Optimization, validation, and application of a liquid chromatography-tandem mass spectrometry method for the determination of 47 banned drug and related chemical residues in livestock urine using graphitized carboxyl multi-walled carbon nanotubes-based QuEChERS extraction.

The establishment of an efficient method for the analysis of drug residues in animal urine facilitates the real-time monitoring of drugs used in the production of animal-derived food. A modified QuEChERS extraction-liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was established for the determination of 47 banned drug and related chemical residues in livestock urine. The sample was extracted with acetonitrile by converting the acid-base environment. The sample cleanup effects of seven solid phase extraction cartridges and two EMR-Lipid products were compared, and three materials, including graphitized carboxyl multi-walled carbon nanotubes (MWCNTs), PSA, and C18, were selected as QuEChERS adsorbents from 24 materials. All analytes showed good linearity, with correlation coefficients (R2) greater than 0.9936. Low limits of quantification could be obtained, ranging from 0.2 to 5.5 ng/mL. The average recoveries at low, medium, and high spiked levels were in the range of 70.8-114.9 %, with intra-day precision ranging from 2.4 % to 11.2 % and inter-day precision ranging from 4.5 % to 16.1 %. Swine urine and bovine urine samples collected from different farms were effectively analyzed using the developed method, and metronidazole was detected in three swine urine samples.

Establishment of a modified QuEChERS extraction and liquid chromatography-tandem mass spectrometry method for multiple pesticide residues followed by determination of the residue levels and exposure assessment in livestock urine.

The establishment of an analytical method for pesticide residues in livestock urine can realize the real-time monitoring of pesticide pollution in livestock breeding. In this study, a novel method was developed for the determination of 106 pesticide residues in livestock urine based on a modified QuEChERS extraction and liquid chromatography-tandem mass spectrometry. Acetonitrile was used to extract target analytes through acidic and alkaline switching of the sample environment. The purification effect of captiva EMR-Lipid on samples was investigated. Three kinds of materials, C18, polar enhanced polymer (PEP), N-propylethylenediamine (PSA), were selected from 20 kinds of materials as adsorbents for QuEChERS. A mass analysis was carried out using simultaneous scanning in both positive and negative ion mode and multiple reaction monitoring mode. All analytes showed good linearity, with correlation coefficients (R2) greater than 0.9923; their limits of quantification were 0.02-1.95 ng/mL. The average recoveries at low, medium, and high spiked levels were in the range of 70.1 %-117.3 %, with intra-day precision ranging from 3.4 % to 16.9 % and inter-day precision ranging from 4.0 % to 19.3 %. The established analytical method was used to analyze the pesticide residue in swine urine and bovine urine collected from farms in Yining, Xinjiang, China. A total of 8 pesticides were detected, and the residue ranged from less than the limit of quantitation to 22.4 ng/mL. The top three pesticides with the highest detection frequency were clothianidin, thiamethoxam, and dinotefuran. The exposure assessment based on the monitored pesticide residue concentration levels showed that the detected pesticides could pose little risk to cattle and pigs.

Determination of restricted dyes in textile raw material solid wastes by ultra-high performance liquid chromatography-tandem mass spectrometry.

A rapid and highly sensitive method for the quantification of 34 restricted dyes (including acid, basic, disperse, direct, and azo dyes) in solid textile raw material wastes was developed by employing ultrasonic extraction coupled with ultra-high performance liquid chromatography-tandem mass spectrometry(UHPLC-MS/MS). More specifically, the proposed method employed methanol as the extraction solvent, while the mobile phases consisted of acetonitrile and 10 mmol/L ammonium acetate + 0.05% ammonia. A good linearity was achieved over the concentration range of 0.01-200 ng/mL with correlation coefficients (R) between 0.991-0.999, limits of detection (LODs) of 0.25-40.0 µg/kg (S/N = 3) and limits of quantification (LOQs) of 0.84-133.4 µg/kg (S/N = 10). 34 dyes were recovered at three levels ranging from 84.5 to 106.9% with relative standard deviation (RSDs) ranging from 0.59% to 10.61%. Further, the method was applied for the accurate analysis of 32 counts of cotton yarn, waste cotton, and printed fabrics within 15 min. The dyestuffs accurately quantified by this rapid chromatographic procedure covered a wide range of carcinogenic and allergenic dyestuffs listed in the Oeko-Tex Standard 100 (version 02.2023) colourants. The ultrasound technique combined with the ultra-high performance liquid chromatography-tandem mass spectrometry method proposed in this work is thus suitable for the rapid screening, confirmation, and quantitative detection of industrial synthetic dyes within solid waste originating from textile raw materials.

Content level and risk assessment of phthalate esters in surface water of Bosten Lake, China.

Bosten Lake is the main fishing and grazing area in Xinjiang. The pollution of phthalate esters (PAEs) in water has attracted much attention, but limited research has been conducted on PAEs in Bosten Lake. The distribution of PAEs in fifteen sampling sites of surface water in the dry and flood seasons were investigated to explore the content level of PAEs in Bosten Lake, and the risk was evaluated. Seventeen PAEs were detected by GC-MS after liquid-liquid and solid-phase purification. Results showed that the content of ∑PAEs in the water during dry and flood seasons is ND-26.226 µg/L and ND-7.179 µg/L. The content of PAEs in the water of Bosten Lake is at a medium level. DBP and DIBP are the main PAEs. The content of PAEs is related to the physicochemical properties of water, and the physicochemical properties of water in dry season have a more serious impact on PAEs. PAEs in water mainly come from domestic pollution and chemical production. The results of health risk assessment indicate that PAEs in water do not pose a carcinogenic risk or a non carcinogenic risk to human, which can meet the conditions of Bosten Lake as a fishing ground and livestock base, but the pollution of PAEs cannot be ignored.

Residual status and source analysis of phthalate esters in Ulungur Lake, China.

Ulungur Lake is the largest lake in northern Xinjiang and undertakes important aquatic tasks. It is the No. 1 fishing ground in northern Xinjiang, and the problem of persistent organic pollution in the water has received much attention. However, there are few studies on phthalate esters (PAEs) in the water of Ulungur Lake. Understanding the pollution levels, distribution characteristics and sources of PAEs is of great significance for the protection and prevention of water. Fifteen sampling sites are established in Ulungur Lake to collect water samples during flood and dry periods, then seventeen PAEs are extracted from the water samples and purified by liquid-liquid extraction-solid-phase purification. Gas chromatography-mass spectrometry is used to detect the pollution levels and distribution characteristics of the 17 PAEs and analyse their sources. Results show that the concentrations of PAEs in the dry and flood periods are 0.451-9.97 µg/L and 0.0490-6.38 µg/L, respectively. The concentration of ∑PAEs with time is characterised by the dry period > the flood period. The change in flow is the main reason for the diverse concentration distributions of PAEs in different periods. The concentration of ΣPAEs in the dry period is much lower on the side near the lake entrance of the Ulungur River and Irtysh River. In the dry period, PAEs mainly come from chemical production and the use of cosmetics and personal care products; in the flood period, they mainly come from chemical production. River input and atmospheric sedimentation are the main sources of PAEs in the lake.

Determination of cyflufenamid residues in 12 foodstuffs by QuEChERS-HPLC-MS/MS.

Agricultural products are often contaminated with trace amounts of pesticide residues. To ensure food safety, a reliable, sensitive, and efficient method that accurately identifies pesticide residues in a wide variety of foodstuffs is needed. This study applied a modified QuEChERS extraction technique, coupled with high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) to optimize the identification of the cyflufenamid, a new broad-spectrum fungicide with unclear mode of action in toxicity, in 12 foodstuffs. The method has been validated according to the European Union SANTE/12682/2017 guidelines for its linearity, limit of detection (LOD), and limit of quantification (LOQ), indicating an excellent performance. The recovery of cyfluenamid in all matrix were ranged between 70.8% and 117.8%, with relative standard deviation (RSD) <15% which is much lower compared to other methods. The method has been used for determine cyfluenamid in foodstuffs followed the ISO17025:2017 measurement technical note, which demonstrated it is suitable for routine quantitative analysis of cyflufenamid in most of the popular commercial agricultural products.

[Determination of 22 acidic dyes in edible packagings by high performance liquid chromatography-tandem mass spectrometry].

A method for the simultaneous determination of 22 acidic dyes (acid yellow 23, acid red 18, acid blue 7, etc) in edible packagings was developed using high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The samples were extracted with acetonitrile-methanol (5:5, v/v) , and then cleaned up with Strata-X-AW solid-phase extractor. The analytes were separated on a Zorbax Eclipse Plus C18 column (100 mm x 3.0 mm, 1.8 µm) by gradient elution with acetonitrile-10 mmol/L ammonium acetate as the mobile phases. The 22 acidic dyes were determined by electrospray negative ion source (ESI-), and multiple reaction monitoring (MRM) mode. The qualitative analysis was based on the retention times and characteristic ion pairs consisting of one parent ion and two fragment ions, and the quantitative analysis was carried out by matrix-matched external standard method. The results showed that the calibration curves had good linearity for the 22 acidic dyes, and the correlation coefficients (r2) were larger than 0. 991. The limits of quantitation (LOQs, S/N ≥ 10) were in the range of 0.1-2.0 mg/kg in three different matrices (plant capsule, gelatine capsule, oblatum). The average recoveries were in the range of 78.4%-109.5% for the 22 acidic dyes with the relative standard deviations (RSDs) from 4.6% to 14.5% at three spiked levels (1 x LOQ, 2 x LOQ and 10 x LOQ). This method is suitable for the determination of acidic dyes in edible packagings with the characteristics of high accuracy and precision.