimethylxanthine (caffeine), commonly found in wastewaters as model compound is reported using cerium (Ce)/titanium dioxide (TiO₂) as catalyst. The effect of pH and loading of ceria on titania were investigated. Effect of reaction conditions on degradation of caffeine based on their pseudo first-order rate constants were compared. The combination of catalyst Ce-TiO₂ and ozone aeration significantly enhanced the degradation of caffeine compared to uncatalysed ozonation. The oxidation of caffeine ensued via the free radical mechanism, through enhanced ozone decomposition into OH radicals. Ce/TiO₂(0.5?wt%) showed good activity in degradation of caffeine at pH 6, in both natural stream and river water samples showing about 60% total organic carbon removal in 2?h ozonation period. Using liquid chromatography-mass spectroscopy, degradation products were analysed. A reaction intermediate and one final product were positively identified. Nano-catalysts with different loadings of Ce on TiO₂ synthesized by sol-gel route were characterized by scanning electron microscope, transmission electron microscopy, BET and powder X-ray diffraction spectrum techniques. The results showed that the material retained a highly ordered mesoporous structure and possessed large surface area.