Determination of Thirteen Antibiotics Residues in Manure by Solid Phase Extraction and High Performance Liquid Chromatography

doi:10.1016/S1872-2040(08)60063-8

Chinese Journal of Analytical Chemistry

Volume 36, Issue 9, September 2008, Pages 1162-1166

https://doi.org/10.1016/S1872-2040(08)60063-8 Get rights and content

Abstract

A method was developed for determination of 5 sulfonamides, 4 tetracyclines, 2 quinolones, furazolidone, and chloramphenicol in liquid manure and chicken dung using the solid phase extraction with the high performance liquid chromatography detection. Acetonitrile and 0.01 M of oxalic acid were used as the mobile phase to separate 4 tetracyclines and chloramphenicol. Five sulfonamides, two quinolones, and furazolidone were separated by acetonitrile and 0.025 M NH₄OAc. The limit of detection and quantization fall into the range of 0.01–0.05 mg l⁻¹ and 0.03–0.167 mg l⁻¹, respectively. Thirteen antibiotics in liquid manure and chicken dung were extracted using a mixture of ACN acidified with citrate buffer and EDTA-McIlvaine buffer, respectively. Then, they were cleaned-up and preconcentrated by the hydrophilic-lipophilic balance (HLB) cartridge. The overall recovery was up to 54%–110%. This method was successfully used in the detection of 13 antibiotics from 4 livestock husbandries in Tianjin, China. Results showed that all the antibiotics could be detected, with the concentration ranges of 0.3–173.2 mg kg⁻¹.

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Vertical distribution of antibiotics and antibiotic resistance genes in a representative municipal solid waste landfill, China
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Five SAs (sulfadiazine, SDZ; sulfamerazine, SM1; sulfadimidine, SM2; sulfamethoxazole, SMZ; sulfadimethoxine, SMT), three TCs (oxytetracycline, OTC; tetracycline, TC; chlortetracycline, CTC), and two MLs (erythromycin, ETM; roxithromycin, RTM), were measured, due to the extensive use in medicine, agriculture and animal husbandry (Zhang et al., 2015). Antibiotics were extracted from 10 g (dry weight) refuse samples with 50 mL 0.1 M Na2EDTA-Mcllvaine buffer (Hu et al., 2008). The samples were vortex-mixed for 10 min and sonicated for 30 min.
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Different copper sources and levels affect growth performance, copper content, carcass characteristics, intestinal microorganism and metabolism of finishing pigs
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Copper (Cu) is an essential trace element in the production of swine. This study was conducted to investigate the effect of 3 different sources of Cu on growth performance, Cu metabolism, and intestinal microorganisms of finishing pigs, so as to estimate the bioavailability of the 3 sources for pigs. A total of 42 male finishing pigs (88.74 ± 5.74 kg) were randomly allocated to 7 treatments. The factors were 3 sources (CuSO₄, Cu-glycine, Cu-proteinate) and 2 levels (5 and 20 mg/kg) of Cu, plus one negative control treatment (0 mg/kg added Cu level) for the entire 28-d experiment. The average daily gain (ADG) and feed to gain ratio (F:G) both increased when Cu was added. The Cu level in liver, bile, kidney, serum, lung, urine and feces rose (P < 0.001) with increasing dietary Cu level regardless of the source. Meanwhile, pigs receiving organic Cu (glycinate or proteinate) retained more Cu and excreted less Cu than those receiving inorganic Cu (CuSO₄), which showed that organic forms were more bioavailable. At the transcriptional level, changes in the level and source of dietary Cu resulted in modulation of transporters. In the jejunal mucosa, import transporter high affinity copper uptake protein 1 (CTR1) and export transporter ATPase copper transporting alpha (ATP7A) in supplemental Cu treatments were down-regulated compared to the control. Also, peptide transporter 1 (PepT1) and lanine-serine-cysteine transporter, type-2 (ASCT2) were significantly (P < 0.01) up-regulated in 20 mg/kg Cu-proteinate and Cu-glycinate treatments, respectively. Microbial diversity was lowest in the 20 mg/kg CuSO₄ treatment, and the ratio of Firmicutes to Bacteroidetes was higher in added Cu treatments, especially Cu-glycinate treatment. These results indicate that uptake of different Cu forms is facilitated by different transporters and transport mechanisms, and compared with inorganic Cu, organic Cu provides benefits to intestinal microflora and reduces Cu excretion.
Antibiotics in aquaculture ponds from Guilin, South of China: Occurrence, distribution, and health risk assessment
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Antibiotics have been widely used to prevent or treat bacterial infections in aquaculture in the past decades. However, large proportions of these compounds are excreted unchanged in feces and urine of animals, given incomplete metabolism, leading to the residual of unmetabolized compounds, and posing a potential risk to the environment. This study investigated the occurrence and distribution of seven antibiotics in surface water, sediments, fish muscle, and fish feed by high-performance liquid chromatography from the aquaculture areas in Guilin, South of China. The highest concentrations of the target antibiotics in water, sediment, fish muscle, and fish feed were 2047.53 ng/L, 13.32 μg/kg, 35.90 μg/kg, and 2203.97 μg/kg, respectively. In contrast, the most abundant antibiotic was enrofloxacin (ENR), followed by ofloxacin (OFL), sulfadimidine (SMZ), and ciprofloxacin (CIP). In this work, the concentrations of antibiotics were lower than those in other breeding areas. Correlation analyses showed significant relationships between sulfadiazine (SDZ) and TP, TN, and COD_Cr in water. In sediment, the release of SDZ was significantly related to TN, TP, and organic matter. The risk quotient (RQ) results revealed that sulfamethoxazole (SMX), CIP, and ENR were at high risk to microorganisms in water; while, SMX and NOR were at high risk in sediments. The result from the estimated daily intakes (health risk quotient, HQ < 1) suggested that the antibiotics might not pose a risk to human health by dietary exposure assessment; however, sediments may become an accumulation reservoir of antibiotics and cause secondary pollution, of which the local management should raise awareness.
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Using animal manure as organic fertilizer to grow fodder crops is causing public health concerns because animal manure is the major reservoir of veterinary antibiotics. In this study, we used a mathematical model to estimate the risk of human exposure to veterinary antibiotics when using swine manure as organic fertilizer to grow alfalfa (Medicago sativa L.). Alfalfa was planted in a greenhouse and fertilized with swine manure spiked with oxytetracycline (OTC, at 0, 150, and 1500 mg/kg of manure), ofloxacin (OFL, at 0, 15, and 150 mg/kg), or sulfamonomethoxine (SMM, at 0, 5, 15 and 150 mg/kg). Alfalfa was harvested at the budding stage and ensiled for 60 days. Results showed that OTC and OFL could be detected in the alfalfa root, stem, and leaf with a concentration ranging from 8.85 to 59.17 μg OTC /kg and from 1.50 to 4.10 μg OFL/kg dry matter, but SMM could only be detected in the root ranging from 29.10 to 63.75 μg/kg dry matter. The ensiling for 60 days decreased the OFL concentration by 68.7% but only slightly decreased the OTC concentration. The maximum daily exposures of humans to OTC and OFL through liquid milk consumption were estimated to be 5.84E-8 and 1.63E-8 μg, respectively, both of which are well below the intake levels of OTC (72 μg) and OFL (54 μg) mandated by the European Union. The results of the present study indicate that using swine manure as organic fertilizer to grow alfalfa poses a limited risk for human exposure to veterinary antibiotics through the consumption of liquid milk.
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Citation Excerpt :
The reason may be that TCs are widely used in the animal breeding industry due to their low price. In addition, the three farms had different antibiotic residual levels, which may be due to the different drug application habits, and different fodder sources etc. [14]. A sensitive and reliable UHPLC-MS/MS method was developed and validated for the determination of 45 VAs in swine manure samples.
A multiresidue method for identification and quantification of 45 veterinary antibiotics (VAs) belonging to 5 different drug classes has been developed, which is the first comprehensive method for pig manure. The proposed method used mixed liquor with methanol: acetonitrile: citrate buffer ratio of 1:1:2 to extract the target VAs from freeze-dried manure. The extracting solution passed through solid-phase extraction (SPE) procedure with Oasis HLB cartridges, which could isolate the target VAs and clean the samples in a single step. After blow-drying and concentrating, the samples were analyzed by ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) in one single injection with a run time of 12 min. The average recovery rates for most of the VAs were in the range of 50–120% with relative standard deviations below 15%. Linearity was studied in the range between 2 and 1000 μg/kg using matrix-matched calibration and pure solvent calibration, to evaluate the matrix effects (MEs). The limits of detection (LDs) and quantification (LQs) were in the range of 0.01–1.54 μg/kg and 0.03–5.13 μg/kg respectively, except for penicillin G. Finally, the proposed method was used to quantify VA residues in real swine manure from three farms with different scales; tetracyclines, sulfonamides, quinolones and macrolides were the most frequently detected compounds.

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: This work was supported by the grants from the National Science Foundation of China (No. 20777041) and Tianjin Municipal Science and Technology Commission of China (Grants 06TXTJJC14000).

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RESEARCH PAPERDetermination of Thirteen Antibiotics Residues in Manure by Solid Phase Extraction and High Performance Liquid Chromatography

Abstract

Environmental Pollution

J. Chromatogr. A

Anal. Chim. Acta

Chemosphere

J. Chromatogr. A

J. Chromatogr. A

J. Chromatogr. A

RESEARCH PAPER
Determination of Thirteen Antibiotics Residues in Manure by Solid Phase Extraction and High Performance Liquid Chromatography