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.     

Diuron in surface runoff and tile drainage from two grass-seed fields

The typical method of cool-season grass-seed production in Mediterranean climates briefly exposes surface waters to potentially high concentrations of the herbicide diuron [3-(3,4-dichlorophenyl)-1,1-dimethyl urea] during the initial season of growth. To better understand the process, and the degree, of diuron transport from agricultural fields, two grass-seed fields in the Willamette Valley of Oregon were monitored for diuron loss in surface runoff and tile drainage during the first wet season after planting. Initial diuron concentrations in surface runoff were high (>1000 microg L(-1) in one field and >100 microg L(-1) in the other), though they decreased by two orders of magnitude by the end of the season. Concentrations in the tile drains were as much as 1000 times lower than in the surface runoff during the first few weeks of runoff events, and they remained lower than surface water concentrations throughout the season. Total losses in surface runoff were between 1.3 and 3% of the amount applied-much higher than losses via the tile drains. It is also shown by means of a simple first-order decay model that, when little information is available, it may be best to describe diuron depletion in runoff water as a function of cumulative rainfall during the wet season.     

Nitrogen and phosphorus status of soils and trophic state of lakes associated with forage-based beef cattle operations in Florida

Forage-based livestock systems have been implicated as major contributors to deteriorating water quality, particularly for phosphorus (P) from commercial fertilizers and manures affecting surface and ground water quality. Little information exists regarding possible magnitudes of nutrient losses from pastures that are managed for both grazing and hay production and how these might impact adjacent bodies of water. We examined the changes that have occurred in soil fertility levels of rhizoma peanut (Arachis glabrata Benth.)-based beef cattle pastures (n = 4) in Florida from 1988 to 2002. These pastures were managed for grazing in spring followed by haying in late summer and were fertilized annually with P (39 kg P2O5 ha(-1)) and K (68 kg K2O ha(-1)). Additionally, we investigated trends in water quality parameters and trophic state index (TSI) of lakes (n = 3) associated with beef cattle operations from 1993 to 2002. Overall, there was no spatial or temporal buildup of soil P and other crop nutrients despite the annual application of fertilizers and daily in-field loading of animal waste. In fact, soil fertility levels showed a declining trend for crop nutrient levels, especially soil P (y = 146.57 - 8.14 x year; r2= 0.75), even though the fields had a history of P fertilization and the cattle were rotated into the legume fields. Our results indicate that when nutrients are not applied in excess, cow-calf systems are slight exporters of P, K, Ca, and Mg through removal of cut hay. Water quality in lakes associated with cattle production was "good" (30-46 TSI) based on the Florida Water Quality Standard. These findings indicate that properly managed livestock operations may not be major contributors to excess loads of nutrients (especially P) in surface water.     

Iron and arsenic release from aquifer solids in response to biostimulation

Biostimulation has been used at various contaminated sites to promote the reductive dechlorination of trichloroethylene (TCE), but the addition of carbon and energy donor also stimulates bacteria that use Fe(III) as the terminal electron acceptor (TEA) in potential competition with dechlorination processes. Microcosm studies were conducted to determine the influence of various carbon donors on the extent of reductive dissolution of aquifer solids containing Fe(III) and arsenic. Glucose, a fermentable and respirable carbon donor, led to the production of 1500 mg Fe(II) kg(-1), or 24% of the total Fe in the aquifer sediment being reduced to Fe(II), whereas the same concentration of carbon as acetate resulted in only 300 mg Fe(II) kg(-1) being produced. The biogenic Fe(II) produced with acetate was exclusively associated with the solid phase whereas with fermentable carbon donors as whey and glucose, 22 and 54% of the Fe(II) was in solution. With fermentation, some of the metabolites appear to be electron shuttling chemicals and chelating agents that facilitate the reductive dissolution of even crystalline Fe(III) oxides. Without the presence of electron shuttling chemicals, only surficial Fe in direct contact with the bacteria was bioavailable, as illustrated when acetate was used. Regardless of carbon donor type and concentration, As concentrations in the water exceeded drinking water standards. The As dissolution appears to have been the result of the direct use of As as an electron acceptor by dissimilatory arsenic reducing bacteria. Our findings indicate that selection of the carbon and energy donor for biostimulation for remediation of chlorinated solvent impacted aquifers may greatly influence the extent of the reductive dissolution of iron minerals in direct competition with dechlorination processes. Biostimulation may also result in a significant release of As to the solution phase, contributing to further contamination of the aquifer.     

Behavior of an aerated submerged fixed-film reactor (ASFFR) under simultaneous organic and ammonium loading

The performance of an aerated submerged fixed-film reactor (ASFFR) under simultaneous organic and ammonium loading and its effect on nitrification was studied. Organic loadings varied in the range of 1.93 to 5.29 g chemical oxygen demand (COD) m-2 d-1 and NH4-N loadings were in the range of 116 to 318 mg NH4-N m-2 d-1. Increments of loading rates were obtained both by increasing the flow rate and increasing the influent substrate in individual pilot runs. Results showed that with organic loading rates up to 3.97 g COD m-2 d-1, complete nitrification was achievable. Although high organic loading such as 5.29 g COD m-2 d-1 could cause nitrification to stop, shifting to lower organic loadings made nitrification start and set rapidly to its previous steady-state concentrations. Comparison of results showed that in the ASFFR, nitrification would be severely affected by an organic loading rate of 5.29 g COD m-2 d-1 by increasing either the flow or the influent substrate. It should be noted that the average value of dissolved oxygen was 3.4 mg L-1 with an air supply of 15 L min-1, and there was no indication of oxygen limitation. The results of this study show the flexibility of ASFFRs under changing organic loads. Furthermore, for achieving complete nitrification and optimum application of these reactors for protecting receiving water from the environmental hazards of ammonium, the maximum organic loading that would present complete nitrification should be considered.     

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.     

Methods for integrated assessment

Integrated assessment is an approach that seeks to involve all disciplines in policy-relevant assessment. The process aims to encompass environmental science, technology and policy problems. The aim is to establish an overview of the environmental issue in question that attempts to avoid the mistakes of the past associated with narrow, one-sided or unidimensional approaches. A number of methods are available for such assessments. However, they are also subject to a number of limitations, difficulties and dilemmas. Integrated methods are inherently complicated and the tradition is that only experts are involved. New more inclusionary procedures have to be devised in order to involve all stakeholders. They have to be involved in the framing of the issue and in the value judgements associated with the approach. The dilemmas cannot be solved by integrated approaches, but they can be mitigated via proper identification, analysis and evaluation of the gains and losses involved. In structuring the analysis the existence of ignorance has to be accounted for and communicated to the managers and the political decision makers. The ignorance/uncertainty aspects can be partially accommodated for via an intensification of feasible monitoring and research so as to minimise the risks of unpleasant surprises. Electronic Publication     

Simultaneous removal of potent cyanotoxins from water using magnetophoretic nanoparticle of polypyrrole: adsorption kinetic and isotherm study

Cyanotoxins, microcystins and cylindrospermopsin, are potent toxins produced by cyanobacteria in potable water supplies. This study investigated the removal of cyanotoxins from aqueous media by magnetophoretic nanoparticle of polypyrrole adsorbent. The adsorption process was pH dependent with maximum adsorption occurring at pH 7 for microcystin-LA, LR, and YR and at pH 9 for microcystin-RR and cylindrospermopsin (CYN). Kinetic studies and adsorption isotherms reflected better fit for pseudo-second-order rate and Langmuir isotherm model, respectively. Thermodynamic calculations showed that the cyanotoxin adsorption process is endothermic and spontaneous in nature. The regenerated adsorbent can be successfully reused without appreciable loss of its original capacity.     

Reclamation and revegetation of fly ash disposal sites - Challenges and research needs

Coal-fired power generation is a principal energy source throughout the world. Approximately, 70-75% of coal combustion residues are fly ash and its utilization worldwide is only slightly above 30%. The remainder is disposed of in landfills and fly ash basins. It is desirable to revegetate these sites for aesthetic purposes, to stabilize the surface ash against wind and water erosion and to reduce the quantity of water leaching through the deposit. Limitations to plant establishment and growth in fly ash can include a high pH (and consequent deficiencies of Fe, Mn, Cu, Zn and P), high soluble salts, toxic levels of elements such as B, pozzalanic properties of ash resulting in cemented/compacted layers and lack of microbial activity. An integrated organic/biotechnological approach to revegetation seems appropriate and should be investigated further. This would include incorporation of organic matter into the surface layer of ash, mycorrhizal inoculation of establishing vegetation and use of inoculated legumes to add N. Leaching losses from ash disposal sites are likely to be site-specific but a sparse number of studies have revealed enriched concentrations of elements such as Ca, Fe, Cd, Pb, and Sb in surrounding groundwater. This aspect deserves further study particularly in the longer-term. In addition, during weathering of the ash and deposition of organic matter during plant growth, a soil will form with properties vastly different to that of the parent ash. In turn, this will influence the effect that the disposal site has on the surrounding environment. Nevertheless, the effects of ash weathering and organic matter accumulation over time on the chemical, physical and biological properties of the developing ash-derived soil are not well understood and require further study.