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.     

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.     

Soil organic carbon sequestration in cotton production systems of the southeastern United States: a review

Past agricultural management practices have contributed to the loss of soil organic carbon (SOC) and emission of greenhouse gases (e.g., carbon dioxide and nitrous oxide). Fortunately, however, conservation-oriented agricultural management systems can be, and have been, developed to sequester SOC, improve soil quality, and increase crop productivity. Our objectives were to (i) review literature related to SOC sequestration in cotton (Gossypium hirsutum L.) production systems, (ii) recommend best management practices to sequester SOC, and (iii) outline the current political scenario and future probabilities for cotton producers to benefit from SOC sequestration. From a review of 20 studies in the region, SOC increased with no tillage compared with conventional tillage by 0.48 +/- 0.56 Mg C ha(-1) yr(-1) (H(0): no change, p < 0.001). More diverse rotations of cotton with high-residue-producing crops such as corn (Zea mays L.) and small grains would sequester greater quantities of SOC than continuous cotton. No-tillage cropping with a cover crop sequestered 0.67 +/- 0.63 Mg C ha(-1) yr(-1), while that of no-tillage cropping without a cover crop sequestered 0.34 +/- 47 Mg C ha(-1) yr(-1) (mean comparison, p = 0.04). Current government incentive programs recommend agricultural practices that would contribute to SOC sequestration. Participation in the Conservation Security Program could lead to government payments of up to Dollars 20 ha(-1). Current open-market trading of C credits would appear to yield less than Dollars 3 ha(-1), although prices would greatly increase should a government policy to limit greenhouse gas emissions be mandated.     

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.     

Soil amendments, plant age, and intercropping impact p,p'-DDE bioavailability to Cucurbita pepo

Field experiments were conducted to optimize the phytoextraction of weathered p,p'-DDE (p,p'-dichlorodiphenyldichloroethylene) by Cucurbita subspecies. The effects of two soil amendments, mycorrhizae or a biosurfactant, on p,p'-DDE accumulation was determined. Also, p,p'-DDE uptake was assessed during plant growth (12, 26, 38, and 62 d), and cultivars that accumulate weathered p,p'-DDE were intercropped with cultivars known not to have that ability. Cucurbita pepo L. ssp. pepo accumulated large amounts of the contaminant, having stem bioconcentration factors, amounts of p,p'-DDE translocated, and contaminant phytoextraction that were 14, 9.9, and 5.0 times greater than C. pepo L. ssp. ovifera (L.) D.S. Decker, respectively. During 62 d, the stem BCF (bioconcentration factor) for p,p'-DDE in subspecies pepo remained constant and the total amount of contaminant accumulated was correlated with plant biomass (r(2) = 0.86). For subspecies ovifera, the stem BCF was highest at 12 d (1.5) but decreased to 0.39 by 62 d, and p,p'-DDE removal was not correlated with plant biomass. Mycorrhizal inoculation increased p,p'-DDE accumulation by both subspecies by an average 4.4 times. For subspecies pepo, mycorrhizae increased the percentage of contaminant extracted from 0.72 to 2.1%. Biosurfactant amendment also enhanced contaminant accumulation by both subspecies, although treatment reduced subspecies ovifera biomass by 60%. The biosurfactant had no effect on the biomass of subspecies pepo, increased the average contaminant concentration by 3.6-fold, and doubled the overall amount of p,p'-DDE removed from the soil. Soil amendments that enhance the mobility of weathered persistent organic pollutants will significantly increase the amount of contaminant phytoextraction by Cucurbita pepo.     

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.