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Land application of biochar reportedly provides many benefits, including reduced risk of nutrient transport, greenhouse gas (GHG) emission mitigation, and increased soil C storage, but additional field validation is needed. We evaluated the effectiveness of biochar in controlling the lability of nutrients in agricultural land. This study was designed to evaluate the impacts of biochar co-applied with various N and P sources on GHG fluxes from a subtropical grassland. Nutrients (inorganic fertilizer and aerobically digested Class B biosolids) were surface applied at a rate of 160 kg plant available N ha -1  yr -1 with or without biochar (applied at 20 Mg ha -1 ). Greenhouse gas (CO 2 , CH 4 , and N 2 O) fluxes were assessed using static chambers and varied significantly, both temporally and with treatments. Greenhouse gas fluxes ranged from 1,247 to 23,160, -0.7 to 42, and -1.4 to 376 mg m -2 d -1 for CO 2 , N 2 O, and CH 4 , respectively. Results of the 3-yr field study demonstrated strong seasonal variability associated with GHG emissions. Nutrient source had no effect on soil CO 2 and CH 4 emissions, but annual and cumulative (3-yr) N 2 O emissions increased with biosolids (8 kg N 2 O ha -1  yr -1 ) compared with inorganic fertilizer (5 kg N 2 O ha -1  yr -1 ) application. Data suggested that environmental conditions played a more important role on GHG fluxes than nutrient additions. Biochar reduced CO 2 emissions modestly (<9%) but had no effects on N 2 O and CH 4 emissions., (© 2020 The Authors. Journal of Environmental Quality © 2020 American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America.)

Despite the numerous benefits of biosolids, concerns over nutrient losses restrict the extent to which biosolids can be beneficially reused. We evaluated the effectiveness of biochar in controlling the lability of nutrients in agricultural land. This study was designed to investigate the potential impacts of co-applying biochar with biosolids or inorganic fertilizer on N and P leaching losses. A companion paper focuses on greenhouse gas responses. Nutrients were surface applied as biosolids (aerobically digested Class B) and inorganic fertilizer (ammonium nitrate and triple superphosphate) to an established perennial pasture at equivalent annual rates typical of field practices. Biochar was applied at an annual rate of 20 Mg ha -1 . Leachate N and P were monitored using passive-capillary drainage lysimeters. Results demonstrated significant temporal variability in leachate N and P, with larger pulses generally occurring during periods of high water table levels or after intensive rainfall. Inorganic fertilizer generally resulted in greater leachate N and P losses than biosolids. No differences in leachate N and P losses between biosolids and control were observed. Approximately 1% of applied N was lost via leaching from biosolids treatments vs. 16% for inorganic fertilizer. Regardless of the P source, negligible (0.1-0.2% of applied P), cumulative P leaching occurred during the 3-yr study. Biochar had no effect on P leaching but reduced N leaching from treatments receiving inorganic fertilizer by 60%. Prudent nutrient management is possible even on biosolids-amended Spodosols with high water tables., (© 2020 The Authors. Journal of Environmental Quality © 2020 American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America.)

Commercial producers of containerized ornamental plants almost exclusively use soilless media as the substrate for growing the plants. Soilless media are composed primarily of organic materials as opposed to mineral soils. Significant amounts of pesticides can leach from pots containing soilless media to which pesticides have been added as drenches or top-dressings. One of the goals of this project was to identify whether individual components comprising soilless media have differing affinities for the pesticides acephate, imidacloprid, metalaxyl, and plant growth regulator paclobutrazol. One-point 24 h equilibrium sorption assays were conducted to characterize sorption of the pesticides to sand, perlite, vermiculite, coir, peat, pine bark, and aluminum-water treatment residuals (Al-WTRs). Five-point isotherms were then constructed for the more sorptive peat and pine bark substrate components, and for the Al-WTRs. Results indicated significant differences in pesticide behavior with each substrate. Sorption of acephate to most of the substrate components was relatively low, comprising 21-31% of the initial amounts for soilless media components and 63% in Al-WTRs. Al-WTRs were highly sorptive for imidacloprid as evidenced by a partition coefficient of K F = 3275.4 L kg -1 . Pine bark was the most sorptive for metalaxyl-M with a measured K F = 195.0 L kg -1 . Peat had the highest affinity for paclobutrazol ( K F = 398.4 L kg -1 ). These results indicate that none of component of soilless media has a universally high attraction for all of the pesticides studied., Competing Interests: The authors declare no competing financial interest., (Copyright © 2019 American Chemical Society.)

Recent evidence suggests an upward trend in surface water phosphorus (P) concentrations in many segments of Florida, including the upper basin of the St. Johns River, a region that currently receives about two-thirds of the state Class B biosolids land application. Concerns about water quality in this area are encouraging reexamination of the regulations governing biosolids programs. The objectives of this study were (i) to identify and thoroughly characterize the main biosolids sources routinely applied in the region, and (ii) to evaluate runoff and leachate N and P losses from a typical Florida Spodosol amended with biosolids or commercial inorganic fertilizer. Biosolids and inorganic fertilizer were surface applied uniformly at a rate equivalent to ∼114 kg P ha, which corresponded to a typical P load associated with nitrogen (N)-based biosolids application. Soluble reactive P (SRP) was the predominant form of P lost in runoff and leachate. Inorganic P fertilizer increased flow-weighted runoff total P concentrations nearly 60-fold relative to control treatment (0.4 vs. 22 mg P L for control and fertilizer treatments, respectively). With exception of biological P removal (BPR) biosolids, all other tested biosolids yielded flow-weighted runoff P concentrations similar to untreated soils. Cumulative P and N losses (as a percentage of P and N applied) were greater from commercial inorganic fertilizer (∼38% of P and 46% of N) than any biosolids source (3% of P and 6% of N). Results demonstrate the value of water-extractable P (WEP) as an indicator of biosolids P loss potential., (© 2019 The Author(s). Re-use requires permission from the publisher.)

Concerns about the negative impacts of crop biomass removal on soil ecological functions have led to questioning the long-term sustainability of bioenergy production. To offset this potential negative impact, use of organic C rich by-products from the bioenergy industries have been proposed as a means to replenish soil C in degraded soils. However, the impact of these by-products application on soil carbon dynamics is not fully understood. We measured biogeochemical changes in soil organic C following a three-year field application of two by-products, biochar (BC) and fermentation-by product (FBP), of bioenergy industry processes in an elephant grass [Pennisetum purpureum (L.) Schum.] field. There was a significant increase in overall soil organic C (SOC) observed in BC (270%) treated plots, however the higher labile SOC (51%) content was present in FBP treated plots. Solid-state 13 C NMR spectroscopy further revealed increased aromatic and alkyl groups in BC amended soils which lend to its significantly higher hydrophobicity index, HI (2.13) compared with FBP amended soils (HI = 0.8). Initial biogeochemical responses of amended soils to drought conditions were also investigated during a short-term experiment with drying and rewetting of soils. Increased concentrations of extractable C and higher stimulation of microbial activities (respiration and enzyme activities) in FBP amended soils were measured. Overall, our results reveal different impacts of the two soil amendments, where FBP soil application can affect the labile SOC availability, and stimulate rapid microbial response in drought affected soils, and biochar soil application lowers the labile SOC and microbial stimulation facilitating C sequestration over time., (Copyright © 2018 Elsevier B.V. All rights reserved.)

A field experiment was conducted from 2005 to 2008 in Fulton County, Western Illinois with biosolids from conventional wastewater treatment applied as corn fertilizer in a series of P rates (0, 163, 325, 488, 650 kg P ha(-1)) along with commercial P fertilizer - triple superphosphate P (TSP) as reference to assess biosolids-P plant availability and potential loss to waterbodies through runoff. Air-dried biosolids and TSP were incorporated into surface soil at end of 2005, and corn (Zea mays) was planted for three consecutive years (2006-2008). Concentrations of soil extractable P except for Mehlich-3 P were always lower in the biosolids than TSP treatments at the same P rates. The soil potentially available P in water extractable P (WEP) and Olsen P derived from biosolids-P estimated by the exponential depletion model was 2-4% and 15-24% of total P in the applied biosolids, respectively. The residence time of biosolids-induced WEP and Olsen P in Midwest soil under annual corn cropping was 5 and 2 years, respectively. Corn tissue analysis showed lower increase in P concentration by biosolids-P than TSP. The elevation rate of soluble reactive P (SRP) concentration in simulated runoff was less by biosolids than TSP. Based on the data in this study, the plant availability and environmental risk of biosolids-P are lower than those of TSP in the Midwest soil, thus use of biosolids as P nutrient for corn would not cause a major impairment to water sources even P applied through biosolids was not completely used by annual crop., (Published by Elsevier Ltd.)

Endocrine-disrupting chemicals (EDCs) occur in reclaimed water (RW), which may serve as an exposure source for humans. The presence of EDCs in RW used to irrigate turf and in nearby water-retention ponds was determined. In addition, the total dislodgeable mass of each EDC was determined after irrigation (using RW) to simulate exposure of a 3-year-child playing in turf grass recently irrigated with RW. Five EDCs (estrone, 17β-estradiol, 17α-ethynylestradiol, bisphenol A, and 4-n-nonylphenol) were quantified in 28 samples of RWs (wastewater-treatment plant effluents) and 88 samples from residential surface water-retention ponds. St. Augustine variety of turf grass was irrigated with spiked RW to study dislodgement of the five EDCs overtime using a drag-sled method. Grass clippings were analyzed to relate masses of EDC on grass with masses dislodged. EDCs were detected in both RW and ponds at ng/L concentrations. Maximum EDC masses were dislodged immediately after irrigation. Dislodged masses of estrone and 17β-estradiol are two separate EDCs, 17β-estradiol and 17α-ethynylestradiol decreased rapidly and were lower than detection limits 4 h after application. Dislodged bisphenol-A and nonylphenol decreased more slowly but were not detected 6 h after application. Avoiding contact with recently irrigated turf grass should decrease the risks of exposure to these EDCs.

Phosphorus (P) is required to maintain healthy, high-quality, warm-season turf. However, excessive P applications to soils with poor P retention capabilities may lead to leaching losses to groundwater. This field study was conducted to determine the maximum P fertilizer application rate to (Walt.) [Kuntze] 'Floratam' St. Augustinegrass (St. Augustinegrass) and 'Empire' zoysiagrass (zoysiagrass) below which P leaching is minimized. Five P levels ranging from 0 to 5.0 g P m yr were surface applied as triple superphosphate. Turf was established on an uncoated, low-P sand with negligible P retention capacity. Leaf and root growth, tissue P concentration, soil P concentration, soil P saturation, leachate volume, and orthophosphate (P) concentration in leachates were measured. Mehlich 1-extractable soil P (M1-P) and soil P saturation ratio (PSR) increased with time as the P rate increased. Lower M1-P and PSR values were measured with St. Augustinegrass, which absorbed more P than did zoysiagrass. The root system of St. Augustinegrass was larger and deeper compared with zoysiagrass, promoting greater P uptake and less P leaching. If tissue analysis indicates that P fertilization is required and the soil has the capacity to retain additional P, application of 0.8 g P m yr to zoysiagrass and 1.07 g P m yr to St. Augustinegrass is appropriate and does not result in increased P leaching., (Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.)

Triclocarban (TCC) is monitored under the USEPA High Production Volume (HPV) chemical program and is predominantly used as the active ingredient in select antibacterial bar soaps and other personal care products. The compound commonly occurs at parts-per-million concentrations in processed wastewater treatment residuals (i.e. biosolids), which are frequently land-applied as fertilizers and soil conditioners. Human and ecological risk assessment parameters measured by the authors in previous studies were integrated with existing data to perform a two-tiered human health and ecological risk assessment of land-applied biosolids-borne TCC. The 14 exposure pathways identified in the Part 503 Biosolids Rule were expanded, and conservative screening-level hazard quotients (HQ values) were first calculated to estimate risk to humans and a variety of terrestrial and aquatic organisms (Tier 1). The majority of biosolids-borne TCC exposure pathways resulted in no screening-level HQ values indicative of significant risks to exposed organisms (including humans), even under worst-case land application scenarios. The two pathways for which the conservative screening-level HQ values exceeded one (i.e. Pathway 10: biosolids➔soil➔soil organism➔predator, and Pathway 16: biosolids➔soil➔surface water➔aquatic organism) were then reexamined using modified parameters and scenarios (Tier 2). Adjusted HQ values remained greater than one for Exposure Pathway 10, with the exception of the final adjusted HQ values under a one-time 5 Mg ha(-1) (agronomic) biosolids loading rate scenario for the American woodcock (Scolopax minor) and short-tailed shrew (Blarina brevicauda). Results were used to prioritize recommendations for future biosolids-borne TCC research, which include additional measurements of toxicological effects and TCC concentrations in environmental matrices at the field level., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Triclosan (TCS) is an antimicrobial compound commonly found in biosolids. Thus, plants grown in biosolids-amended soil may be exposed to TCS. We evaluated the plant toxicity and accumulation potential of biosolids-borne TCS in two vegetables (lettuce and radish) and a pasture grass (bahia grass). Vegetables were grown in growth chambers and grass in a greenhouse. Biosolids-amended soil had TCS concentrations of 0.99, 5.9, and 11 mg/kg amended soil. These TCS concentrations represent typical biosolids containing concentrations of 16 mg TCS/kg applied at agronomic rates for 6 to 70 consecutive years, assuming no TCS loss. Plant yields (dry wt) were not reduced at any TCS concentration and the no observed effect concentration was 11 mg TCS/kg soil for all plants. Significantly greater TCS accumulated in the below-ground biomass than in the above-ground biomass. The average bioaccumulation factors (BAFs) were 0.43 ± 0.38 in radish root, 0.04 ± 0.04 in lettuce leaves, 0.004 ± 0.002 in radish leaves, and <0.001 in bahia grass. Soybean (grain) and corn (leaves) grown in our previous field study where soil TCS concentrations were lower (0.04-0.1 mg/kg) had BAF values of 0.06 to 0.16. Based on the data, we suggest a conservative first approximate BAF value of 0.4 for risk assessment in plants., (Copyright © 2012 SETAC.)

Triclosan (TCS) is a common constituent of personal care products and is frequently present in biosolids. Application of biosolids to land transfers significant amounts of TCS to soils. Because TCS is an antimicrobial and is toxic to some aquatic organisms, concern has arisen that TCS may adversely affect soil organisms. The objective of the present study was to investigate the toxicity and bioaccumulation potential of biosolids-borne TCS in terrestrial micro- and macro-organisms (earthworms). Studies were conducted in two biosolids-amended soils (sand, silty clay loam), following U.S. Environmental Protection Agency (U.S. EPA) guidelines. At the concentrations tested herein, microbial toxicity tests suggested no adverse effects of TCS on microbial respiration, ammonification, and nitrification. The no observed effect concentration for TCS for microbial processes was 10 mg/kg soil. Earthworm subchronic toxicity tests showed that biosolids-borne TCS was not toxic to earthworms at the concentrations tested herein. The estimated TCS earthworm lethal concentration (LC50) was greater than 1 mg/kg soil. Greater TCS accumulation was observed in earthworms incubated in a silty clay loam soil (bioaccumulation factor [BAF] = 12 ± 3.1) than in a sand (BAF = 6.5 ± 0.84). Field-collected earthworms had a significantly smaller BAF value (4.3 ± 0.7) than our laboratory values (6.5-12.0). The BAF values varied significantly with exposure conditions (e.g., soil characteristics, laboratory vs field conditions); however, a value of 10 represents a reasonable first approximation for risk assessment purposes., (Copyright © 2011 SETAC.)

Land application of biosolids can constitute an important source of triclosan (TCS) input to soils, with uncertain effects. Several studies have investigated the degradation potential of TCS in biosolids-amended soils, but the results vary widely. We conducted a laboratory degradation study by mixing biosolids spiked with [¹⁴C]-TCS (final concentration = 40 mg/kg) with Immokalee fine sand and Ashkum silty clay loam soils at an agronomic application rate (22 Mg/ha). Biosolids-amended soils were aerobically incubated in biotic and inhibited conditions for 18 weeks. Subsamples removed at 0, 2, 4, 6, 9, 12, 15, and 18 weeks were sequentially extracted with an operationally defined extraction scheme to determine labile and nonlabile TCS fractions. Over the 18-week incubation, the proportion of [¹⁴C] in the nonlabile fraction increased and the labile fraction decreased, suggesting decreasing availability to biota. Partitioning of TCS into labile and nonlabile fractions depended on soil characteristics. Less than 0.5% of [¹⁴C]-TCS was mineralized to carbon dioxide (¹⁴CO₂) in both soils and all treatments. A degradation metabolite, methyl triclosan (Me-TCS), was identified in both soils only in the biotic treatment, and increased in concentration over time. Even under biotic conditions, biosolids-borne TCS is persistent, with a primary degradation (TCS to Me-TCS) half-life of 78 d in the silty clay loam and 421 d in the fine sand. A half-life of approximately 100 d would be a conservative first approximation of TCS half-life in biosolids-amended soils for risk estimation., (Copyright © 2011 SETAC.)

Rapid infiltration basins (RIBs) are effective tools for wastewater treatment and groundwater recharge, but continuous application of wastewater can increase soil P concentrations and subsequently impact groundwater quality. The objectives of this study were to (1) investigate the effects of reclaimed water infiltration rate and "age" of RIBs on soil P concentrations at various depths, and (2) estimate the degree (percentage) of sorption equilibrium reached between effluent P and soil attained during reclaimed water application to different RIBs. The study was conducted in four contrasting cells of a RIB system with up to a 25 year history of secondary wastewater application. Soil samples were collected from 0 to 300 cm depth at 30 cm intervals and analyzed for water extractable phosphorus (WEP) and oxalate extractable P, Al, and Fe concentrations. Water extractable P and P saturation ratio (PSR) values were generally greater in the cells receiving reclaimed water compared to control soils, suggesting that reclaimed water P application can increase soil P concentrations and the risk of P movement to greater depths. Differences between treatment and control samples were more evident in cells with longer histories of reclaimed water application due to greater P loading. Data also indicated considerable spatial variability in WEP concentrations and PSR values, especially within cells from RIBs characterized by fast infiltration rates. This occurs because wastewater-P flows through surface soils much faster than the minimum time required for sorption equilibrium to occur. Studies should be conducted to investigate soil P saturation at deeper depths to assess possible groundwater contamination.

Two aluminum water treatment residuals (Al-WTRs) from water treatment plants in Manatee County, FL and Punta Gorda, FL were evaluated as potential permeable reactive barrier (PRB) media to reduce groundwater phosphorus (P) losses. Short-term (<24h) P sorption kinetics and long-term P sorption capacity were determined using batch equilibration studies. Phosphorus desorption was characterized following P loadings of 10, 20, 30, 40 and >70 g kg(-1). Sorption and desorption studies were conducted on the <2.0mm material and three size fractions within the <2.0mm material. The effect of dissolved organic carbon (DOC) on P retention was determined by reacting Al-WTRs with P-spiked groundwater samples of varying initial DOC concentrations. Phosphorus sorption kinetics were rapid for all size fractions of both Al-WTRs (>98% P sorption effectiveness at shaking times ≥2 h). The effect of DOC was minimal at <150 mg DOCL(-1), but modest reductions (<22%) in P sorption effectiveness occurred at 587 mg DOC L(-1). The P sorption capacities of the Manatee and Punta Gorda Al-WTRs (<2.0mm) are ∼44 g kg(-1) and >75 g kg(-1), respectively, and the lifespan of an Al-WTR PRB is likely many decades. Desorption was minimal (<2% of the P sorbed) for cumulative P loadings <40 g kg(-l), but increased (<9% of the P sorbed) at cumulative P loads >70 g kg(-1). The <2.0mm Manatee and Punta Gorda Al-WTRs are regarded as ideal PRB media for P remediation., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Triclocarban (TCC) toxicity and bioaccumulation data are primarily limited to direct human and animal dermal exposures, animal ingestion exposures to neat and feed-spiked TCC, and/or aquatic organism exposures. Three non-human, terrestrial organism groups anticipated to be the most highly exposed to land-applied, biosolids-borne TCC are soil microbes, earthworms, and plants. The three ecological receptors are expected to be at particular risk due to unique modes of exposure (e.g. constant, direct contact with soil; uptake of amended soil and pore water), inherently greater sensitivity to environmental contaminants (e.g. increased body burdens, permeable membranes), and susceptibility to minute changes in the soil environment. The toxicities of biosolids-borne TCC to Eisenia fetida earthworms and soil microbial communities were characterized using adaptations of the USEPA Office of Prevention, Pesticides, and Toxic Substances (OPPTS) Guidelines 850.6200 (Earthworm Subchronic Toxicity Test) and 850.5100 (Soil Microbial Community Toxicity Test), respectively. The resultant calculated TCC LC50 value for E. fetida was 40 mg TCC kg amended fine sand(-1). Biosolids-borne TCC in an amended fine sand had no significant effect on soil microbial community respiration, ammonification, or nitrification. Bioaccumulation of biosolids-borne TCC by E. fetida and Paspulum notatum was measured to characterize potential biosolids-borne TCC movement through the food chain. Dry-weight TCC bioaccumulation factor (BAF) values in E. fetida and P. notatum ranged from 5.2-18 and 0.00041-0.007 (gsoil gtissue(-1)), respectively., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

Transport models that incorporate retention/release characteristics of organic compounds in soils and sediments typically assume that organic-carbon normalized partition coefficients (K(OC)) apply to all solid matrices and that the partitioning process is completely reversible. Partition coefficients (K(d)) (from which the K(OC) was calculated), and retention/release characteristics of triclocarban (TCC) and triclosan (TCS) in biosolids, soils, and biosolids-amended soils were determined. Four soils of different physicochemical properties amended with biosolids at 10 g/kg, together with unamended soils, and several biosolids were separately spiked with either [(14)C]TCC or [(14)C]TCS for the various determinations. The hysteresis coefficient values of the two compounds were consistently <1 in all three solid matrices, suggesting strong hysteresis. Multiple desorption steps (24 h each) over several days revealed incomplete desorption of the two compounds from all three solid matrices. The K(d) values determined in biosolids (log K(d) 3.34 +/- 0.13 for TCC and 3.76 +/- 0.39 for TCS) were greater than those determined in soils (log K(d) 1.71 +/- 0.09 for TCC and 2.25 +/- 0.26 for TCS) and biosolids-amended soils (log K(d)1.90 +/- 0.16 for TCC and 2.31 +/- 0.19 for TCS), however, the K(OC) values of all three solid matrices were similar (log K(OC) of 3.82 +/- 0.16 for TCC and 4.26 +/- 0.31 for TCS). Thus, it was concluded that a single or a narrow range of K(OC) values for TCC and TCS may be appropriate to describe retention of the compounds in soils and sediments. However, models that assume complete reversibility of the retention/release processes of the compounds in soils and sediments may not adequately describe the retention/release characteristics of the compounds in soils and sediments, especially when the chemicals are biosolids borne., (Copyright 2010 SETAC.)

Triclocarban (TCC) is an active ingredient in antibacterial bar soaps, a common constituent of domestic wastewater, and the subject of recent criticism by consumer advocate groups and academic researchers alike. Activated sludge treatment readily removes TCC from the liquid waste stream and concentrates the antimicrobial in the solid fraction, which is often processed to produce biosolids intended for land application. Greater than half of the biosolids generated in the US are land-applied, resulting in a systematic release of biosolids-borne TCC into the terrestrial and, potentially, the aquatic environment. Multiple data gaps in the TCC literature (including basic physicochemical properties and biosolids concentrations) prevent an accurate, quantitative risk assessment of biosolids-borne TCC. We utilized the USEPA Office of Prevention, Pesticides, and Toxic Substances (OPPTS) harmonized test guidelines to measure TCC solubility and log K(ow) values as 0.045 mg L(-1) and 3.5, respectively. The measured physicochemical 2 properties differed from computer model predictions. The mean concentration of TCC in 23 biosolids representative of multiple sludge processing methods was 19+/-11 mg kg(-1)., (Copyright (c) 2010 Elsevier B.V. All rights reserved.)

Triclocarban (TCC) is an antibacterial compound commonly detected in biosolids at parts-per-million concentrations. Approximately half of the biosolids produced in the United States are land-applied, resulting in a systematic release of TCC into the soil environment. The extent of biosolids-borne TCC environmental transport and potential human/ecological exposures will be greatly affected by its bioavailability and the rate of degradation in amended soils. To investigate these factors, radiolabeled TCC ((14)C-TCC) was incorporated into anaerobically digested biosolids, amended to two soils, and incubated under aerobic conditions. The evolution of (14)CO2 (biodegradation) and changes in chemical extractability (bioavailability) was measured over time. Water extractable TCC over the study period was low and significantly decreased over the first 3 weeks of the study (from 14% to 4% in a fine sand soil and from 3 to <1% in a silty clay loam soil). Mineralization (i.e. ultimate degradation), as measured by evolution of (14)CO(2), was <4% over 7.5 months. Methanol extracts of the amended soils were analyzed by radiolabel thin-layer chromatography (RAD-TLC), but no intermediate degradation products were detected. Approximately 20% and 50% of the radioactivity in the amended fine sand and silty clay loam soils, respectively, was converted to bound residue as measured by solids combustion. These results indicate that biosolids-borne TCC becomes less bioavailable over time and biodegrades at a very slow rate., (Copyright (c) 2010 Elsevier B.V. All rights reserved.)

Land application of drinking-water treatment residuals (WTR) has been shown to control excess soil soluble P and can reduce off-site P losses to surface and ground water. To our knowledge, no field study has directly evaluated the impacts of land application of WTRs on ground water quality. We monitored the effects of three organic sources of P (poultry manure, Boca Raton biosolids, Pompano biosolids) or triple superphosphate co-applied with an aluminum-based WTR (Al-WTR) on soil and ground water P and Al concentrations under natural field conditions for 20 mo in a soil with limited P sorption capacity. The P sources were applied at two rates (based on P or nitrogen [N] requirement of bahiagrass) with or without Al-WTR amendment and replicated three times. Without WTR application, applied P sources increased surface soil soluble P concentrations regardless of the P source or application rate. Co-applying the P sources with Al-WTR prevented increases in surface soil soluble P concentrations and reduced P losses to shallow ground water. Total dissolved P and orthophosphate concentrations of shallow well ground water of the N-based treatments were greater (>0.9 and 0.3 mg L(-1), respectively) in the absence than in the presence ( approximately 0.6 and 0.2 mg L(-1), respectively) of Al-WTR. The P-based application rate did not increase ground water P concentrations relative to background concentrations. Notwithstanding, Al-WTR amendment decreased ground water P concentrations from soil receiving treatments with P-based application rates. Ground water total dissolved Al concentrations were unaffected by soil Al-WTR application. We conclude that, at least for the study period, Al-WTR can be safely used to reduce P leaching into ground water without increasing the Al concentration of ground water.

Several studies have shown that drinking-water treatment residuals (WTR) could be used to control mobility of excess phosphorus (P) and other oxyanions in poorly sorbing soils. Presently, only "aged" WTRs (those left, or manipulated, to dewater) are land applied. However, if demand for WTRs increase in the near future, freshly-generated WTRs could be considered for land application. To our knowledge, few studies have examined the reactivity and equilibration time of freshly-generated alum-based WTR (Al-WTR). A laboratory thermal incubation study was, therefore, conducted to determine various extractable Al forms in Al-WTR as a function of WTR "age", and the time required for freshly generated Al-WTR to stabilize. Freshly-generated Al-WTR samples were collected directly from the discharge pumps of a drinking-water treatment plant, and thermally incubated at 52 degrees C, either with or without moisture control, for < or = 24 wk. Additional dewatered Al-WTR samples of various ages (2 wk- to 2 y old) were also included in the study. Various methods of extracting Al [total-, oxalate (200 and 5 mM), and Mehlich 1 extractants] were utilized to assess Al extractability over time. Freshly-generated Al-WTR samples were potentially more reactive (as reflected in greater 5 mM oxalate extractable Al concentration) than dewatered Al-WTR samples stockpiled for > or = 6 mo. Aluminum reactivity of the freshly-generated Al-WTR decreased with time. At least 6 wk of thermal incubation (corresponding to > or = 6 mo of field drying) was required to stabilize the most reactive Al form (5mM oxalate extractable Al concentration) of the Al-WTR. Although no adverse Al-WTR effects have been reported on plants and grazing animals (apparently because of low availability of free Al(3+) in Al-WTR), land application of freshly-generated Al-WTRs (at least, those with similar physicochemical characteristics as the one utilized for the study) should be avoided.

Water treatment residuals (WTR) can reduce runoff P loss and surface co-application of P-sources and WTR is a practical way of land applying the residuals. In a rainfall simulation study, we evaluated the effects of surface co-applied P-sources and an Al-WTR on runoff and leacheate bioavailable P (BAP) losses from a Florida sand. Four P-sources, namely poultry manure, Boca Raton biosolids (high water-soluble P), Pompano biosolids (moderate water-soluble P), and triple super phosphate (TSP) were surface applied at 56 and 224 kg P ha(-1) (by weight) to represent low and high soil P loads typical of P- and N-based amendments rates. The treatments further received surface applied WTR at 0 or 10 g WTR kg(-1) soil. BAP loss masses were greater in leachate (16.4-536 mg) than in runoff (0.91-46 mg), but were reduced in runoff and leachate by surface applied WTR. Masses of total BAP lost in the presence of surface applied WTR were less than approximately 75% of BAP losses in the absence of WTR. Total BAP losses from each of the organic sources applied at N-based rates were not greater than P loss from TSP applied at a P-based rate. The BAP loss at the N-based rate of moderate water-soluble P-source (Pompano biosolids) was not greater than BAP losses at the P-based rates of other organic sources tested. The hazards of excess P from applying organic P-sources at N-based rates are not greater than observed at P-based rates of mineral fertilizer. Results suggest that management of the environmental P hazards associated with N-based rates of organic materials in Florida sands is possible by either applying P-sources with WTR or using a moderate water-soluble P-source.

Communities around the world face increasingly severe fresh water supply shortages, largely due to expanding populations and associated food supply, economic development, and health issues. Intentional reuse of degraded waters (e.g., wastewater effluents, irrigation return flows, concentrated animal feeding operations [CAFO] effluents, stormwater, and graywater) as substitutes for fresh waters could be one solution to the challenge. We describe the various degraded water types and reuse options and limitations and restrictions to their use. Emphasis is given to reuse scenarios involving degraded water applications to soil. The potential for degraded water reuse is enormous, but significant barriers exist to widespread adoption. Barriers include research questions (some addressable by traditional soil science approaches, but others requiring novel techniques and advanced instrumentation), the lack of unifying national regulations, and public acceptance. Educational programs, based on hard science developed from long-term field studies, are imperative to convince the public and elected officials of the wisdom and safety of reusing degraded waters.

Incorporating applied phosphorus (P) sources can reduce P runoff losses and is a recommended best management practice. However, in soils with low P retention capacities, leaching can be a major mechanism for off-site P loss, and the P-source application method (surface or incorporation) may not significantly affect the total amount of off-site P loss. We utilized simulated rainfall protocols to investigate effects of P-source characteristics and application methods on the forms and amounts of P losses from six P sources, including five biosolids materials produced and/or marketed in Florida, and one inorganic fertilizer (triple superphosphate). A typical Florida Spodosol (Immokalee fine sand; sandy, siliceous, hyperthermic Arenic Alaquods) was used for the study, to which the P sources were each applied at a rate of 224 kg P ha(-1) (approximately the P rate associated with N-based biosolids applications). The P sources were either surface-applied to the soil or incorporated into the soil to a depth of 5 cm. Amended soils were subjected to three simulated rainfall events, at 1-d intervals. Runoff and leachate were collected after each rainfall event and analyzed for P losses in the form of soluble reactive P (SRP), total dissolved P (TDP), total P (TP), and bioavailable P (BAP) (in runoff only). Cumulative masses (runoff + leachate for the three rainfall events) of P losses from all the P sources were similar, whether the amendments were surface-applied or incorporated into the soil. The solubility of the amendment, rather than application method, largely determines the P loss potential in poorly P-sorbing Florida Spodosols.

Most regulations governing biosolids land application do not consider that phosphorus (P) solubility can vary widely among biosolids. Current regulations typically group all biosolids together in one category or group biosolids together with manures. Research has shown that not all biosolids have the same potential to affect the environment when land applied, but the database is limited. The purpose of this study was to characterize P release from several biosolids produced and/or marketed in Florida. A small soil column dynamic laboratory incubation was conducted to assess P release potential. Eleven biosolids and a mineral fertilizer (triple super phosphate) were individually mixed with a typical low-P sorbing Florida soil (Immokalee fine sand) at 56 and 224 kg P ha(-1). Columns were periodically leached over 5.5 mo to attain 60 mL (1/2 pore volume) of drainage in each leaching. Soluble reactive P was determined and summed over the eight leachings to represent total P source release. Cumulative P release (as a percentage of P applied) was greatest from biological P removal (BPR) and BPR-like biosolids and least from heat-dried materials. Phosphorus release from biosolids depends on biosolids treatment type (digestion) and P chemistry, suggesting that biosolids regulations must account for differences in P lability to accurately gauge environmental risk.

Florida Spodosols are sandy, inherently low in Fe- and Al-based minerals, and sorb phosphorus (P) poorly. We evaluated runoff and leachate P losses from a typical Florida Spodosol amended with biosolids and triple superphosphate (TSP). Phosphorus losses were evaluated with traditional indoor rainfall simulations but used a double-deck box arrangement that allowed leaching and runoff to be determined simultaneously. Biosolids (Lakeland, OCUD, Milorganite, and Disney) represented contrasting values of total P, percent water-extractable P (PWEP), and percentage of solids. All P sources were surface applied at 224 kg P ha(-1), representing a soil P rate typical of N-based biosolids application. All biosolids-P sources lost less P than TSP, and leachate-P losses generally dominated. For Lakeland-amended soil, bioavailable P (BAP) was mainly lost by runoff (81% of total BAP losses). This behavior was due to surface sealing and drying after application of the slurry (31 g kg(-1) solids) material. For all other P sources, BAP losses in leachate were much greater than in runoff, representing 94% of total BAP losses for TSP, 80% for Milorganite, 72% for Disney, and 69% for OCUD treatments. Phosphorus leaching can be extreme and represents a great concern in many coarse-textured Florida Spodosols and other coastal plain soils with low P-sorption capacities. The PWEP values of P sources were significantly correlated with total P and BAP losses in runoff and leachate. The PWEP of a source can serve as a good indicator of potential P loss when amended to sandy soils with low P-retention capacities.

Water treatment residuals (WTR) are useful soil amendments to control excessive soluble phosphorus (P) in soils, but indiscriminate additions can result in inadequate control or excessive immobilization of soluble P, leading to crop deficiencies. We evaluated the influence of application rates of an Al-WTR and various P-sources on plant yields, tissue P concentrations, and P uptake and attempted to identify a basis for determining WTR application rates. Bahiagrass (paspalum notatum Fluggae) was grown in a P-deficient soil amended with four P-sources at two application levels (N- and P-based rates) and three WTR rates (0, 10, and 25 g kg(-1) oven dry basis) in a glasshouse pot experiment. The glasshouse results were compared with data from a 2-yr field experiment with similar treatments that were surface applied to an established bahiagrass. Soil P storage capacity (SPSC) values increased with application rate of WTR, and the increase varied with sources of P applied. Soil soluble P concentrations increased as SPSC was reduced, and a change point was identified at 0 mg kg(-1) SPSC in the glasshouse and the field studies. A change point was identified in the bahiagrass yields at a tissue P concentration of 2.0 g kg(-1), corresponding to zero SPSC. Zero SPSC was shown to be an agronomic threshold above which yields and P concentrations of plants declined and below which there is little or no yield response to increased plant P concentrations. Applying P-sources at N-based rates, along with WTR sufficient to give SPSC value of 0 mg kg(-1) SPSC, enhanced the environmental benefits (reduced P loss potential) without negative agronomic impacts.

Time constraints associated with conducting long-term (>20 yr) field experiments to test the stability of drinking water treatment residuals (WTR) sorbed phosphorus (P) inhibit improved understanding of the fate of sorbed P in soils when important soil properties (e.g., pH) change. We used artificially aged samples to evaluate aging and pH effects on lability of WTR-immobilized P. Artificial aging was achieved through incubation at elevated temperatures (46 or 70 degrees C) for 4.5 yr, and through repeated wetting and drying for 2 yr. Using a modified isotopic ((32)P) dilution technique, coupled with a stepwise acidification procedure, we monitored changes in labile P concentrations over time. This technique enabled evaluation of the effect of pH on the lability of WTR-immobilized P. Within the pH range of 4 to 7, WTR amendment, coupled with artificial aging, ultimately reduced labile P concentrations by > or = 75% relative to the control (no-WTR) samples. Soil samples with different physicochemical properties from two 7.5-yr-old, one-time WTR-amended field sites were utilized to validate the trends observed with the artificially aged samples. Despite the differences in physicochemical properties among the three (two field-aged and one artificially aged) soil samples, similar trends of aging and pH effects on lability of WTR-immobilized P were observed. Labile P concentrations of the WTR-amended field-aged samples of the two sites decreased 6 mo after WTR amendment and the reduction persisted for 7.5 yr, ultimately resulting in > or = 70% reduction, compared to the control plots. We conclude that WTR application is capable of reducing labile P concentration in P-impacted soils, doing so for a long time, and that within the commonly encountered range of pH values for agricultural soils WTR-immobilized P should be stable.

Excessive soluble P in runoff is a common cause of eutrophication in fresh waters. Evidence indicates that drinking water treatment residuals (WTRs) can reduce soluble P concentrations in P-impacted soils in the short term (days to weeks). The long-term (years) stability of WTR-immobilized P has been inferred, but validating field data are scarce. This research was undertaken at two Michigan field sites with a history of heavy manure applications to study the longevity of alum-based WTR (Al-WTR) effects on P solubility over time (7.5 yr). At both sites, amendment with Al-WTR reduced water-soluble P (WSP) concentration by >or=60% as compared to the control plots, and the Al-WTR-immobilized P (WTR-P) remained stable 7.5 yr after Al-WTR application. Rainfall simulation techniques were utilized to investigate P losses in runoff and leachate from surface soils of the field sites at 7.5 yr after Al-WTR application. At both sites, amendment with Al-WTR reduced dissolved P and bioavailable P (BAP) by >50% as compared to the control plots, showing that WTR-immobilized P remained nonlabile even 7.5 yr after Al-WTR amendment. Thus, WTR-immobilized P would not be expected to dissolve into runoff and leachate to contaminate surface waters or groundwater. Even if WTR-P is lost via erosion to surface waters, the bioavailability of the immobilized P should be minimal and should have negligible effects on water quality. However, if the WTR particles are destroyed by extreme conditions, P loss to water could pose a eutrophication risk.

Sequential extractions of metals can be useful to study metal distributions in various soil fractions. Although several sequential extraction procedures have been suggested in the literature, most were developed for temperate soils and may not be suitable for tropical soils with high contents of Mn and Fe oxides. The objective of this study was to develop a sequential fractionation procedure for Cu and Zn in tropical soils. Extractions were performed on surface (0-20 cm) samples of ten representative soils of Sao Paulo State, Brazil. Chemically reactive Mn forms were satisfactorily assessed by the new modified procedure. Amorphous and crystalline Fe oxides were more selectively extracted in a new two-step extraction. Soil-born Zn and Cu were primarily associated with recalcitrant soil fractions. The proposed procedure provided more detailed information on metal distribution in tropical soils and better characterization of the various components of the soil matrix. The new procedure is expected to be an important tool for predicting the potential effects of environmental changes and land application of metals on the redistribution of chemical forms of metals in tropical soils.

Long-term depositions of animal manures affect P dynamics in soils and can pose environmental risks associated with P losses. Laboratory studies were done on P solubility characteristics in a manure-impacted Immokalee soil (sandy, siliceous, hyperthermic Arenic Alaquod) and the effectiveness of water treatment residual (WTR) in controlling P leaching. Soil samples with contrasting initial total P concentrations were prepared by mixing samples of a manure-impacted surface A horizon and a minimally P-impacted E horizon. Effects of mixing various ratios of A and E horizons, WTR rates (0, 25, 50, and 100 g kg(-1)), and depths of WTR incorporation (mixed throughout the soil column or partially incorporated) on P leaching were determined. Between 62 and 77% of total P was released from the soil mixes by successive water extractions, suggesting a considerable buffering capacity of this manure-impacted soil to resupply P into solution. Between 224 and 408 mg kg(-1) P were leached during the 36-wk leaching period in the absence of WTR. Mixing WTRs with soil reduced soluble P concentration in leachates by as much as 99.8% compared with samples without WTR. Thoroughly mixing WTR with the entire soil column (15 cm) was much more efficient than mixing WTR with only the top 7.5 cm of soil. Calcium- and Mg-P forms appear to control P release in soils without WTR, whereas sorption-desorption reactions probably determine P leaching in WTR-treated samples. Soil P distribution in various chemical forms was affected by WTR additions. Data suggest that WTR-immobilized P is stable in the long term.

Runoff losses of dissolved and particulate phosphorus (P) may occur when rainfall interacts with manures and biosolids spread on the soil surface. This study compared P levels in runoff losses from soils amended with several P sources, including 10 different biosolids and dairy manure (untreated and treated with Fe or Al salts). Simulated rainfall (71 mm h(-1)) was applied until 30 min of runoff was collected from soil boxes (100 x 20 x 5 cm) to which the P sources were surfaced applied. Materials were applied to achieve a common plant available nitrogen (PAN) rate of 134 kg PAN ha(-1), resulting in total P loading rates from 122 (dairy manure) to 555 (Syracuse N-Viro biosolids) kg P ha(-1). Two biosolids produced via biological phosphorus removal (BPR) wastewater treatment resulted in the highest total dissolved phosphorus (13-21.5 mg TDP L(-1)) and total phosphorus (18-27.5 mg TP L(-1)) concentrations in runoff, followed by untreated dairy manure that had statistically (p = 0.05) higher TDP (8.5 mg L(-1)) and TP (10.9 mg L(-1)) than seven of the eight other biosolids. The TDP and TP in runoff from six biosolids did not differ significantly from unamended control (0.03 mg TDP L(-1); 0.95 mg TP L(-1)). Highest runoff TDP was associated with P sources low in Al and Fe. Amending dairy manure with Al and Fe salts at 1:1 metal-to-P molar ratio reduced runoff TP to control levels. Runoff TDP and TP were not positively correlated to TP application rate unless modified by a weighting factor reflecting the relative solubility of the P source. This suggests site assessment indices should account for the differential solubility of the applied P source to accurately predict the risk of P loss from the wide variety of biosolids materials routinely land applied.

Iron (Fe) and aluminum (Al) hydroxides are highly reactive components in environmental processes, such as contaminant fate and transport. Phosphorus (P) sorption by these components can decrease environmental problems associated with excess accumulation of P in soils. The long-term stability of P sorbed by Fe/Al hydroxides is of major concern. Synthetic Fe and Al hydroxides coprecipitated with P (1:1 metal:P molar ratio) were incubated at 70 degrees C for 24 months to simulate natural long-term weathering processes that could influence the stability of sorbed P. Heat incubation (70 degrees C) of the untreated (no P) Al hydroxides resulted in drastic decreases (within the first month of incubation) in oxalate-Al extractability, specific surface area (SSA), and micropore volume with time. These changes were consistent with the formation of pseudoboehmite. Untreated Fe hydroxides showed no formation of crystalline components following heating (70 degrees C) for 24 months. Much smaller changes in oxalate-Al, P extractability, and SSA values were observed in the P-treated Al particles when compared with the untreated. Phosphorus treatment of both Fe and Al hydroxides stabilized the particle surfaces and prevented structural arrangements toward a long-range ordered phase. Slight reduction in SSA of the P-treated particles was related to dehydration phenomena during heating at 70 degrees C. Monitoring of physicochemical properties of the solids after heating at 70 degrees C for 2 years showed that sorbed P may be stable in the long-term. Understanding long term physicochemical properties may help engineers to optimize the Fe/Al hydroxides performance in several environmental/industrial applications.

Drinking-water treatment residuals (WTRs) are nonhazardous materials that can be obtained free-of-charge from drinking-water treatment plants to reduce soluble phosphorus (P) concentrations in poorly P sorbing soils. Phosphorus sorption capacities of WTRs can vary 1-2 orders of magnitude, on the basis of short-term equilibration times (up to 7 d), but studies dealing with long-term (weeks to months) P retention by WTRs are lacking. Properties that most affect long-term P sorption capacities are pertinent to the efficacy of WTRs as amendments to stabilize P in soils. This research addressed the long-term (up to 80 d) P sorption/desorption characteristics and kinetics for seven WTRs, including the influence of specific surface area (SSA), porosity, and total C content on the overall magnitude of P sorption by seven WTRs. The data confirm a strong but variable affinity for P by WTRs. Aluminum-based WTRs tended to have higher P sorption capacity than Fe-based WTRs. Phosphorus sorption with time was biphasic in nature for most samples and best fit to a second-order rate model. The P sorption rate dependency was strongly correlated with a hysteretic P desorption, consistent with kinetic limitations on P desorption from micropores. Oxalate-extractable Al + Fe concentrations of the WTRs did not effectively explain long-term (80 d) P sorption capacities of the WTRs. Micropore (CO2-based) SSAs were greater than BET-N2 SSAs for most WTRs, except those with the lowest (<80 g kg(-1)) total C content. There was a significant negative linear correlation between the total C content and the CO2/N2 SSA ratio. The data suggest that C in WTRs increases microporosity, but reduces P sorption per unit pore volume or surface area. Hence, variability in C content confounds direct relations among SSA, porosity, and P sorption. Total C, N2-based SSA, and CO2-based SSAs explained 82% of the variability in the long-term P sorption capacities of the WTRs. Prediction of long-term P sorption capacities for different WTRs may be achieved by taking into account the three proposed variables.

Man has land-applied societal nonhazardous wastes for centuries as a means of disposal and to improve the soil via the recycling of nutrients and the addition of organic matter. Nonhazardous wastes include a vast array of materials, including manures, biosolids, composts, wastewater effluents, food-processing wastes, industrial by-products; these are collectively referred to herein as residuals. Because of economic restraints and environmental concerns about land-filling and incineration, interest in land application continues to grow. A major lesson that has been learned, however, is that the traditional definition of land application that emphasizes applying residuals to land in a manner that protects human and animal health, safeguards soil and water resources, and maintains long-term ecosystem quality is incomplete unless the earning of public trust in the practices is included. This overview provides an introduction to a subset of papers and posters presented at the conference, "Sustainable Land Application," held in Orlando, FL, in January 2004. The USEPA, USDA, and multiple national and state organizations with interest in, and/or responsibilities for, ensuring the sustainability of the practice sponsored the conference. The overriding conference objectives were to highlight significant developments in land treatment theory and practice, and to identify future research needs to address critical gaps in the knowledge base that must be addressed to ensure sustainable land application of residuals.

Drinking-water treatment residuals (WTRs) can immobilize excess soil phosphorus (P), but little is known about the long-term P retention by WTRs. To evaluate the long-term P sorption characteristics of one Fe- and one Al-based WTR, physicochemical properties pertinent to time-dependency and hysteresis of P sorption were assessed. This study also investigated the P sorption mechanisms that could affect the long-term stability of sorbed P by WTRs. Phosphorus sorption kinetics by the WTRs exhibited a slow phase that followed an initial rapid phase, as typically occurs with metal hydroxides. Phosphorus sorption maxima for both Fe- and Al-based WTRs exceeded 9100 mg of P kg(-1) and required a greater specific surface area (SSA) than would be available based on BET-N2 calculations. Electron microprobe analyses of cross-sectional, P-treated particles showed three-dimensional P sorption by WTRs. Carbon dioxide gas sorption was greater than N2, suggesting steric restriction of N2 diffusion by narrow micropore openings. Phosphorus-treated Co2 SSAs were reduced by P treatment, suggesting P sorption by micropores (5-20 A). Mercury intrusion porosimetry indicated negligible macroporosity (pores > 500 A). Slow P sorption kinetics by WTRs may be explained by intraparticle P diffusion in micropores. Micropore-bound P should be stable and immobilized over long periods.

Phosphorus (P) has been recognized as one of the major limiting nutrients that are responsible for eutrophication of surface waters, worldwide. Efforts have been concentrated on reducing P loads reaching water bodies, via surface runoff and/or leaching through a soil profile. Use of drinking water treatment residuals (WTRs) is an emerging cost-effective practice to reduce soluble P in poorly P-sorbing soils or systems high in P. Literature suggests that WTRs have huge P sorption capacities. We hypothesized that P sorption would be limited by diffusional constraints imposed by the WTR particles. Selected chemical and physical (specific surface area, particle size distribution) characteristics of an iron-based WTR were measured. Sorption P isotherms at room temperature were constructed, and sorption kinetics were monitored. An intraparticle diffusion model was utilized to fit the kinetic data. Results showed that the WTR dramatically reduced soluble P, showing nonequilibrium characteristics, even after 80 d of reaction. Specific surface area (SSA) measured with CO2 gas was significantly greater than the traditional BET-N2 value (28 versus 3.5 m2 g(-1)), suggesting that a large amount of internal surfaces might be present in the WTR. The intraparticle P diffusion model was modified to include the wide particle size distribution of the WTR. The intraparticle diffusion model fitted the data well (r2 = 0.83). We calculated a maximum apparent P diffusion coefficient value of 4 x 10(-15) cm2 s(-1), which agrees with published values for intraparticle diffusion in microporous sorbents. This work may be useful for predicting long-term sorption characteristics of WTRs, since WTRs have been suggested as potential long-term immobilizers of sorbed P in P-sensitive ecosystems.

Efficient utilization of biosolids P for agronomic purposes requires accounting for differences in the phytoavailability of P in various biosolids. Greenhouse studies were conducted with a common pasture grass grown in two P-deficient soils amended with 12 biosolids and a commercial fertilizer (triple superphosphate, TSP) to quantify P uptake and to assess the relative phytoavailabilities of the P sources. Biosolids were grouped into three general categories of phytoavailability relative to TSP: high (> 75% of TSP), moderate (25-75% of TSP), and low (< 25% of TSP). Two biosolids, produced via biological phosphorus removal (BPR) processes, were in the high category, and mimicked fertilizer P with regard to P phytoavailability. Most biosolids produced by conventional wastewater and solids digestion and additional treatments like composting were in the moderate category. Also included in this category was a BPR that had been pelletized and another BPR supplemented with Al. The low category included biosolids containing greater than normal (> 50 g kg(-1)) total Fe and Al concentrations and processed to high (> 60%) solids content.

Phosphorus-based nutrient management will inevitably be required for land application of biosolids. Water-extractable phosphorus (WEP) in livestock manures is an indicator of phosphorus loss from agricultural watersheds and this study evaluated its use for biosolids. The WEP to total phosphorus percentage (PWEP) in 41 biosolids (representing a variety of wastewater and solids treatment processes) was compared to dairy and poultry manures and triple superphosphate fertilizer. The mean PWEP for conventionally treated and stabilized biosolids was 2.4%, which was significantly lower than inorganic fertilizer (85%), dairy manure (52%), and poultry manure (21%). Low biosolids PWEP is attributed to elevated aluminum and iron content from chemical additions during wastewater treatment and solids dewatering operations. Facilities using biological phosphorus removal had the highest mean biosolids PWEP (approximately 14%), whereas heat-dried biosolids had the lowest average PWEP (< approximately 0.5%). Paired samples of digested cake and the corresponding biosolids treated by processes to further reduce pathogens (i.e., thermal treatment, composting, and advanced alkaline stabilization) showed that these processes tended to reduce biosolids PWEP. Biosolids composition and processing mode exert a controlling influence on the potential for off-site phosphorus migration at land-application sites. Nutrient management policies for land-based recycling should account for the widely varying potential of organic amendments to cause soluble phosphorus losses in runoff and leaching.

Laboratory and greenhouse studies compared the ability of water treatment residuals (WTRs) to alter P solubility and leaching in Immokalee sandy soil (sandy, siliceous, hyperthermic Arenic Alaquod) amended with biosolids and triple superphosphate (TSP). Aluminum sulfate (Al-WTR) and ferric sulfate (Fe-WTR) coagulation residuals, a lime softening residual (Ca-WTR) produced during hardness removal, and pure hematite were examined. In equilibration studies, the ability to reduce soluble P followed the order Al-WTR > Ca-WTR = Fe-WTR >> hematite. Differences in the P-fixing capacity of the sesquioxide-dominated materials (Al-WTR, Fe-WTR, hematite) were attributed to their varying reactive Fe- and Al-hydrous oxide contents as measured by oxalate extraction. Leachate P was monitored from greenhouse columns where bahiagrass (Paspalum notatum Flugge) was grown on Immokalee soil amended with biosolids or TSP at an equivalent rate of 224 kg P ha(-1) and WTRs at 2.5% (56 Mg ha(-1)). In the absence of WTRs, 21% of TSP and 11% of Largo cake biosolids total phosphorus (PT) leached over 4 mo. With co-applied WTRs, losses from TSP columns were reduced to 3.5% (Fe-WTR), 2.5% (Ca-WTR), and <1% (Al-WTR) of applied P. For the Largo biosolids treatments all WTRs retarded downward P flux such that leachate P was not statistically different than for control (soil only) columns. The phosphorus saturation index (PSI = [Pox]/ [Al(ox) + Fe(ox)], where Pox, Al, and Fe(ox) are oxalate-extractable P, Al, and Fe, respectively) based on a simple oxalate extraction of the WTR and biosolids is potentially useful for determining WTR application rates for controlled reduction of P in drainage when biosolids are applied to low P-sorbing soils.

Increasing emphasis on phosphorus (P)-based nutrient management underscores the need to understand P behavior in soils amended with biosolids and manures. Laboratory and greenhouse column studies characterized P forms and leachability of eight biosolids products, chicken manure (CM), and commercial fertilizer (triple superphosphate, TSP). Bahiagrass (Paspalum notatum Flugge) was grown for 4 mo on two acid, P-deficient Florida sands, representing both moderate (Candler series: hyperthermic, uncoated Typic Quartzipsamments) and very low (Immokalee series: sandy, siliceous, hyperthermic Arenic Alaquods) P-sorbing capacities. Amendments were applied at 56 and 224 kg P(T) ha(-1), simulating P-based and N-based nutrient loadings, respectively. Column leachate P was dominantly inorganic and lower for biosolids P sources than TSP. For Candler soil, only TSP at the high P rate exhibited P leaching statistically greater (alpha = 0.05) than control (soil-only) columns. For the high P rate and low P-sorbing Immokalee soil, TSP and CM leached 21 and 3.0% of applied P, respectively. Leachate P for six biosolids was <1.0% of applied P and not statistically different from controls. Largo biosolids, generated from a biological P removal process, exhibited significantly greater leachate P in both cake and pelletized forms (11 and 2.5% of applied P, respectively) than other biosolids. Biosolids P leaching was correlated to the phosphorus saturation index (PSI = [Pox]/[Al(ox) + Fe(ox)]) based on oxalate extraction of the pre-applied biosolids. For hiosolids with PSI < or = approximately 1.1, no appreciable leaching occurred. Only Largo cake (PSI = 1.4) and pellets (PSI = 1.3) exhibited P leaching losses statistically greater than controls. The biosolids PSI appears useful for identifying biosolids with potential to enrich drainage P when applied to low P-sorbing soils.

An experiment was designed to assess the mineral status of 60 Angus yearling beef steers grazing bahiagrass pastures fertilized with large amounts of biosolids from three sources: Baltimore, MD; Tampa, FL; and Largo, FL. Biosolids were classified as exceptional quality and thus had no regulatory restrictions on loading rate. They differed primarily in concentration of Mo (12 to 56 mg/kg of DM). Residual treatments (biosolids applied only the previous year) for Baltimore biosolids were applied at 22.4 and 44.8 t/ha, and Tampa biosolids were either 16.8 or 33.6 t/ ha. The reapplied treatments (applied in consecutive years) for both Baltimore and Tampa sludges were applied at 22.4, 44.8, 16.8 , and 33.6 t/ha, respectively. The two Largo biosolids treatments were either 56 or 112 t/ha and were applied only in the 2nd yr. Liver biopsies and blood samples were collected on d 1, 95, and 180. Liver and plasma were analyzed for minerals and blood was analyzed for hemoglobin, hematocrit, and superoxide dismutase of polymorphonuclear neutrophils. Experimental animals were generally adequate in macromineral status and Co, Fe, and Mn throughout the experiment. Copper deficiency was evident based on the clinical signs of hair coat discoloration, very low plasma Cu at d 95, and the continuous decline in liver Cu over 180 d. A sharp decline in plasma Cu was observed for all treatments from d 1 to 95, after which Cu concentrations rebounded to normal concentrations (> 0.65 microg/mL) by d 180. Liver Mo was well below concentrations indicating toxicity (> 5.0 mg/kg). The steep decline in liver Cu over the first 95 d reflects the dietary Cu deficiency and the possibility of high forage S (0.26 to 0.52%) interfering with Cu metabolism. Biosolids application to bahiagrass pastures was not detrimental to mineral status except for declining Cu stores; however, the controls likewise declined, but to a lesser degree.

Legumes grown in biosolids-amended soils and then fed to ruminants can represent problematic sources of molybdenum (Mo), but few field data are available to quantify the risk. We used a set of fields amended to high cumulative biosolids Mo loads (>18 kg ha(-1)) over 27 yr to generate additional data. Soybean [Glycine max (L.) Merr.] was grown on 29 fields (pH values>6.8) amended to a wide range of soil Mo loads. Soybean grain harvested from each field was analyzed for Mo and the concentrations regressed against soil Mo loads estimated from actual soil Mo concentrations in the 0- to 15-cm depth. Slopes of such linear regressions represent uptake coefficients (UC values) used by the USEPA to assess risk of biosolids Mo to ruminants fed forage grown on biosolids-amended land. The UC value for all 29 fields was estimated as 1.66, which agrees with the few soybean grain data in the literature. The UC value, however, is well below a conservative UC value of 4, recently recommended for all fresh legume materials fed to cattle. Soybean grain can contain high concentrations of Mo (>10 mg kg(-1)) and have low (<2:1) Cu to Mo ratios, which can exacerbate molybdenosis problems in cattle. However, soybean grain normally constitutes only -10% of dairy cattle diet, and other constituents (e.g., corn grain, stover, mineral supplements) are sufficient, or can be manipulated, to control molybdenosis.

The USEPA standards (40 CFR Part 503) for the use or disposal of sewage sludge (biosolids) derived risk-based numerical values for Mo for the biosolids --> land --> plant --> animal pathway (Pathway 6). Following legal challenge, most Mo numerical standards were withdrawn, pending additional field-generated data using modern biosolids (Mo concentrations <75 mg kg(-1) and a reassessment of this pathway. This paper presents a reevaluation of biosolids Mo data, refinement of the risk assessment algorithms, and a reassessment of Mo-induced hypocuprosis from land application of biosolids. Forage Mo uptake coefficients (UC) are derived from field studies, many of which used modern biosolids applied to numerous soil types, with varying soil pH values, and supporting various crops. Typical cattle diet scenarios are used to calculate a diet-weighted UC value that realistically represents forage Mo exposure to cattle. Recent biosolids use data are employed to estimate the fraction of animal forage (FC) likely to be affected by biosolids applications nationally. Field data are used to estimate long-term Mo leaching and a leaching correction factor (LC) is used to adjust cumulative biosolids application limits. The modified UC and new FC and LC factors are used in a new algorithm to calculate biosolids Mo Pathway 6 risk. The resulting numerical standards for Mo are cumulative limit (RPc)=40 kg Mo ha(-1), and alternate pollutant limit (APL) = 40 mg Mo kg(-1) We regard the modifications to algorithms and parameters and calculations as conservative, and believe that the risk of Mo-induced hypocuprosis from biosolids Mo is small. Providing adequate Cu mineral supplements, standard procedure in proper herd management, would augment the conservatism of the new risk assessment.

The soil solid phase components most responsible for P sorption in Florida soils are Fe and Al oxides. Thus, we hypothesized that land application of biosolids would significantly increase a soil's P retention by increasing its content of P-sorbing solids, especially when biosolids with high Fe and Al concentrations are applied to soils that sorb P poorly. Biosolids effects were quantified by a series of single-point isotherms on soils from two field studies sampled for up to 4 yr after initial biosolids application. Biosolids additions had little effect on P retention in a soil with abundant oxalate-extractable Fe and Al and a correspondingly large native P-sorbing capacity. However, biosolids significantly increased P retention in a soil with low oxalate-extractable Fe and Al content and low native P-sorbing capacity. Biosolids effects on P retention lasted 1 to 3 yr after application, depending on biosolids source and rate of application, and generally mimicked persistence of increased extractable Fe and Al concentrations in the poorly P-sorbing soil. Disappearance of added Fe and Al (and, hence, P retention capacity) from the surface horizons over time was relatively rapid, perhaps due to abundant organic acid production associated with biosolids degradation. Phosphorus in biosolids containing (or tailored to contain) abundant Fe and/or Al can be expected to behave as a slowly available P source, and to be less subject to leaching losses than completely soluble P sources.

This study was part of a larger effort to generate field data appropriate to the assessment of biosolids molybdenum (Mo) risk to ruminants. Corn (Zea mays L.) is an important component of cattle diet, and is a logical crop for biosolids amendment owing to its high N requirement. Paired soil and corn stover samples archived from two unique field experiments were analyzed to quantify the relationship (uptake coefficient, UC) between stover Mo and soil Mo load. Both studies used biosolids with total Mo concentrations typical of modern materials. Data from long-term (continuous corn) plots in Fulton County, IL confirm expected low Mo accumulation by corn stover, even at very high biosolids loads and soil Mo loads estimated to be near 18 kg Mo ha(-1). Uptake slopes were actually negative, but USEPA protocol would assign UC values of 0.001. Data from plots in Minnesota also suggested essentially no correlations between stover Mo and soil Mo loads for continuous corn. However, greater Mo accumulation in corn grown following soybean [Glycine max (L.) Merr.] suggests the possibility of enhanced Mo bioavailability to corn in corn-soybean rotations. Nevertheless, molybdenosis risk to cattle consuming corn stover produced on biosolids-amended land is small as stover Mo concentrations were always low and stover Cu to Mo ratios exceeded 2:1, which avoids molybdenosis problems.

Angus x Hereford heifers (n = 50) were randomly assigned to bahiagrass pastures treated with biosolids varying in mineral content and evaluated for mineral status, with special attention to Cu. Biosolids and NH4NO3 were all applied at the rate of either 179 kg N/ha (X) or twice this (2X). Fertilizer was applied to .81-ha pastures for the following treatments: 1) Baltimore biosolids (1X = 179 kg N/ha); 2) Baltimore biosolids (2X = 358 kg N/ha); 3) Tampa biosolids (1X = 179 kg N/ha); 4) Tampa biosolids (2X = 358 kg N/ha); or 5) control NH4NO3 (1X = 179 kg N/ha) applied at two times. Pastures were divided into five blocks with each treatment represented once in each block. Copper loads varied from 8.8 to 42.2 kg/ha, and Mo loads varied from .27 to 1.11 kg/ha. Heifers (two per pasture) grazed their assigned pastures exclusively for 176 d. Liver biopsies were taken from all animals at d 1, 99, and 176, and blood samples on d 1, 50, 99, 135, and 176. Liver and plasma were analyzed for selected mineral contents, and blood was analyzed for hemoglobin and hematocrit. Experimental animals were generally low in mineral status when assigned to pastures and deficient in Se and P. By d 50, plasma Ca, Mg, Se, P, and Zn were adequate for all treatments. Plasma Cu declined (P < .03) for all treatments from d 50 to 176. Plasma Cu reflected depleted liver Cu storage, with the two Tampa and highest Baltimore treatment means lower in plasma Cu than the control at 176 d. Liver Fe concentrations were adequate for all treatments, and Mo concentrations (< 2.18 mg/kg) did not approach levels indicative of toxicity. Liver Cu declined (P < .05) with time for all treatments. By d 99, animals receiving the two Baltimore treatments and the lowest Tampa application rate had lower (P < .05) liver Cu than the control, and all treatments were lower at 176 d. The decline of animal Cu status (liver and plasma) reflects the low Cu status of bahiagrass and the possibility of high forage S (.30 to .47%) interfering with Cu metabolism. Forage Mo was low but was slightly higher in biosolids-treated pastures. High levels of biosolids applications to bahiagrass pastures were not detrimental to mineral status except Cu, which had a tendency to decline in plasma and for all biosolids treatments declined in liver.

Numerous toxic organic chemicals (TOs), with a wide range of chemical properties, can occur in sewage sludges. The vast majority of sludge-borne TOs occur at low concentrations, and even lower TO concentrations are expected in sludge-amended soils. Further, most TOs are so strongly reactive in the soil-sludge matrix that their bioavailabilities to plants are expected to be low. A host of experimental techniques have been employed to measure TO plant uptake and to relate bioavailability to TO chemical and physical properties. The strengths and weaknesses of several experimental approaches are examined, and the resulting data are evaluated. Sound experimental data, especially field data and/or data from studies with endogenously sludge-borne TOs, indicate negligible contamination of crop plants with TOs in sludge-amended soils. Assessing the potential for plant uptake of sludge-borne TOs involves determining: (a) which TOs are most likely present in biosolids and what are their toxicities; (b) what quantities of TOs are likely to be added to the growth media via biosolids application; (c) what effects various dissipation/dispersion reactions have on the potential bioavailability of TOs; and (d) what are the various mechanisms for plant uptake/metabolism of TOs.

Background: The rapid recovery from mivacurium- induced neuromuscular block has encouraged omission of its reversal. The purpose of this study was to determine, in children and in adults, whether failure to reverse mivacurium neuromuscular block was associated with residual neuromuscular block on arrival in the postanesthesia care unit., Methods: In 50 children, aged 2-12 yr, and 50 adults, aged 20-60 yr, anesthesia was induced and maintained with propofol and fentanyl, and neuromuscular block was achieved by an infusion of mivacurium, to maintain one or two visible responses to train-of-four (TOF) stimulation of the ulnar nerve. At the end of surgery, mivacurium infusion was stopped, and 10 min later, reversal was attempted with saline or 0.5 mg x kg(-1) edrophonium by random allocation. On arrival in the postanesthesia care unit, a blinded observer assessed patients clinically and by stimulation of the ulnar nerve with a Datex electromyogram in the uncalibrated TOF mode., Results: Children arrived in the postanesthesia care unit 8.2 +/- 3-4 min after reversal of neuromuscular block and showed no sign of weakness, either clinically or by TOF stimulation. Although TOF ratio was greater in children who had received edrophonium (1.00 +/- 0.05 vs. 0.93 +/- 0.01, P<0.01), TOF was >0.7 in all children. Adults arrived in the postanesthesia care unit 12.9 +/- 5.3 min after reversal of neuromuscular block(P<0.01 vs. children). Six in the saline group demonstrated weakness (two required immediate reversal of neuromuscular block, and TOF was <0.7 in four others), compared with TOF <0.7 in only one of the edrophonium group (P<0.05)., Conclusions: This study demonstrated that, in adults, failure to reverse mivacurium neuromuscular block was associated with an increased incidence of residual block. Such weakness was not observed in children receiving similar anesthetic and neuromuscular blocking regimens.