Evaluation of a pH- and time-dependent model for the sorption of heavy metal cations by poultry litter-derived biochar.

Common isotherm and kinetic models cannot describe the pH-dependent sorption of heavy metal cations by biochar. In this paper, we evaluated a pH-dependent, equilibrium/kinetic model for describing the sorption of cadmium (Cd), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn) by poultry litter-derived biochar (PLB). We performed sorption experiments across a range of solution pH, initial metal concentration, and reaction time. The sorption of all five metals increased with increasing pH. For Cd, Cu, and Pb, kinetics experiments demonstrated that sorption rates were greater at pH 6.5 than at pH 4.5. For each metal, all sorption data were described using single set of four adjustable parameters. Sorption edge and isotherm data were well described with R2 > 0.93 in all cases. Time-dependent sorption was well described (R2 ≥ 0.90) for all metals except Pb (R2 = 0.77). We then used the best-fit model parameters to calculate linear distribution coefficients (KD) and equilibration times as a function of pH and initial solution concentration. These calculations provide a more robust way of characterizing biochar affinity for metal cations than Freundlich distribution coefficients or Langmuir sorption capacity. Because this model can characterize metal cation sorption by biochar across a wider range of reaction conditions than traditional isotherm or kinetic models, it is better suited for estimating metal cation/biochar interactions in engineered or natural systems.

Evaluation of phosphorus runoff from sandy soils under conservation tillage with surface broadcasted recovered phosphates.

Potential new sources of phosphorus (P) fertilizer are the recovered P from livestock wastewater through chemical precipitation and the ash from combusting animal manures. Although most of the research on P losses from conservation tillage include high water-soluble P compounds from commercial fertilizer sources, information on the use of non-conventional, low water-soluble, recycled P sources is scarce. Particularly for sandy soils of the United States (US) Southeastern Coastal Plain region, research driven information on P loss into the environment is needed to determine recommendations for a direct use of new recycled P sources as crop P fertilizers. The objective of this study is to investigate the potential P runoff from sandy soils under conservation tillage, fertilized with recovered P from liquid swine manure and turkey litter ash in comparison with commercial P fertilizer triple superphosphate (TSP). The field study included two typical sandy soils of the US Southeastern Coastal Plain region, the Noboco and Norfolk. Simulated rain corresponding to the annual 30-min rainfall in the study site (Florence County, South Carolina) was applied to plots treated with recovered P from liquid swine manure, turkey litter ash, and TSP, including a control with no P added. The runoff was monitored and sampled every 5 min during the test and composite soil samples were collected from the top (0-15 cm) and subsurface (15-30 cm) soil layers in each plot. Laboratory analyses were conducted to quantify both total P (TP) and soluble reactive P (SRP) in runoff samples, and the soil test P in the soil layers. Two-way analyses of variances show significant treatment effects on both TP and SRP runoff. The quantities of SRP runoff from plots treated with the recovered P from swine manure and turkey litter ash represent respectively 1% and 7-8% of SRP runoff from plots treated with TSP. Hence, the use of the recovered P materials as crop P fertilizers through surface broadcast application present less environmental risks compared to commercial TSP.

Magnesium activation affects the properties and phosphate sorption capacity of poultry litter biochar.

Biochars with a high affinity for phosphorus (P) are promising soil amendments for reducing P in agricultural run-off. Poultry litter (PL) is an abundant biochar feedstock. However, PL-derived biochars are typically high in soluble P and therefore require chemical modification to become effective P sorbents. This study investigated the effect of magnesium (Mg) activation on extractable P (EP) and P sorption capacities of PL-derived biochars. Biochar was produced at 500-900 °C from PL activated with 0-1 M Mg. Three differentially aged PL feedstocks were evaluated (1-, 3-5-, and 7-9-year-old). Increased Mg activation level and pyrolysis temperature both resulted in EP reductions from the biochars. Specifically, biochars produced at temperatures ≥ 700 °C from PL activated with ≥ 0.25 M Mg had negligible EP. X-ray diffractograms indicated that increased Mg loading favored the formation of stable Mg3(PO4)2 phases while increasing temperature favored the formation of both Mg3(PO4)2 and Ca5(PO4)3OH. Maximum P sorption capacities (Pmax) of the biochars were estimated by fitting Langmuir isotherms to batch sorption data and ranged from 0.66-10.35 mg g-1. Average Pmax values were not affected by PL age or pyrolysis temperature; however, biochars produced from 1 M Mg-activated PL did have significantly higher average Pmax values (p < 0.05), likely due to a greater abundance of MgO. Overall, the results demonstrated that Mg activation is an effective strategy for producing PL-derived biochars with the potential ability to reduce P loading into environmentally sensitive ecosystems.

The Occurrence of Legacy P Soils and Potential Mitigation Practices Using Activated Biochar.

The long-term application of manures in watersheds with dense animal production has increased soil phosphorus (P) concentration, exceeding plant and soil assimilative capacities. The P accumulated in soils that are heavily manured and contain excess extractable soil P concentrations is known as legacy P. Runoff and leaching can transport legacy P to ground water and surface water bodies, contributing to water quality impairment and environmental pollution, such as eutrophication. This review article analyzes and discusses current and innovative management practices for soil legacy P. Specifically, we address the use of biochar as an emerging novel technology that reduces P movement and bioavailability in legacy P soils. We illustrate that properties of biochar can be affected by pyrolysis temperature and by various activating chemical compounds and by-products. Our approach consists of engineering biochars, using an activation process on poultry litter feedstock before pyrolysis to enhance the binding or precipitation of legacy P. Finally, this review article describes previous examples of biochar activation and offers new approaches to the production of biochars with enhanced P sorption capabilities.

Earthworms increase the potential for enzymatic bio-activation of biochars made from co-pyrolyzing animal manures and plastic wastes.

We assessed the enzymatic activation of four different biochars produced from pyrolyzing swine manure and poultry litter, and by co-pyrolyzing these livestock residues with agricultural spent mulch plastic film wastes (plastichars). Enzymatic activation consisted of incubating biochars in soil inoculated with earthworms (Lumbricus terrestris), which acted as biological vectors to facilitate retention of extracellular enzymes onto biochar surface. The activity of carboxylesterase ‒a pesticide-detoxifying enzyme‒ was measured in non-bioturbed soils (reference), linings of the burrows created by earthworms, casts (feces) and biochar particles recovered from the soil. Our results revealed that: 1) biochar increased soil carboxylesterase activity respect to biochar-free (control) soils, which was more prominent in the presence of earthworms. 2) The maximum enzyme activity was found in soils amended with plastichars. 3) The plastichars showed higher enzyme binding capacities than that of the biochars produced from animal manure alone, corroborating the pattern of enzyme distribution found in soil. 4) The presence of earthworms in soil significantly increased the potential of the plastichars for enzymatic activation. These findings suggest that the plastichars are suitable for increasing and stabilizing soil enzyme activities with no toxicity on earthworms.

A simple mathematical method to estimate ammonia emission from in-house windrowing of poultry litter.

In-house windrowing between flocks is an emerging sanitary management practice to partially disinfect the built-up litter in broiler houses. However, this practice may also increase ammonia (NH3) emission from the litter due to the increase in litter temperature. The objectives of this study were to develop mathematical models to estimate NH3 emission rates from broiler houses practicing in-house windrowing between flocks. Equations to estimate mass-transfer areas form different shapes windrowed litter (triangular, rectangular, and semi-cylindrical prisms) were developed. Using these equations, the heights of windrows yielding the smallest mass-transfer area were estimated. Smaller mass-transfer area is preferred as it reduces both emission rates and heat loss. The heights yielding the minimum mass-transfer area were 0.8 and 0.5 m for triangular and rectangular windrows, respectively. Only one height (0.6 m) was theoretically possible for semi-cylindrical windrows because the base and the height were not independent. Mass-transfer areas were integrated with published process-based mathematical models to estimate the total house NH3 emission rates during in-house windrowing of poultry litter. The NH3 emission rate change calculated from the integrated model compared well with the observed values except for the very high NH3 initial emission rate from mechanically disturbing the litter to form the windrows. This approach can be used to conveniently estimate broiler house NH3 emission rates during in-house windrowing between flocks by simply measuring litter temperatures.

Improved water quality and reduction of odorous compounds in anaerobic lagoon columns receiving pre-treated pig wastewater.

Large volumes of wastewater from confined pig production are stored in anaerobic lagoons. Control methods are needed to reduce air pollution by foul odors released from these lagoons. In a pilot-scale experiment, we evaluated the effect of pig wastewater pre-treatment on reducing the concentration of selected malodor compounds in lagoons receiving liquid from: (1) flocculant enhanced solid-liquid separation (SS), and (2) solid-liquid separation plus biological N treatment using nitrification-denitrification (SS+NDN). A conventional anaerobic lagoon was included as a control. Concentrations of five selected malodorous compounds (phenol, p-cresol, 4-ethylphenol, indole, and skatole) and water quality parameters (ammonia-nitrogen and chemical oxygen demand) were determined in lagoon effluents. The SS+NDN pretreatment was more efficient than the SS in reducing odorous compounds in the lagoon liquid. The SS+NDN reduced by about 99% the liquid concentrations of all selected compounds. An odor panel test revealed that SS was ineffective to reduce the human sense of malodor with respect to the control. Whereas the SS+NDN had the significant lowest odor intensity and unpleasantness. These results are supported by the strong correlations found between the sum of odorous compound concentration with odor panel results and concentrations of both ammonium-nitrogen and chemical oxygen demand in lagoon liquid samples.

Ammonia and Nitrous Oxide Emissions from Broiler Houses with Downtime Windrowed Litter.

An emerging poultry manure management practice is in-house windrowing to disinfect the litter. However, this practice is likely to increase emissions of ammonia (NH) and nitrous oxide (NO) from the windrowed litter. The objective of this study was to quantitatively compare NH and NO emissions from broiler houses with and without in-house windrowing. Two broiler houses at a commercial farm were used to compare the NH and NO emissions. Gas emission measurements were conducted continuously and simultaneously for both the control house (without windrowing) and the house with windrowing during the same production periods. The house emission rates were calculated by multiplying the hourly mean gas concentrations and the ventilation rates. The windrowed litter temperature was significantly higher than that of the control litter. The impact of downtime (the time lapse between flocks, during which the bird house is empty) windrowing litter on pathogen reduction was inconclusive because of very low or no recovery of both and spp. from control or windrowed litter samples, respectively. The windrowing house NH emissions were 26.2 and 16.6 kg d house, whereas for the control house, they were 14.6 and 12.8 kg d house in 2012 and 2013, respectively. The NO emissions from the windrowing house were also higher than those from the control house. The total NH and NO emissions from broiler houses practicing windrowing litter management were estimated to be 35.0 and 4.43 g bird, respectively, compared with 31.9 and 3.89 g bird for the control house, respectively.

Phosphorus recovery from pig manure solids prior to land application.

Land disposal of pig manure is an environmental concern due to an imbalance of the nitrogen to phosphorus (N:P) ratio for crop production, leading to excess phosphorus (P) in soils and potential risks of water pollution. A process called "quick wash" was investigated for its feasibility to extract and recover P from pig manure solids. This process consists of selective dissolution of P from solid manure into a liquid extract using mineral or organic acid solutions, and recovery of P from the liquid extract by adding lime and an organic polymer to form a P precipitate. Laboratory tests confirmed the quick wash process selectively removed and recovered up to 90% of the total (TP) from fresh pig manure solids while leaving significant amounts of nitrogen (N) in the washed manure residue. As a result of manure P extraction, the washed solid residue became environmentally safer for land application with a more balanced N:P ratio for crop production. The recovered P can be recycled and used as fertilizer for crop production while minimizing manure P losses into the environment.

Water quality and nitrogen mass loss from anaerobic lagoon columns receiving pretreated influent.

Control methods are needed to abate NH losses from swine anaerobic lagoons to reduce the contribution of confined swine operations to air pollution. In a 15-mo meso-scale column study, we evaluated the effect of manure pretreatment on water quality, reduction of N losses, and sludge accumulation in swine lagoons using (i) enhanced solid-liquid separation with polymer (SS) and (ii) solid-liquid separation plus biological N treatment using nitrification-denitrification (SS + NDN). A conventional anaerobic lagoon was included as a control. Concentrations of total Kjeldahl N (TKN), total ammoniacal N (TAN), and NO-N were monitored during the course of the study, and the volumes of column liquid and sludge were used to estimate N mass flows. At the end of the study, TKN and TAN concentrations in the liquid of SS columns were 35 and 37% lower than the control, respectively, and TKN and TAN concentrations in SS + NDN were 97 and 99% lower than the control. The N mass flow analysis revealed that SS reduced total N inflow by 30% and SS + NDN by 82% compared with the control. The SS was ineffective at reducing NH losses compared with the control. Instead, SS + NDN effectively reduced total NH losses by 50%, most of which occurred during the first 6 mo of the study. Although both pretreatments can stop the mass accumulation of total N in sludge, SS + NDN had the advantage of improving water quality and abating NH emissions from treated lagoons. As an additional environmental benefit, SS + NDN effluents could be used for crop irrigation without the risk of NH losses during land application.

Partial nitritation of swine wastewater in view of its coupling with the anammox process.

Partial nitritation (PN) of swine wastewater was investigated in a sequencing batch reactor (SBR) using a high-performance nitrifying sludge. Characteristics of the wastewater used were low content of biodegradable organic matter and a high alkalinity-to-ammonium ratio. The target oxidation of ammonium nitrogen (NH-N) to nitrite nitrogen (NO-N) was 57% (1.32 g NO-N g NH-N), which corresponds with the reaction ratio of the anaerobic ammonium oxidation (anammox). This target was successfully achieved at 32°C by controlling the inflow rate and the corresponding nitrogen loading rate (NLR). An average NLR of 1.47 g NH-N L d was applied to the partial nitritation sequencing batch reactor during a period of 70 d. The nitrite production rate obtained was 0.91 g NO-N L d. No nitrate was produced. The PN effluent contained 1.38 g NO-N g NH-N, which was within 5% of the target ratio. Under steady composition of the wastewater, the pH was shown to be a good indicator of the PN process performance. Furthermore, in a second sequencing batch reactor, the anaerobic ammonium oxidation process was effectively applied to the PN effluent, attaining a nitrogen conversion rate of 0.36 g N L d (14.3 mg N g volatile suspended solids h).

Anammox sludge immobilized in polyvinyl alcohol (PVA) cryogel carriers.

This study evaluated the use of PVA cryogels to encapsulate slow-growing anammox bacteria for deammonification treatment of wastewater. The cryogel pellets were prepared by freezing-thawing at -8 °C. On average, pellets contained 11.8 mg-TSS/g-pellet of enriched anammox sludge NRRL B-50286 (Candidatus Brocadia caroliniensis) in 4-mm cubes. They were tested with synthetic and partially nitrified swine wastewater using continuous stirred-tank reactors packed at 20% (w/v). The immobilized gel was retained inside the reactor by a screen that eliminated the need of sludge recycling. The stoichiometry of anammox reaction was maintained for more than 5 months under non-sterile conditions. The process was not limited by substrates availability unless quite low N concentration (<5 mg/L) achieving >93% removal efficiency. In mass balances, >80% of the potential N conversion activity was achieved (2920 mg-N/kg-pellet/d). In addition, the immobilized bacteria were resilient to inhibition at high nitrite concentrations (244-270 mg-N/L).

Long-term preservation of anammox bacteria.

Deposit of useful microorganisms in culture collections requires long-term preservation and successful reactivation techniques. The goal of this study was to develop a simple preservation protocol for the long-term storage and reactivation of the anammox biomass. To achieve this, anammox biomass was frozen or lyophilized at two different freezing temperatures (-60°C and in liquid nitrogen (-200°C)) in skim milk media (with and without glycerol), and the reactivation of anammox activity was monitored after a 4-month storage period. Of the different preservation treatments tested, only anammox biomass preserved via freezing in liquid nitrogen followed by lyophilization in skim milk media without glycerol achieved stoichiometric ratios for the anammox reaction similar to the biomass in both the parent bioreactor and in the freshly harvested control treatment. A freezing temperature of -60°C alone, or in conjunction with lyophilization, resulted in the partial recovery of the anammox bacteria, with an equal mixture of anammox and nitrifying bacteria in the reactivated biomass. To our knowledge, this is the first report of the successful reactivation of anammox biomass preserved via sub-zero freezing and/or lyophilization. The simple preservation protocol developed from this study could be beneficial to accelerate the integration of anammox-based processes into current treatment systems through a highly efficient starting anammox biomass.

Characterization of a microbial community capable of nitrification at cold temperature.

While the oxidation of ammonia is an integral component of advanced aerobic livestock wastewater treatment, the rate of nitrification by ammonia-oxidizing bacteria is drastically reduced at colder temperatures. In this study we report an acclimated lagoon nitrifying sludge that is capable of high rates of nitrification at temperatures from 5 degrees C (11.2mg N/g MLVSS/h) to 20 degrees C (40.4 mg N/g MLVSS/h). The composition of the microbial community present in the nitrifying sludge was investigated by partial 16S rRNA gene sequencing. After DNA extraction and the creation of a plasmid library, 153 partial length 16S rRNA gene clones were sequenced and analyzed phylogenetically. Over 80% of these clones were affiliated with the Proteobacteria, and grouped with the beta- (114 clones), gamma- (7 clones), and alpha-classes (2 clones). The remaining clones were affiliated with the Acidobacteria (1 clone), Actinobacteria (8 clones), Bacteroidetes (16 clones), and Verrucomicrobia (5 clones). The majority of the clones belonged to the genus Nitrosomonas, while other clones affiliated with microorganisms previously identified as having floc forming or psychrotolerance characteristics.

Evaluation of second-generation multistage wastewater treatment system for the removal of malodors from liquid swine waste.

Wastewater quality and malodors in a second generation implementation of environmentally superior technology (EST) were monitored over three cycles of pig (Sus scrofa) production and 15 mo. The wastewater treatment system consisted of three modules: solids separation, biological N removal, and P recovery/wastewater disinfection. While approximately more than 90% of the wastewater suspended solids were removed in the first stage of treatment, little reduction in malodorous compounds occurred, indicating that malodors largely remained with the liquid waste stream. The greatest improvements in wastewater quality occurred in the N treatment module where ammonium was removed through nitrification/denitrification processes: there was more than 99% reduction in aromatic malodorous compounds (e.g., p-cresol, skatole) and almost 90% reduction in volatile fatty acids (e.g., propanoate and butanoate) in N module effluent as compared to raw flushed manure. The system performed consistently well in wastewater odor removal, even during the first cycle of livestock production when system performance was being optimized. These findings showed that the combination of the processes of solids removal and biological N treatment into a practical treatment system can be very effective in reducing malodors from livestock wastewater.

Development of a second-generation environmentally superior technology for treatment of swine manure in the USA.

New swine waste management systems in North Carolina need to meet high performance standards of an environmentally superior technology (EST) regarding nitrogen, phosphorus, heavy metals, pathogens, ammonia and odor emissions, and remain affordable and simple to operate. The objective of this study was to develop a second-generation treatment system that can achieve high EST standards at reduced costs. The system used solids separation, nitrification/denitrification and phosphorus removal/disinfection, and was demonstrated at full-scale on a 5145-head swine farm during three production cycles (15-months). Removal efficiencies were: 98% suspended solids, 97% ammonia, 95% phosphorus, 99% copper and zinc, 99.9% odors, and 99.99% pathogens. The system met EST standards at 1/3 the cost of the previous version. Animal health and productivity were enhanced; hog sales increased 32,900 kg/cycle (5.6%). These results demonstrated that: (1) significant cost reductions were achieved by on-farm implementation and continued engineering improvements, and (2) the new waste management system substantially benefited livestock productivity.

Removal of phosphorus from livestock effluents.

For removal of phosphorus (P) from swine liquid manure before land application, we developed a treatment process that produces low P effluents and a valuable P by-product with minimal chemical addition and ammonia losses. The new wastewater process included two sequential steps: (i) biological nitrification and (ii) increasing the pH of the nitrified wastewater to precipitate P. We hypothesized that by reduction of inorganic buffers (NH(4)(+) and carbonate alkalinity) via nitrification, P could be selectively removed by subsequent hydrated lime [Ca(OH)(2)] addition. The objective of the study was to assess if this new treatment could consistently reduce inorganic buffer capacity with varied initial concentrations of N (100-723 mg NH(4)(+) L(-1)), P (26-85 mg TP L(-1)), and alkalinity (953-3063 mg CaCO(3) L(-1)), and then efficiently remove P from swine lagoon liquid. The process was tested with surface lagoon liquids from 10 typical swine farms in North Carolina. Each lagoon liquid received treatment in a nitrification bioreactor, followed by chemical treatment with Ca(OH)(2) at Ca rates of 0, 2, 4, 6, 8, 10, and 12 mmol L(-1) to precipitate P. This configuration was compared with a control that received the same Ca rates but without the nitrification pretreatment. The new process significantly reduced >90% the inorganic buffers concentrations compared with the control and prevented ammonia losses. Subsequent lime addition resulted in efficient pH increase to > or = 9.5 for optimum P precipitation in the nitrified liquid and significant reduction of effluent total P concentration versus the control. With this new process, the total P concentration in treated liquid effluent can be adjusted for on-farm use with up to >90% of P removal. The recovered solid Ca phosphate material can be easily exported from the farm and reused as P fertilizer. Therefore, the new process can be used to reduce the P content in livestock effluents to levels that would diminish problems of excess P accumulation in waste-amended soils.

Water quality improvements of wastewater from confined animal feeding operations after advanced treatment.

Current trends of animal production concentration and new regulations promote the need for environmentally safe alternatives to land application of liquid manure. These technologies must be able to substantially remove nutrients, heavy metals, and emissions of ammonia and odors and disinfect the effluent. A new treatment system was tested full-scale in a 4360-swine farm in North Carolina to demonstrate environmentally superior technology (EST) that could replace traditional anaerobic lagoon treatment. The system combined liquid-solids separation with nitrogen and phosphorus removal processes. Water quality was monitored at three sites: (i) the treatment plant as the raw manure liquid was depurated in the various processes, (ii) the converted lagoon as it was being cleaned up with the treated effluent, and (iii) an adjacent traditional anaerobic lagoon. The treatment plant removed 98% of total suspended solids (TSS), 76% of total solids (TS), 100% of 5-d biochemical oxygen demand (BOD(5)), 98% of total Kjeldahl nitrogen (TKN) and NH(4)-N, 95% of total phosphorus (TP), 99% of Zn, and 99% of Cu. The quality of the liquid in the converted lagoon improved rapidly as cleaner effluent from the plant replaced anaerobic lagoon liquid. The converted lagoon liquid became aerobic (dissolved oxygen, 6.95 mg L(-1); Eh, 342 mv) with the following mean reductions in the second year of the conversion: 73% of TSS, 40% of TS, 77% of BOD(5), 85% of TKN, 92% of NH(4)-N, 38% of TP, 37% of Zn, and 39% of Cu. These findings overall showed that EST can have significant positive impacts on the environment and on the livestock industries.

Development of environmentally superior treatment system to replace anaerobic swine lagoons in the USA.

A full-scale treatment system for swine manure was developed to eliminate discharge to surface and ground waters and contamination of soil and groundwater by nutrients and heavy metals, along with related release of ammonia, odor, and pathogens. The system greatly increased the efficiency of liquid-solid separation by polymer injection to increase solids flocculation. Nitrogen management to reduce ammonia emissions was accomplished by passing the liquid through a module where bacteria transformed ammonia into harmless nitrogen gas. Subsequent alkaline treatment of the wastewater in a phosphorus module precipitated phosphorus and killed pathogens. Treated wastewater was recycled to clean swine houses and for crop irrigation. The system was tested during one year in a 4400-head finishing farm as part of the Agreement between the Attorney General of North Carolina and swine producers Smithfield Foods, Premium Standard Farms and Frontline Farmers to replace traditional waste treatment anaerobic lagoons with environmentally superior technology. The on-farm system removed 97.6% of the suspended solids, 99.7% of BOD, 98.5% of TKN, 98.7% of soluble ammonia (NH(4)(+)-N), 95.0% of total P, 98.7% of copper and 99.0% of zinc. It also removed 97.9% of odor compounds in the liquid and reduced pathogen indicators to non-detectable levels. Based on performance obtained, it was determined that the treatment system met the Agreement's technical performance standards that define an environmentally superior technology. These findings overall showed that cleaner alternative technologies are technically and operationally feasible and that they can have significant positive impacts on the environment and the livestock industry.

Free Fatty acids and sterols in swine manure.

Free fatty acids and sterols were assessed in fresh manure and anaerobic lagoon sludge from swine production facilities in North Carolina. Eight free fatty acids and five sterols were identified and quantified in both manure and sludge samples. Compound identification was performed by gas chromatography/mass spectroscopy (GC-MS), and compound quantities were determined by gas chromatography after solid phase extraction with a 50:50 mixture of diethyl ether and hexane. The free fatty acids occurring in greatest abundance in both fresh manure and lagoon sludge were palmitic, oleic, and stearic. Free fatty acid content in fresh manure ranged from approximately 3 microg g(-1) dry weight (dw) to over 45 microg g(-1) dw. In lagoon sludge, free fatty acid content ranged from about 0.8 microg g(-1) dw to nearly 4 microg g(-1) dw. Coprostanol and epicoprostanol were the sterols in largest concentrations in fresh manure and lagoon sludge samples. Total sterol content ranged from approximately 0.5 microg g(-1) dw to around 11 microg g(-1) dw in fresh manure and from 3.5 microg g(-1) dw to almost 9 microg g(-1) dw in lagoon sludge. Fresh manure and lagoon sludge both had high levels of inorganic cations (e.g., Ca, Mg, Fe) capable of binding free fatty acids and forming insoluble complexes, thereby potentially reducing fatty acid biodegradation. In anaerobic lagoons, sterols are an organic fraction of sludge that are resistant to bacterial degradation. In the case of fresh manure, fatty acids could represent a potential source of energy via the manufacture of biodiesel fuel, if efficient means for their extraction and transesterification can be devised.