Quantitative analysis of conjugated and free estrogens in swine manure: Solutions to overcome analytical problems due to matrix effects

Singh, Ashok K.; Gupta, Sumit; Kumar, Kuldip; Gupta, Satish C.; Chander, Yogesh; Gupta, Arun; Saxena, Richa

doi:10.1016/j.chroma.2013.06.026

Cited by 15 publications

(12 citation statements)

References 57 publications

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“…Acidified manure liquid and solid samples pre-mixed with 13 C labeled E2, gE2 and sE2 (0.25 mM) were spiked with an internal standard mixture containing deuterium labeled conjugated and free estrogens and then extracted as described by Singh et al (2013) and in the supplementary section II.1.4. The water extract was analyzed using HPLC-MS/MS for conjugated hormones and metabolites (supplementary section II.1.3) and the ethyl acetate/methanol extracts were analyzed using GC-MS/MS for free estrogens as described in the Supplementary Information.…”

Section: Quantitative Analysis Of Individual Estrogens and Metabolitementioning

confidence: 99%

Fate of Conjugated and Free Estrogens in Swine Manure Collected from areas Housing Piglets, Pregnant Sows and Finisher Pigs

Ashok¹

2016

JAS

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Occurrence and fate of estrogens and their metabolites were studied in pig manure collected during winter and summer seasons from sites housing piglets (Nursery (Nur)-manure), pregnant and nursing sows (PS manure) and finisher pigs (FPig manure). The liquid and solid fractions of manure were analyzed for (1) total solids (TS), volatile solids (VS) and total organic carbon (TOC), (2) E coli and M fujisawaense enumeration, (3) total and individual estrogens and (4) estrogenic activity. This study showed that VS and OC values, E coli and M fujisawaense enumerations, estrogen concentrations and estrogenic activity exhibited the following pattern: Nur-manure << FPig-manure < PS-manure. The values for summer and winter Nur-manure did not differ significantly, while the values in summer PS-manure or FPig manure samples were significantly higher than values in corresponding winter samples. Although, estrogens distributed between liquid and solid fractions of manure, concentrations of free, but not conjugated, estrogens depended on manures’ TOC values: an increase in TOC associated with an increase in free estrogen concentrations in liquid manure. However, an increase in TOC decreased the bacterial population in manure liquid by increasing their translocation from liquid into the in solids and ensuing bacterial stabilization. This may increase estrogens’ deconjugation and/or degradation. Estrone (E1) sulfate (sE1), free E1 (fE1), E1 glucuronide (gE1) and E1 metabolites were major steroids present in Nur- and PS-manure, while fE2 and gE2 were predominant estrogens in FPig-manure. In total, the winter estrogen load in liquid was 5.1 mg/L and the load in solid was 4.93 mg/kg. Assuming that 2.3 x 108 kg of manure is produced in the USA per day, approximate hormone load will be 2.3 tons/day. However, manure contains microorganisms that hydrolyze estrogens, thus actual hormone load will be considerably lower.

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Section: Quantitative Analysis Of Individual Estrogens and Metabolitementioning

confidence: 99%

Fate of Conjugated and Free Estrogens in Swine Manure Collected from areas Housing Piglets, Pregnant Sows and Finisher Pigs

Ashok¹

2016

JAS

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“…Individual cEs (E2 glucuronate (E2G), E2 sulfate (E2S), E1G, E1S, E3G and E3S) were analyzed using an Applied BioSystems binary High Performance Liquid Chromatograph (HPLC) equipped with a triple-stage quadruple mass spectrometer ( Figure S4A). Individual fEs (estradiol (fE2), estrone (fE1) and estriol (fE3)) were derivatized to the silyl ethers in using pyridine:bis(trimethylsilyl)-trifluoroacetamide before analysis by GC-MS (Agilent 7000 series gas chromatograph Mass Spectrometer, Agilent, Palo Alto, CA, USA) ( Figure S4B) [8]. The detailed analytical procedures are described in the Supplementary section (Tables S1 and S2).…”

Section: Methodsmentioning

confidence: 99%

“…Part-2 manure was mixed with internal standards and poured into a fritted glass column. Conjugated estrogens were eluted with 100 mL of pure water and free estrogens were eluted with 100 mL methanol [8]. The two effluxes were concentrated to 5 mL under nitrogen and reduced pressure.…”

Section: Methodsmentioning

confidence: 99%

“…Mammals excrete two main forms of steroid hormones: (i) the biologically active free-estrogens (fEs) are excreted through feces (accounting for 10% of total steroid excretion); and (ii) the biologically inactive conjugated steroids (cEs) are excreted through urine [7]. Since cEs are the predominant form of estrogens found in manure [7,8], there is a presumption that manure may have poor estrogenic activity. However, earlier studies have shown that storage may increase manure's estrogenic potency due to the hydrolysis of conjugated hormones by glucuronidase and sulfatase enzymes present in manure microorganisms [9,10].…”

Section: Introductionmentioning

confidence: 99%

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Aerobic and Anaerobic Transformations in Estrogens and Nutrients in Swine Manure: Environmental Consequences

Singh

2015

Agriculture

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Pig manure is an excellent fertilizer and rich source of organic carbon and nitrogen compounds such organic nitrogen (O-N) (95% of total nitrogen) that is plant-unavailable-nitrogen (PUN) and mineralized nitrogen (about 1% of total nitrogen) such as ammonium (NH4 + ) and nitrate (NO3) that are plant-available-nitrogen (PAN). In addition, manure also contains two forms of estrogens: (i) poorly estrogenic thus essentially nontoxic conjugated estrogens (cEs) such as estrone (cE1), estradiol (cE2) and estriol (cE3); and (ii) highly estrogenic and toxic free estrogens (fEs) such as fE2, fE1 and fE3. This study showed that aerobic processing reduced concentrations of total carbon (TC), O-N, PAN and NH4 + /NH3 ratio, transiently hydrolyzed cEs (cE2 > cE1 > cE3) into corresponding fEs, transiently increased estrogenic activity and potential toxicity, and rapidly degraded fEs (fE2, fE1 > fE3), thus reducing the estrogenic activity in manure. Unlike aerobic processing, anaerobic processing stabilized and increased PAN and NH4 + /NH3 ratio, thus increasing the manure's fertilizer value. However, anaerobic processing, relative to aerobic processing, poorly hydrolyzed cEs (reducing transient toxicity and increasing reserve toxicity potential) and poorly degraded fEs (increasing toxicity) in manure. Thus, aerobic and anaerobic environments have distinct effects on manures' PAN and estrogenic activity, presenting an interesting dilemma: anaerobic incubation that increases manures' PAN does not effectively degrade estrogens, while aerobic incubation that effectively degrades estrogens (after transiently increasing their estrogenic activity) also decreases PAN, thus making manure less profitable. New techniques are need to fully use manure as organic fertilizer. OPEN ACCESSAgriculture 2015, 5 698

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“…They are produced by animal glands or synthetically. Steroids have been used as growth‐promoting agents for restoring animal muscle strength and increasing muscle size . Nitroimidazoles have antibacterial and antigenic effects, and some of them increase feed conversion rates .…”

Section: Introductionmentioning

confidence: 99%

Syringe cleanup with UHPLC–MS/MS for nitroimidazoles and steroids detection in manure‐based fertilizers

Tong

Wang

et al. 2018

J of Separation Science

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A syringe-dispersive solid-phase extraction method was developed for the determination of seven nitroimidazoles and nine steroids in manure-based fertilizers by ultra-high performance liquid chromatography with tandem mass spectrometry. Methanol and acetonitrile were used to extract the sample, and mixed dispersive sorbents dispersed in the syringe were used for purification. The extract was separated with an HSS-T3 column and detected in positive or negative multiple reaction monitoring mode. Under the optimal conditions, the recoveries of the 16 compounds ranged from 70.3 to 112.3% at the four spiked levels (3, 10, 20, and 50 μg/kg) and the relative standard deviations ranged from 1.0 to 12.4%. The limits of detection and quantification were 0.22-0.86 and 0.73-2.87 μg/kg, respectively. This method is simple, fast, and reliable, and can be used to simultaneously screen and determine nitroimidazoles and steroids in manure-based fertilizers.

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Quantitative analysis of conjugated and free estrogens in swine manure: Solutions to overcome analytical problems due to matrix effects

Cited by 15 publications

References 57 publications

Fate of Conjugated and Free Estrogens in Swine Manure Collected from areas Housing Piglets, Pregnant Sows and Finisher Pigs

Fate of Conjugated and Free Estrogens in Swine Manure Collected from areas Housing Piglets, Pregnant Sows and Finisher Pigs

Aerobic and Anaerobic Transformations in Estrogens and Nutrients in Swine Manure: Environmental Consequences

Syringe cleanup with UHPLC–MS/MS for nitroimidazoles and steroids detection in manure‐based fertilizers

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