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.     

Effect of manure application timing, crop, and soil type on nitrate leaching

Timing of manure application affects N leaching. This 3-yr study quantified N losses from liquid manure application on two soils, a Muskellunge clay loam and a Stafford loamy sand, as affected by cropping system and timing of application. Dairy manure was applied at an annual rate of 93 800 L ha(-1) on replicated drained plots under continuous maize (Zea mays L.) in early fall, late fall, early spring, and as a split application in early and late spring. Variable rates of supplemental sidedress N fertilizer were applied as needed. Manure was applied on orchardgrass (Dactylis glomerata L.) in split applications in early fall and late spring, and early and late spring, with supplemental N fertilizer topdressed as NH4NO3 in early spring at 75 kg N ha(-1). Drain water was sampled at least weekly when lines were flowing. Three-year FWM (flow-weighted mean) NO3-N concentrations on loamy sand soil averaged 2.5 times higher (12.7 mg L(-1)) than those on clay loam plots (5.2 mg L(-1)), and those for fall applications on maize-cropped land averaged >10 mg L(-1) on the clay loam and >20 mg L(-1) on the loamy sand. Nitrate-N concentrations among application seasons followed the pattern early fall > late fall > early spring = early + late spring. For grass, average NO3-N concentrations from manure application remained well below 10 mg L(-1). Fall manure applications on maize show high NO3-N leaching risks, especially on sandy soils, and manure applications on grass pose minimal leaching concern.     

Bedding and within-pen location effects on feedlot pen runoff quality using a rainfall simulator

Soluble salts, nutrients, and pathogenic bacteria in feedlot-pen runoff have the potential to cause pollution of the environment. A 2-yr study (1998-1999) was conducted at a beef cattle (Bos taurus) feedlot in southern Alberta, Canada, to determine the effect of bedding material [barley (Hordeum vulgare L.) straw versus wood chips] and within-pen location on the chemical and bacterial properties of pen-floor runoff. Runoff was generated with a portable rainfall simulator and analyzed for chemical content (nitrogen [N], phosphorus [P], soluble salts, electrical conductivity [EC], sodium adsorption ratio [SAR], dissolved oxygen [DO], and pH) and populations of three groups of bacteria (Escherichia coli, total coliforms, total aerobic heterotrophs at 27 degrees C) in 1998 and 1999. Bedding had a significant (P < or = 0.05) effect on NH4-N concentration and load in 1999, SO4 load in 1998, SO4 concentration and load in 1999, and total coliforms in both years; where these three variables were higher in wood than straw pens. Location had a significant effect on EC and concentrations of total Kjeldahl nitrogen (TKN), Na, K, SO4, and Cl in 1998, and total coliforms in both years. These seven variables were higher at the bedding pack than pen floor location, indicating that bedding packs were major reservoirs of TKN, soluble salts, and total coliforms. Significantly higher dissolved reactive phosphorus (DRP), total P, and NH4-N concentrations and loads at the bedding pack location in wood pens in 1998, and a similar trend for TKN concentration in 1999, indicated that this bedding-location treatment was a greater source of nutrients to runoff than the other three bedding-location treatments. Bedding, location, and their interaction may therefore be a potential tool to manage nutrients, soluble salts, and bacteria in feedlot runoff.     

Phosphorus and nitrogen in rainfall simulation runoff after fresh and composted beef cattle manure application

Fresh beef cattle (Bos taurus) manure has traditionally been applied to cropland in southern Alberta, but there has been an increase in application of composted manure to cropland in this region. However, the quality of runoff under fresh manure (FM) versus composted manure (CM) has not been investigated. Our objective was to compare runoff quality under increasing rates (0, 13, 42, 83 Mg ha(-1) dry wt.) of FM and CM applied for two consecutive years to a clay loam soil cropped to irrigated barley (Hordeum vulgare L.). We determined total phosphorus (TP), particulate phosphorus (PP), dissolved reactive phosphorus (DRP), total nitrogen (TN), NH4-N, and NO3-N concentrations and loads in runoff after one (1999) and two (2000) applications of FM and CM. We found significantly (P < or = 0.05) higher TP, DRP, and NH4-N concentrations, and higher DRP and TN loads under FM than CM after 2 yr of manure application. The TP loads were also higher under FM than CM at the 83 Mg ha(-1) rate in 2000, and DRP loads were higher for FM than CM at this high rate when averaged over both years. Application rate had a significant effect on TP and DRP concentrations in runoff. In addition, the slope values of the regressions between TP and DRP in runoff versus application rate were considerably higher for FM in 2000 than for FM in 1999, and CM in both 1999 and 2000. Significant positive relationships were found for TP and DRP in runoff versus soil Kelowna-extractable P and soil water-extractable P for FM and CM in 2000, indicating that interaction of runoff with the soil controlled the release of P. Total P and DRP were the variables most affected by the treatments. Overall, our study found that application of CM rather than FM to cropland may lower certain forms of P and N in surface runoff, but this is dependent on the interaction with year, application rate, or both.     

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.     

Electroosmotic dewatering of dredged sediments: bench-scale investigation

The Indiana Harbor (Indiana, USA) has not been dredged since 1972 due to lack of a suitable disposal site for dredged sediment. As a result of this, over a million cubic yards of highly contaminated sediment has accumulated in the harbor. Recently, the United States Army Corps of Engineers (USACE) has selected a site for the confined disposal facility (CDF) and is in the process of designing it. Although dredging can be accomplished rapidly, the disposal in the CDF has to be done slowly to allow adequate time for consolidation to occur. The sediment possesses very high moisture content and very low hydraulic conductivity, which cause consolidation to occur slowly. Consolidation of the sediment is essential in order to achieve adequate shear strength of sediments and also to provide enough air space to accommodate the large amount of sediment that requires disposal. Currently, it has been estimated that if a one 3-foot (0.9-m) thick layer of sediment was disposed of at the CDF annually, it would take approximately 10 years to dispose of all the sediment that is to be dredged from the Indiana Harbor. This study investigated the feasibility of using an electroosmotic dewatering technology to accelerate dewatering and consolidation of sediment, thereby allowing more rapid disposal of sediment into the CDF. Electroosmotic dewatering essentially involves applying a small electric potential across the sediment layer, thereby inducing rapid flow as a result of physico-chemical and electrochemical processes. A series of bench-scale electrokinetic experiments were conducted on actual dredged sediment samples from the Indiana Harbor to investigate dewatering rates caused by gravity alone, dewatering rates caused by gravity and electric potential, and the effects of the addition of polymer flocculants on dewatering of the sediments. The results showed that electroosmotic dewatering under an applied electric potential of 1.0VDC/cm could increase the rate of dewatering and consolidation by an order of magnitude as compared to gravity drainage alone. Amending the sediment with polymers at low concentrations (0.5-1% by dry weight) will enhance this dewatering process; however, the optimal polymer concentration and the cost-effectiveness of using polymers should be investigated further.     

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.