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.     

Nitrogen and phosphorus leaching from growing season versus year-round application of wastewater on seasonally frozen lands

Land application of wastewater has become an important disposal option for food-processing plants operating year-round. However, there are concerns about nutrient leaching from winter wastewater application on frozen soils. In this study, P and N leaching were compared between nongrowing season application of tertiary-treated wastewater plus growing season application of partially treated wastewater (NGS) vs. growing season application of partially treated wastewater (GS) containing high levels of soil P. As required by the Minnesota Pollution Control Agency (MPCA), the wastewater applied to the NGS fields during October through March was treated such that it contained < or =6 mg L(-1) total phosphorus (TP), < or =10 mg L(-1) NO3-N, and < or =20 mg L(-1) total Kjeldahl nitrogen (TKN). The only regulation for wastewater application during the growing season (April through September) was that cumulatively it did not exceed the agronomic N requirements of the crop in any sprayfield. Application of tertiary-treated wastewater during the nongrowing season plus partially treated wastewater during the growing season did not significantly increase NO3-N leaching compared with growing season application of nonregulated wastewater. However, median TP concentration in leachate was significantly higher from the NGS (3.56 mg L(-1)) than from the GS sprayfields (0.52 mg L(-1)) or nonirrigated sites (0.52 mg L(-1)). Median TP leaching loss was also significantly higher from the NGS sprayfields (57 kg ha(-1)) than from the GS (7.4 kg ha(-1)) or control sites (6.9 kg ha(-1)). This was mainly due to higher hydraulic loading from winter wastewater application and limited or no crop P uptake during winter. Results from this study indicate that winter application of even low P potato-processing wastewater to high P soils can accelerate P leaching. We conclude that the regulation of winter wastewater application on frozen soils should be based on wastewater P concentration and permissible loading. We also recommend that winter irrigation should take soil P saturation into consideration.     

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.     

Phosphorus sequestration by chemical amendments to reduce leaching from wastewater applications

Phosphorus-immobilizing amendments can be useful in minimizing P leaching from high P soils that may be irrigated with wastewater. This study tested the P-binding ability of various amendment materials in a laboratory incubation experiment and then tested the best amendment in a field setup using drainage lysimeters. The laboratory experiment involved incubating 100-g samples of soil (72 mg kg(-1) water-extractable phosphorus, WEP) with various amendments at different rates for 63 d at field moisture capacity and 25 degrees C. The amendments tested were alum [Al2SO4)3.14H2O], ferric chloride (FeCl3), calcium carbonate (CaCO3), water treatment residual (WTR), and sugarbeet lime (SBL). Ferric chloride and alum at rates of 1.5 and 3.9 g kg(-1), respectively, were the most effective amendments that decreased WEP to 20 mg kg(-1), below which leaching has previously been shown to be low. Alum (1.3 kg m(-2)), which is less sensitive to redox conditions, was subsequently tested under field conditions, where it reduced WEP concentration in the 0- to 0.15-m layer from 119 mg kg(-1) on Day 0 to 36.1 mg kg(-1) (85% decrease) on Day 41. Lysimeter breakthrough tests using tertiary-treated potato-processing wastewater (mean total phosphorus [TP] = 3.4 mg L(-1)) showed that alum application reduced leachate TP and soluble reactive phosphorus (SRP) concentrations by 27 and 25%, respectively. These results indicate that alum application may be an effective strategy to immobilize P in high P coarse-textured soils. The relatively smaller decreases in TP and SRP in the leachate compared to WEP suggest some of the P may be coming from depths below 0.2 m. Thus, to achieve higher P sequestration, deeper incorporation of the alum may be necessary.     

Carbon and nitrogen mineralization rates after application of organic amendments to soil

The objective of this study was to quantify C and N mineralization rates from a range of organic amendments that differed in their total C and N contents and C quality, to gain a better understanding of their influence on the soil N cycle. A pelletized poultry manure (PP), two green waste-based composts (GWCa, GWCb), a straw-based compost (SBC), and a vermi-cast (VER) were incubated in a coarse-textured soil at 15 degrees C for 142 d. The C quality of each amendment was determined by chemical analysis and by 13C nuclear magnetic resonance (NMR). Carbon dioxide (CO2-C) evolution was determined using alkali traps. Gross N mineralization rates were calculated by 15N isotopic pool dilution. The CO2-C evolution rates and gross N mineralization rates were generally higher in amended soils than in the control soil. With the exception of GWCb all amendments released inorganic N at concentrations that would be high enough to warrant a reduction in inorganic N fertilizer application rates. The amount of N released from PP was high indicating that application rates should be reduced, or alternative amendments used, to minimize leaching losses in regions where ground water quality is of concern. There was a highly significant relationship between CO2-C evolution and gross N mineralization (R2= 0.95). Some of the chemically determined C quality parameters had significant relationships (p < 0.05) with both the cumulative amounts of C and N evolved. However, we found no significant relationships between 13C NMR spectral groupings, or their ratios, and either the CO2-C evolved or gross N mineralized from the amendments.     

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 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.     

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.     

Demonstration of methods to reduce E. coli runoff from dairy manure application sites

Contamination by bacteria is a leading cause of impairment in U.S. waters, particularly in areas of livestock agriculture. We evaluated the effectiveness of several practices in reducing Escherichia coli levels in runoff from fields receiving liquid dairy (Bos taurus) manure. Runoff trials were conducted on replicated hay and silage corn (Zea mays L.) plots using simulated rainfall. Levels of E. coli in runoff were approximately 10(4) to 10(6) organisms per 100 mL, representing a significant pollution potential. Practices tested were: manure storage, delay between manure application and rainfall, manure incorporation by tillage, and increased hayland vegetation height. Storage of manure for 30 d or more consistently and dramatically lowered E. coli counts in our experiments, with longer storage providing greater reductions. Manure E. coli declined by > 99% after approximately 90 d of storage. On average, levels of E. coli in runoff were 97% lower from plots receiving 30-d-old and > 99% lower from plots receiving 90-d-old manure than from plots where fresh manure was applied. Runoff from hayland and cornland plots where manure was applied 3 d before rainfall contained approximately 50% fewer E. coli than did runoff from plots that received manure 1 d before rainfall. Hayland vegetation height alone did not significantly affect E. coli levels in runoff, but interactions with rainfall delay and manure age were observed. Manure incorporation alone did not significantly affect E. coli levels in cornland plot runoff, but incorporation could reduce bacteria export by reducing field runoff and interaction with rainfall delay was observed. Extended storage that avoids additions of fresh manure, combined with application several days before runoff, incorporation on tilled land, and higher vegetation on hayland at application could substantially reduce microorganism loading from agricultural land.     

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.