Dissipation of oxytetracycline, chlortetracycline, tetracycline and doxycycline using HPLC-UV and LC/MS/MS under aquatic semi-field microcosm conditions

A mixture of four tetracyclines; oxytetracycline (OTC), chlortetracycline (CTC), tetracycline (TC), and doxycycline (DC) was applied in fifteen 12000l outdoor microcosms at four treatment levels plus controls each with three replicates (n = 3). The dissipation times of parent compounds were monitored and half-lives (DT50) of 1-4 days, depending on treatment level were recorded. This is in accordance with half-lives from previous findings in bench-top experiments. Parent compound DT50, were determined using HPLC-UV. Furthermore, the samples were analyzed for ten different tetracycline products using LC/MS/MS. Two products were found for chlortetracycline; 4-epi-anh-chlortetracyline and the iso-chlortetracycline. Iso-forms were only found for CTC and only at the highest treatment (300 microg l(-1)). The half-lives, trajectories, and relative amounts of the products were analogous for all four tetracyclines. DT50 for products were less than 1.2 days. Formation of 4-epi-anh-tetracyclines, occurred at neutral to weak alkaline conditions.     

Occurrence and distribution of heavy metals and tetracyclines in agricultural soils after typical land use change in east China

Land use in east China tends to change from paddy rice to vegetables or other high-value cash crops, resulting in high input rates of organic manures and increased risk of contamination with both heavy metals (HMs) and antibiotics. This investigation was conducted to determine the accumulation, distribution and risks of HMs and tetracyclines (TCs) in surface soils and profiles receiving different amounts of farmyard manure. Soil samples collected from suburbs of Hangzhou city, Zhejiang province were introduced to represent three types of land use change from paddy rice to asparagus production, vineyards and field mustard cultivation, and divided into two portions, one of which was air-dried and sieved through 2-, 0.3- and 0.149-mm nylon mesh for determination of pH and heavy metals. The other portion was frozen at ?20 °C, freeze-dried and sieved through a 0.3-mm nylon mesh for tetracyline determination. HM and TC concentrations in surface soils of 14-year-old mustard fields were the highest with total Cu, Zn, Cd and ∑TCs of 50.5, 196, 1.03 mg?kg^?1 and 22.9 μg?kg^?1, respectively, on average. The total Cu sequence was field mustard?>?vineyards?>?asparagus when duration of land use change was considered; oxytetracycline (OTC) and doxycycline were dominant in soils used for asparagus production; OTC was dominant in vineyards and chlortetracycline (CTC) was dominant in mustard soils. There were positive pollution relationships among Cu, Zn and ∑TCs, especially between Cu and Zn or Cu and ∑TCs. Repeated and excessive application of manures from intensive farming systems may produce combined contamination with HMs and TCs which were found in the top 20 cm of the arable soil profiles and also extended to 20–40 cm depth. Increasing manure application rate and cultivation time led to continuing increases in residue concentrations and movement down the soil profile.     

超声波降解四环素类抗生素废水

采用超声波降解模拟废水中四环素类抗生素(TCs):土霉素(OTC)、四环素(TC)和金霉素(CTC),考查废水初始浓度、初始pH、超声波输入功率密度、曝气量和自由基清除剂(正丁醇)对降解效率的影响。结果表明,超声波可以快速高效地降解废水中的TCs,CTC最易被降解,TC和OTC次之;在OTC、TC和CTC初始浓度0.25 mg/L,初始pH=8.2,声功率密度1.2 W/mL,气水体积比30∶1的条件下,超声波辐照20 min后去除率分别达到76.8%、84.0%和94.4%。在实验研究条件下,TCs去除率均随初始浓度(0.25~2.00 mg/L)的增大而降低,但总去除浓度升高;碱性条件有利于TCs降解,去除率随初始pH(6~11)升高而升高;功率密度(0.24~1.96 W/mL)越高,TCs去除率也越高;曝气后TCs的去除率明显升高,随着气水比(10∶1~60∶1)的增大,去除率逐渐上升;正丁醇有效抑制TCs超声波降解,可推断TCs主要降解途径为自由基氧化。TCs超声波降解过程符合伪一级动力学反应特征。     

The influence of light exposure,water quality and vegetation on the removal of sulfonamides and tetracyclines: A laboratory-scale study

The effect of aquatic vegetation (Spyrogira sp. and Zannichellia palustris), light exposure and water quality (secondary-treated wastewater vs. ultrapure water) on the removal efficiency of six antibiotics (sulfonamides and tetracyclines) is studied in laboratory-scale reactors. After 20 d of treatment, 3–59% of sulfonamides were eliminated in the reactors exposed to light. Removal was about 10% in unplanted reactors in darkness. The elimination of tetracycline (TC) and oxytetracycline (OTC) ranged between 83% and 97% in both planted and unplanted reactors. However, in dark unplanted reactors, OTC was largely removed (88%) while only 15% of TC was eliminated. These results suggest that TC was mainly removed by photodegradation whereas biodegradation or hydrolysis process seems to be significant processes for OTC. Sulfonamides were mainly eliminated by biodegradation or indirect photodegradation processes. Pseudo-first order kinetics removal rates ranged from 0.003 and 0.007 d^?1 for Sulfamethazine and TC in the covered control reactors to 0.13 and 0.21 d^?1 for TC and OTC in the uncovered control reactors, with half-lives from 3 to 350 d. A TC photodegradation product was tentatively identified in uncovered reactors. This study highlights the important role played by light exposure in the elimination of antibiotics in polishing ponds.     

水中四环素类化合物在不同光源下的光降解

研究了模拟太阳光和实际室外太阳光下四环素类化合物在水溶液中的光降解。结果表明,四环素类化合物(TCs)在模拟太阳光照射下均能发生直接光降解,且其降解速率随pH不同变化很大。四环素(TC)、土霉素(OTC)、金霉素(CTC)和多西环素(DTC)的光降解速率随溶液pH升高明显加快,而米诺环素(MTC)在水中的光降解速率随溶液pH升高略有下降。天然水体pH范围内,模拟太阳光照下四环素类化合物表观光降解速率常数在0.004～0.026 min-1范围内,降解半衰期在26～136 min范围内。在室外实际太阳光照下,四环素类化合物光降解反应速率与太阳光强成正比例关系。晴朗无云天气下,四环素类化合物降解半衰期在春冬季节较长、夏季节较短;四环素在东江实际水体中表观光降解速率很快,在冬季晴天天气下,其平均半衰期仅为8.2 min。     

Effect of fipronil on biogas production performance during anaerobic digestion of chicken manure and corn straw

Fipronil is a broad-spectrum insecticide that has a good control effect on pests of commercial poultry. Although many studies have reported the environmental fate of fipronil, the influence of residual fipronil in poultry waste on biogas production has not been further explored yet. In this article, an experimental comparative study on anaerobic digestion (AD) of chicken manure (CM) and corn straw (CS) with different fipronil concentrations (FCs) was carried at 8% of total solid (TS) and mid-temperature (35?±?1)°C. The results showed that fipronil had a significant effect on biogas production during AD of CM and CS. When the FC is at a low level (≤10?mg·kg^?1), the biogas production rate is increased and the digestion period was shortened, while higher FC (≥ 20?mg·kg^?1) showed an inhibitory effect. During the monitoring of enzyme activity, low FC showed no significant effect on cellulase and saccharase, but the urease activity increased in the early stage. High FC showed inhibition of activity of cellulase and urease, but the saccharase activity was significantly inhibited until FC reached 40?mg·kg^?1. This study also confirms that the environment in anaerobic digester is favorable for the degradation of fipronil, and its half-life is about 15.83?days.     

Tetracycline resistance in semi-arid agricultural soils under long-term swine effluent application

Annually, millions pounds of antibiotics are released unmetabolized into environment along with animal wastes. Accumulation of antibiotics in soils could potentially induce the persistence of antibiotic resistant bacteria. Antibiotics such as tetracyclines and tetracycline-resistant bacteria have been previously detected in fields fertilized with animal manure. However, little is known about the accumulation of tetracyclines and the development of tetracycline resistance in semi-arid soils. Here we demonstrate that continuous land application with swine effluent, containing trace amounts of chlortetracycline, does not necessarily induce tetracycline resistance in soil bacteria. Based on the testing of more than 3,000 bacteria isolated from the amended soils, we found no significant increase in the occurrence and level of chlortetracycline resistant bacteria in soils after 15 years of continuous swine effluent fertilization. To account for a possible transfer of tetracycline-resistant bacteria originated from the swine effluent to soils, we analyzed two commonly found tetracycline resistant genes, tet(O) and tet(M), in the swine effluent and fertilized soils. Both genes were present in the swine effluent, however, they were not detectable in soils applied with swine effluent. Our data demonstrate that agronomic application of manure from antibiotic treated swine effluent does not necessarily result in the development of antibiotic bacterial resistance in soils. Apparently, concentrations of chlortetracycline present in manure are not significant enough to induce the development of antibiotic bacterial resistance.     

Ammonia volatilization loss from surface applied livestock manure

Ammonia (NH₃) emission from livestock manures used in agriculture reduces N uptake by crops and negatively impacts air quality. This laboratory study was conducted to evaluate NH₃emission from different livestock manures applied to two soils: Candler fins sand (CFS; light-textured soil, pH 6.8 and field capacity soil water content of 70 g kg^{? 1}) from Lake Alfred, Florida and Ogeechee loamy sand (OLS; medium-textured soil, pH 5.2 and field capacity soil water content of 140 g kg^{? 1}) from Savannah, Georgia. Poultry litter (PL) collected from a poultry farm near Douglas, Georgia, and fresh solid separate of swine manure (SM) collected from a farm near Clinton, North Carolina were used. Each of the soil was weighed in 100 g sub samples and amended with either PL or SM at rates equivalent to either 0, 2.24, 5.60, 11.20, or 22.40 Mg ha^{? 1} in 1L Mason jars and incubated in the laboratory at field capacity soil water content for 19 days to monitor NH₃ volatilization. Results indicated a greater NH₃ loss from soils amended with SM compared to that with PL. The cumulative NH₃volatilization loss over 19 days ranged from 4 to 27% and 14 to 32% of total N applied as PL and SM, respectively. Volatilization of NH₃ was greater from light-textured CFS than that from medium-textured OLS. Volatilization loss increased with increasing rates of manure application. Ammonia volatilization was lower at night time than that during the day time. Differences in major factors such as soil water content, temperature, soil type and live stock manure type influenced the diurnal variation in volatilization loss of NH₃ from soils. A significant portion (> 50%) of cumulative NH₃ emission over 19 d occurred during the first 5–7 d following the application of livestock manures. Results of this study demonstrate that application of low rates of livestock manure (≤ 5.60 Mg ha^{? 1}) is recommended to minimize NH₃ emissions.     

Development of an efficient extraction method for oxytetracycline in animal manure for high performance liquid chromatography analysis

Oxytetracycline (2-(amino-hydroxy-methylidene)-4-dimethylamino-5,6,10,11,12a-pentahydroxy-6-methyl-4,4a,5,5a-tetrahydrotetracene-1,3,12-trione) is a major member of the tetracycline antibiotics family of which are widely administered to animals in concentrated animal feeding operations for purposes of therapeutical treatment and health protection. With the disposal of animal manure as fertilizer into agricultural land, tetracyclines enter the environment. However, tetracyclines chelate with multivalent cations and proteins, resulting in low extraction efficiencies from animal manure for tetracycline residue analysis. In this study an efficient extraction method for oxytetracycline from steer manure using methanol/water solution amended with chelating organic acid was developed for the analysis of high performance liquid chromatography. The effect of species and amount of amendment acids, shaking time, methanol/water ratio, manure weight, and repeated times of extraction was investigated. It was optimized to amend 2.5 g citric acid and 1.1 g oxalic acid with 10.0 g manure sample in a 50-ml centrifuge tube and extract with 15 ml methanol/water (9:1 in volume) by vigorously shaking for 30 min in a reciprocating shaker. After centrifugation at 11,000 rpm, supernatant is collected. Sample was extracted for a total of 3 times. The developed extraction method was further applied to extract oxytetracycline from fresh and aged cow manure, swine and poultry manure, and soil. Satisfactory recoveries ranging from (84.1 ± 2.4) % to (102.0 ± 3.1) % were obtained, demonstrating that the optimized extraction method is robust for oxytetracycline from different manure sample matrixes.     

Transformation kinetics and pathways of tetracycline antibiotics with manganese oxide

Tetracycline antibiotics including tetracycline (TTC), oxytetracycline (OTC) and chlorotetracycline (CTC) undergo rapid transformation to yield various products in the presence of MnO₂ at mild conditions (pH 4-9 and 22 °C). Reaction rates follow the trend of CTC > TTC > OTC, and are affected by pH and complexation of TCs with Mg²⁺ or Ca²⁺. Experimental results of TTC indicate that MnO₂ promotes isomerization at the C ring to form iso-TTC and oxidizes the phenolic-diketone and tricarbonylamide groups, leading to insertion of up to 2 O most likely at the C9 and C2 positions. In contrast, reactions of OTC with MnO₂ generate little iso-OTC, but occur mainly at the A ring’s dimethylamine group to yield N-demethylated products. CTC yields the most complicated products upon reactions with MnO₂, encompassing transformation patterns observed with both TTC and OTC. The identified product structures suggest lower antibacterial activity than that of the parent tetracyclines.     

Chlortetracycline and tylosin runoff from soils treated with antimicrobial containing manure

This study assessed the runoff potential of tylosin and chlortetracycline (CTC) from soils treated with manure from swine fed rations containing the highest labeled rate of each chemical. Slurry manures from the swine contained either CTC at 108 μ g/g or tylosin at 0.3 μ g/g. These manures were surface applied to clay loam, silty clay loam, and silt loam soils at a rate of 0.22 Mg/ha. In one trial, tylosin was applied directly to the soil surface to examine runoff potential of water and chemical when manure was not present. Water was applied using a sprinkler infiltrometer 24-hr after manure application with runoff collected incrementally every 5 min for about 45 min. A biofilm crust formed on all manure-treated surfaces and infiltration was impeded with > 70% of the applied water collected as runoff. The total amount of CTC collected ranged from 0.9 to 3.5% of the amount applied whereas tylosin ranged from 8.4 to 12%. These data indicate that if surface-applied manure contains antimicrobials, runoff could lead to offsite contamination.     

Biohydrogen production from dairy manures with acidification pretreatment by anaerobic fermentation

Background, aim, and scope  

Hydrogen is a clean and efficient energy source and has been deemed as one of the most promising carriers of new energy for the future. From an engineering point of view, producing hydrogen by mixed cultures is generally preferred because of lower cost, ease of control, and the possible use of organic waste as feedstock. The biological hydrogen production has been intensively studied in recent decades. So far, most investigates of biohydrogen production are still confined to using pure carbohydrates and carbohydrate-rich wastewater. Nowadays, the large amounts of livestock manure, which come from cattle feedlots, poultry, and swine buildings, are causing a major environmental issue because it has become a primary source of odors, gases, dust, and groundwater contamination. The increasingly stringent requirements for pollution control on livestock manures are challenging the scientific community to develop new waste treatment strategies. Thus, there is a pressing need to develop nonpolluting and renewable energy source utilizing the organic waste (e.g., livestock manure). It is well known that anaerobic digestion had successfully been used for the disposal of manures to produce methane in the last two decades. Recently, an alternative strategy has been developed to convert livestock manures (e.g., dairy manures) to biohydrogen as a high value-added clean energy source instead of methane. However, little information is available on hydrogen production from dairy manure via the mixed anaerobic microbe. As far as we know, the hydrogen production is habitually accompanied with production of volatile fatty acids (VFAs), such as acetate, butyrate, and propionate, which are also an optimal feedstock for production of methane by anaerobic digestion. Provided that the biohydrogen production from dairy manure is further combined with the anaerobic digestion of the effluent from the producing hydrogen reactor that would be a one-stone two-bird paradigm, it not only produces a clean and readily usable biologic energy but also cleans up simultaneously the environment in a sustainable fashion.     

New insights into the characterization of the binding of tetracycline analogues with lysozyme: a biophysical study

Tetracycline (TC), chlortetracycline (CTC) and oxytetracycline (OTC) are the most common members of the widely used veterinary drug tetracyclines, the residue of which in the environment can enter human body, being potentially harmful. Lysozyme is a monomeric protein widely distributed in the nature including human beings, having many physiological and pharmaceutical functions. The aim of this study was to examine the interaction of lysozyme with the three tetracyclines (TC, CTC and OTC) through spectroscopic and molecular modeling methods. The experimental results revealed that all the three tetracyclines (TCs) can interact with lysozyme with one binding site to form TCs-lysozyme complex, mainly through electrostatic forces with the affinity order: CTC > TC > OTC. The binding of TCs can cause conformational and some microenvironmental changes of lysozyme. Furthermore, molecular docking was applied to define the specific binding sites, the results of which show that all the three TCs can bind into lysozyme cleft and interact with the key active-site residues Glu 35 or Asp 52, resulting in competitive inhibition of lysozyme activity. The accurate and full basic data in the work is beneficial to clarifying the binding mechanism of TCs with lysozyme in vivo.     

Removal of tetracyclines,sulfonamides, and quinolones by industrial-scale composting and anaerobic digestion processes

This study evaluated and compared the removal of antibiotics by industrial-scale composting and anaerobic digestion at different seasons. Twenty compounds belonged to three classes of widely used veterinary antibiotics (i.e., tetracyclines, sulfonamides, and quinolones) were investigated. Results show that of the three groups of antibiotics, tetracyclines were dominant in swine feces and poorly removed by anaerobic digestion with significant accumulation in biosolids, particularly in winter. Compared to that in winter, a much more effective removal (>?97%) by anaerobic digestion was observed for sulfonamides in summer. By contrast, quinolones were the least abundant antibiotics in swine feces and exhibited a higher removal by anaerobic digestion in winter than in summer. The overall removal of antibiotics by aerobic composting could be more than 90% in either winter or summer. Nevertheless, compost products from livestock farms in Beijing contained much higher antibiotics than commercial organic fertilizers. Thus, industrial composting standards should be strictly applied to livestock farms to further remove antibiotics and produce high quality organic fertilizer.     

Residual veterinary antibiotics in swine manure from concentrated animal feeding operations in Shandong Province, China

The scientific interest in the occurrence and fate of antibiotics in animal husbandry has increased during the past decades because of the emergence and development of antimicrobial resistance in pathogenic bacteria. This study developed a method for simultaneous detection of five sulfonamides, three tetracyclines and one macrolide in swine manure with stable recoveries (73.0-110.6%) and high sensitivity (limit of quantification <90 μg kg⁻¹). Thereafter, a total of 126 swine manure samples, collected from 21 concentrated animal feeding operations (CAFOs) in Shandong Province of China during summer and winter, were analyzed. The potential influences of different sampling seasons, swine types and food sources on residual antibiotic concentrations were examined in detail. The maximum concentration of residual antibiotic could reach up to 764.4 mg kg⁻¹ (chlortetracycline), and the detection frequencies were 84.9-96.8% for tetracyclines, 0.8-51.6% for sulfonamides and 4.8% for macrolide. These data reveal that antibiotics were extensively used in CAFOs in this district and the manure may act as a non-specific source of antibiotic residue in farmlands and aquatic environments.     

A comparison of antibiotics,antibiotic resistance genes,and bacterial community in broiler and layer manure following composting

Animal manure is an important source of antibiotics and antibiotic resistance genes (ARGs) in the environment. However, the difference of antibiotic residues and ARG profiles in layer and broiler manure as well as their compost remains unexplored. In this study, we investigated the profiles of twelve antibiotics, seventeen ARGs, and class 1 integrase gene (intI1) in layer and broiler manure, and the corresponding compost at large-scale. Compared with layer manure, broiler manure exhibited approximately six times more residual tetracyclines, especially chlortetracycline. The relative abundances of qnrS and ermA genes in broiler manure were significantly higher than those in layer manure. The concentration of tetracyclines not only had a significantly positive correlation with tetracycline resistance genes (tetA and tetC) but was also positively correlated with quinolone resistance (qepA, qnrB, and qnrS) and macrolide resistance (ermA and ermT). Most ARGs in manure were reduced after composting. However, the relative abundance of sulfonamide resistance gene sul1 increased up to 2.41% after composting, which was significantly higher than that of broiler (0.41%) and layer (0.62%) manure. The associated bacterial community was characterized by high-throughput 16S rRNA gene sequencing. The relative abundances of thermophilic bacteria had significant positive correlations with the abundance of sul1 in compost. The composting has a significant impact on the ARG-associated gut microbes in poultry manure. Variation partitioning analysis indicated that the change of bacterial community compositions and antibiotics contributed partially to the shift in ARG profiles. The results indicate that at industry-scale production broiler manure had more antibiotics and ARGs than layer manure did, and composting decreased most ARG abundances in poultry manure except for sulfonamide resistance genes.

     

Primary biodegradation of veterinary antibiotics in aerobic and anaerobic surface water simulation systems

The primary aerobic and anaerobic biodegradability at intermediate concentrations (50-5000 microg/l) of the antibiotics olaquindox (OLA), metronidazole (MET), tylosin (TYL) and oxytetracycline (OTC) was studied in a simple shake flask system simulating the conditions in surface waters. The purpose of the study was to provide rate data for primary biodegradation in the scenario where antibiotics pollute surface waters as a result of run-off from arable land. The source of antibiotics may be application of manure as fertilizer or excreta of grazing animals. Assuming first-order degradation kinetics, ranges of half-lives for aerobic degradation of the four antibiotics studied were 4-8 days (OLA), 9.5-40 days (TYL), 14-104 days (MET) and 42-46 days (OTC). OLA and OTC were degraded with no initial lag phase whereas lag phases from 2 to 34 days (MET) and 31 to 40 days (TYL) were observed for other substances. The biodegradation behaviour was influenced by neither the concentrations of antibiotics nor the time of the year and location for sampling of surface water. Addition of 1 g/l of sediment or 3 mg/l of activated sludge from wastewater treatment increased the biodegradation potential which is believed to be the result of increased bacterial concentration in the test solution. Biodegradation was significantly slower in tests conducted in absence of oxygen. Assessments of the toxic properties of antibiotics by studying the influence on the biodegradation rates of 14C-aniline at different concentrations of antibiotics showed that no tests were conducted at toxic concentrations.     

A UK inventory of nitrous oxide emissions from farmed livestock

A UK inventory of the nitrous oxide (N₂O) emissions from farmed livestock was compiled to identify areas where potential abatement practices may be effective. Where possible, emission factors based on direct experimental data gathered under UK conditions were used, but published data were used when this was not feasible, together with statistical information, which included details of numbers of animals within each category of a species, animal liveweights, number of days housed, excretal rates and volumes of manures in stores. Total N₂O emissions were calculated for each component of livestock production systems, i.e. animal houses, manure stores, following application of manures to land and during grazing. Emissions were also estimated from land used for forage conservation and tillage. Total annual N₂O emissions from UK farmed livestock, based mainly on 1996 animal census data, were estimated to be 38.27 kt. The two main terms were 22.66 kt N₂O from mineral fertilisers after application to soils and 5.61 kt N₂O from stored manures (mainly in the form of farmyard manure). Within buildings, poultry were the largest contributors of N₂O, 2.97 kt, followed by cattle, 1.62 kt. Within the total emissions from stored manures, cattle were the largest contributors of N₂O, 3.58 kt, followed by poultry, 1.86 kt. Dietary manipulation and a move from solid manure based systems to slurry based systems appear to be promising abatement practices.     

Occurrence and distribution of veterinary antibiotics and tetracycline resistance genes in farmland soils around swine feedlots in Fujian Province, China

Six antibiotics, tetracyclines (TCs), and quinolones (QNs) in farmland soils from four coastal cities in Fujian Province of China were investigated. Oxytetracycline was most frequently detected, followed by enrofloxacin, ciprofloxacin, chlorotetracycline, ofloxacin, and tetracycline, with maximum concentrations of 613.2, 637.3, 237.3, 2668.9, 205.7, and 189.8 μg kg^?1, respectively. Samples from Putian City contained the highest maximum concentration of ∑TCs (3,064.2 μg kg^?1), whereas those from Fuzhou City contained the highest maximum concentration of ∑QNs (897.8 μg kg^?1). It is noteworthy that the ∑TCs and ∑QNs in 46.4 and 28.6 % of samples exceeded the ecotoxic effect trigger value (100 μg kg^?1), respectively. The concentrations of these antibiotics and five tetracycline resistance genes in four soil plots at depth profiles were quantified thereafter. In most cases, both antibiotics and resistance genes decreased with the increase of depth. Some antibiotics can be detected at a depth of 60–80 cm where the abundance of tetO, tetM, and tetX reached up to 10⁷ copies g^?1. Additionally, the sum of all tet genes (normalized to 16S rRNA genes) correlated with ∑TCs significantly (r?=?0.676). Our results suggest that resistance determinants can migrate to deeper soil layers and would probably contaminate groundwater by vertical transport.     

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 μ g g^?1 dry weight (dw) to over 45 μ g g^?1 dw. In lagoon sludge, free fatty acid content ranged from about 0.8 μ g g^?1 dw to nearly 4 μ g 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 μ g g^?1 dw to around 11 μ g g^?1 dw in fresh manure and from 3.5 μ g g^?1 dw to almost 9 μ g 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.