Multiresidue Method Research Articles

An integrative review on the analysis of pesticide multiresidues in sweet pepper samples using the QuEChERS method and chromatographic techniques

Since foods are complex matrices that contain pesticides of different classes, multiresidue sample preparation methods such as QuEChERS (Quick, Easy, Cheap, Effective, Rugged, Safe) are used and modified to obtain more accurate and sensitive results. This work was developed through an integrative review in the journal databases Capes, Science Direct, Scielo, and Scientia Chromatographic, from 2011 to 2021, to answer the following question: “What is the most efficient and advantageous sample preparation method for the determination of multiresidue pesticides of interest in sweet pepper samples, when chromatographic techniques are used for detection?” The sweet pepper was chosen because the Pesticide Residue Analysis in Food Program (PARA) suggests that it is the sample with the highest percentage of irregularities related to active ingredients not allowed or above the Maximum Residue Limit (MRL). A total of 391 articles were found, 11 of which met the inclusion criteria established. Several analyses were studied. The organophosphates were the most studied class of pesticide, with seven articles. In addition, there was a predominance of nonpolar analytes (log Kow > 1). The use of different extracting solvents, such as methanol, acetonitrile, ethyl acetate, and acetone, was observed, with acetonitrile presenting the best analytical parameters in most cases. The use of different sorbents such as secondary and primary secondary amine (PSA), ocatadecyllane (C18), graphite carbon (GCB), and carbon black was noted, as well. The authors highlight the difficulties in the analysis when the matrix effect is significant (except for fensulfothion, tensulfothion, flonicamid, and its metabolite TFNA-AM) and the degradation of analytes through the analysis process (flonicamid, captan, folpet, thiophanate methyl and benomyl). Finally, the statistical test Analysis of Variance (ANOVA) was used to identify if there was a significant difference between the different methods used for the same analysis or when the same method used for the different analytes.

Comparison of Extraction and Clean-up Methods Modified in Different Ways for the Determination of Pesticide Residues in Bees

As a result of the unconscious use of pesticides, honeybees are adversely affected, thus causing colony losses all over the world. In this research, different extraction and clean-up methods were compared on bee samples based on the QuEChERS method which is the most widely used pesticide analysis method in food. This research includes application studies for the multi residue method (MRM), which allows analysis of more than one pesticide. During the extraction phase, 7 different methods were compared, while the method with the most suitable repeatability and recovery values among these methods was taken to the clean-up phase. In the clean-up phase, 5 different clean-up methods were tried on the method which yielded the best values in extraction. In terms of average percentage recovery values, the 1stextraction method ranks first with 72 active substances between 70-120%, and the 3rd clean-up method with 92 active substances. Thus, while the number of active substances with suitable recovery values in the selected extraction method was 72, it increased to 92 with the continuation of the clean-up method, achieving a success rate of 92%. It is recommended to use this method in pesticide residue analyzes in bees with its outstanding features such as completing the analyzes in a short time, working easily with the infrastructure that can be found in all control laboratories, low analysis costs, ease of use, and reliability.

Development and Validation of Benzophenone Derivatives in Packaged Cereal-Based Foods by Solid-Liquid Extraction and Ultrahigh-Performance Liquid Chromatography-Tandem Mass Spectrometry.

We established and validated a sensitive multi-residue analytical method for identifying benzophenone (BP) and nine BP derivatives (2,4-dihydroxybenzophenone [BP-1], 2,2′,4,4′-tetrahydroxydroxybenzophenone, 2-hydroxy-4-methoxy benzophenone, 2,2′-dihydroxy 4-methoxy benzophenone, 2-hydroxybenzophenone [2-OHBP], 4-hydroxybenzophenone, 4-methylbenzophenone [4-MBP], methyl-2-benzoylbenzoate, and 4-benzoylbiphenyl). Solid–liquid extraction pretreatment and ultra-high-performance liquid chromatography–tandem mass spectrometry (UHPLC–MS/MS) were employed in an analysis of 85 packaged cereal-based food samples (25 pastry, 50 rice, and 10 noodle samples). The method had satisfactory linearity (R2 ≥ 0.995), low limits of detection (pastry: 0.02–4.2 ng/g; rice and noodle: 0.02–2 ng/g), and favorable precision, with within-run and between-run coefficient of variation ranges of 1–29% and 1–28%, respectively. BP and 4-MBP were detected in 100% of the pastry samples, and BP-1 and 2-OHBP were found in 76% and 56% of the pastry samples, respectively. BP and 2-OHBP were found in 92% and 38% of the rice samples, respectively. BP was found in 50% of the noodle samples. BP contributed the most to the total level of BPs in pastries, with significantly higher mean ± standard deviation (range) levels for pastries (26.8 ± 32.6 [1.8–115.4] ng/g) than rice (1.2 ± 2.0 [0.4–13.4] ng/g) and noodles (0.7 ± 0.7 [0.4–1.9] ng/g); p < 0.0001). The trace levels of 4-MBP identified in the samples demonstrate the need for the development of analytical methods with high sensitivity and specificity; the proposed method satisfies this need.

Determination and level investigation of 45 hormones in edible bird's nest by solid phase extraction-high performance liquid chromatography-tandem mass spectrometry

建立了固相萃取-高效液相色谱-串联质谱(SPE-HPLC-MS/MS)同时测定食用燕窝中皮质激素、雌激素、雄激素及孕激素等5类45种激素的多残留分析方法。采用乙腈-乙酸乙酯(1∶1, v/v)超声辅助提取、亲水亲脂平衡固相萃取柱净化,甲醇洗脱。分别在正、负电喷雾电离源、多反应监测模式下检测45种激素。正离子模式下的流动相为乙腈-0.1%甲酸水溶液,负离子模式下的流动相为乙腈-水,色谱柱为Phenomenex Kinetex C18柱(100 mm×2.1 mm, 2.6 μm)。在优化条件下,45种激素在0.20~20.0 μg/L范围内线性关系良好,相关系数(R2)≥0.9990,方法的检出限(LOD)为0.04~0.70 μg/kg,定量限(LOQ)为0.16~2.00 μg/kg。按三水平(2.0、4.0、20.0 μg/kg)进行加标回收试验,氟米龙、布地奈德、醛固酮、醋酸氟轻松、炔雌醇的回收率为40.2%~63.6%,可对这5种激素进行定性分析,其余40种激素的平均加标回收率为72.2%~112.3%,相对标准偏差(RSD)为2.5%~11.6%,该方法可对40种激素进行准确定性定量,精密度好,灵敏度高,简便、快速。从2017~2021年,通过研究建立的方法对来自马来西亚、印度尼西亚、泰国和越南等国家的1021个燕窝样品进行监测,仅勃地酮、雄烯二酮、孕酮有检出(大于检出限),其他激素均小于检出限。孕酮检出率为100%,勃地酮、雄烯二酮检出率分别为79%和89%, 3种激素含量范围分别为0.097~3.58、0~0.096和0~1.77 μg/kg。与同为动物源性食品的鸡蛋、纯牛奶、乳制品相比,所有测定的鸡蛋样品中均检出雄烯二酮,含量比其他3类产品略高;勃地酮在4类产品中的含量差别不大,均为微量;孕酮含量在鸡蛋中最高,其次是纯牛奶,燕窝中含量最低。研究结果表明,食用燕窝带入的激素种类少,含量低,对健康影响小。

Health risk associated with pesticide residues in vegetables from Incheon region of Korea.

This study was conducted to investigate the pesticide residue concentrations and assess potential human health risks from vegetable consumption in Incheon. A total of 960 samples were collected from the Incheon areas of Korea in 2019. The pesticide residues were analyzed by the multi-residue method of the Korean Food Code for 373 different pesticides using GC-MS/MS, LC-MS/MS, GC-ECD/NPD, and HPLC-UVD. Among the vegetable samples, 869 samples (90.5%) were free from detectable residues, while 91 samples (9.5%) contained residues, and 16 samples (1.7%) had residues exceeding the Korean maximum residue limit (MRLs). A total of 33 different pesticide residues were found, and 11 residues exceeded MRLs. The most frequently detected pesticide residues were chlorfenapyr, fludioxonil, pyridalyl, hexaconazole, and procymidone. Samples exceeding the MRLs were found in aster scaber, coastal hog fennel, lettuce (leaves), mustard green, mustard leaf, perilla leaves, Pimpinella brachycarpa, radish leaves, shepherd' purse, spinach, and winter-grown cabbage. The potential health risk assessment of pesticides was estimated by calculating the estimated daily intake (EDI) and the acceptable daily intake (ADI). The range of HQs was 0.002-90.621%, which was below 100%. Therefore, the results of this study show that the detected pesticide could not be considered a serious public health problem through the consumption of vegetables.

Comprehensive screening of polar emerging organic contaminants including PFASs and evaluation of the trophic transfer behavior in a freshwater food web

Bioaccumulation and trophic transfer of persistent legacy contaminants have been intensively characterized, but little is known on the contaminants of emerging concern (CECs) in freshwater food webs. Herein, we comprehensively screened CECs with a focus on polar substances and further evaluated their trophic transfer behavior in selected items from the food web of Lake Templin, Germany. Weselected one plankton, two mussel, and nine fish samples covering three trophic levels. With an effective multi-residue sample preparation method and high-resolution mass spectrometry-based target, suspect, and non-target screening, we characterized 477 targets and further screened unknown features in complex biota matrices. Of the 477 targets, 145 were detected and quantified in at least one species (0.02–3640 ng/g, dry weight). Additionally, the suspect and non-target analysis with experimental mass spectra libraries and in silico techniques (MetFrag and SIRIUS4/CSI:FingerID) enabled further identification of 27 unknown compounds with 19 confirmed by reference standards. Overall, the detected compounds belong to a diverse group of chemicals, including 71 pharmaceuticals, 27 metabolites, 26 pesticides, 16 per- and polyfluoroalkyl substances (PFASs), 4 plasticizers, 3 flame retardants, 11 other industrial chemicals and 14 others. Moreover, we determined the trophic magnification factor (TMF) of 34 polar CECs with >80% detection frequency, among which 6 PFASs including perfluorooctane sulfonic acid (PFOS), perfluorodecanoic acid (PFDA), perfluorohexane sulfonic acid (PFHxS), perfluorotridecanoic acid (PFTrA), perfluorotetradecanoic acid (PFTeA), and perfluoroundecanoic acid (PFUnA), exhibited biomagnification potential (TMF =1.8 - 4.2, p < 0.05), whereas 5 pharmaceuticals (phenazone, progesterone, venlafaxine, levamisole, and lidocaine) and 1 personal care product metabolite (galaxolidone) showed biodilution potential (TMF = 0.4 - 0.6, p < 0.05).

Multiresidue analytical method for high production volume chemicals in dust samples, occurrence and human exposure assessment

A multiresidue analytical method based on pressurised liquid extraction and gas-chromatography mass spectrometry was developed to determine 22 compounds belonging to different chemical families in indoor dust.: Seven organophosphate esters, six phthalate esters, three benzotriazoles, five benzothiazoles and four benzenesulfonamides were included in the present study, all of them belonging to the category of high production volume chemicals (HPVCs). Apparent recoveries ranged between 45% and 123% and method quantification limits ranged from 0.03 μg/g to 3.8 μg/g. The occurrence of the selected HPVCs was evaluated in indoor dust from different locations in the Tarragona (Catalonia, Spain) region. Two benzenesulfonamides, ortho-toluenesulfonamide and para-toluenesulfonamide, were detected in dust samples for the first time. Phthalate esters and organophosphate esters were the most abundant compounds found, and di-(2-ethylhexyl) phthalate (DEHP) was determined at the highest concentrations. With the data obtained, human exposure was assessed by calculating the estimated daily intakes (EDI) via ingestion and dermal contact. Non-carcinogenic and carcinogenic risk assessments found no risks in any of the scenarios tested, which included two age classes (children and adults) and two possible exposure scenarios (median and worst-case scenario), except for the evaluation of carcinogen risk due to ingestion of DEHP in the worst-case scenario.

Method validation and risk assessment for sulfonamides and tetracyclines in bees’ honey from Egypt, Libya and Saudi Arabia

Several studies worldwide have reported contamination of bees’ honey by antibiotics, which may pose a hazard to consumers’ health. The present study was thus established to: (1) introduce a validated multi-residue method for determining sulfonamides (SAs) and tetracyclines (TCs) in honey; and (2) characterize the potential risk due to the exposure to SAs and TCs in honey samples from Egypt, Libya, and Saudi Arabia. SAs and TCs were simultaneously extracted using solid-phase extraction and matrix solid phase dispersion methods. SAs and TCs were screened using HPLC–MS/MS and HPLC–DAD. The results confirmed detection limits for SAs and TCs by HPLC–MS/MS of 0.01 and 0.02–0.04 (ng g−1), respectively. The limits were 2.5–5.6 and 12.0–21.0 (ng g−1) for SAs and TCs by HPLC–DAD, respectively. The obtained accuracy rates were in the ranges of 83.07–86.93% and 86.90–91.19%, respectively, for SAs and TCs, with precision rates lower than 9.54%. Concerning the occurrence of antibiotics, the positive samples constituted 57.6%, 75%, and 77.7% of the Egyptian, Saudi Arabian, and Libyan samples, respectively. Notably, SAs antibiotics were the most prevalent in the Egyptian and Saudi Arabian samples; in contrast, TCs were the most dominant in Libya. Calculated parameters of risk assessment, concerning the aggregated exposure to SAs and TCs, showed no potential adverse effects from the exposure to contaminated honey in studied countries.

A validated multiresidue method for the determination of 34 pesticide residues in different types of tea bags using QuEChERS method with LC-ESI-MS/MS

A validated multiresidue method for the determination of 34 pesticide residues in different types of tea bags using QuEChERS method with LC-ESI-MS/MS

Multi-class, multi-residue determination of 132 veterinary drugs in milk by magnetic solid-phase extraction based on magnetic hypercrosslinked polystyrene prior to their determination by high-performance liquid chromatography – tandem mass spectrometry

A quantitative multi-class multi-residue analytical method was developed for the determination of veterinary drugs in milk by high-performance liquid chromatography – tandem mass spectrometry (HPLC-MS/MS). A total of 132 veterinary drugs investigated belonged to almost 15 classes including sulfonamides, β-lactams, tetracyclines, quinolones, macrolides, nitrofurans, nitroimidazoles, phenicols, lincosamides, pleuromutilins, macrocyclic lactones, quinoxaline antibiotics, benzimidazoles, anthelmintics, coccidiostats and some others. A magnetic solid-phase extraction procedure was developed using magnetic hypercrosslinked polystyrene (HCP/Fe3O4) for the sample preparation prior to HPLC-MS/MS without deproteinization step. The results indicated recoveries of 85–107% for 14 sulfonamides, 85–120% for 13 β-lactams, 89–115% for 4 tetracyclines, 82–119% for 14 quinolones, 82–115% for 8 macrolides, 97–109% for 4 nitrofurans, 84–115% for 10 nitroimidazoles, 89–114% for 3 phenicols, 86–111% for 3 lincosamides, 97–102% for 2 pleuromutilins, 72–88% for 4 macrocyclic lactones, 87–104% for 4 quinoxaline antibiotics, 76–119% for 21 benzimidazoles, 79–115% for 12 anthelmintics, 81–118% for 12 coccidiostats and 75–119 % for 5 unclassified drugs, with relative standard deviations (RSDs) of less than 20%, and the LOQs ranged from 0.05 to 1 μg kg−1. This methodology was then applied to field-collected real milk samples and trace levels of some veterinary drugs were detected.

Analytical method to monitor contaminants of emerging concern in water and soil samples from a non-conventional wastewater treatment system

Nonconventional wastewater treatments, such as vegetation filters (VFs), are propitious systems to attenuate contaminants of emerging concern (CECs) in small municipalities. The development of standardised multiresidue and multimatrix methods suitable for measuring a reliable number of CEC in environmental samples is crucial for monitoring infiltrating concentrations and for ensuring these systems’ treatment capacity. The objective of this study is to develop and validate an analytical method for the simultaneous determination of CECs, including transformation products (TPs), with diverse physico-chemical properties, in environmental samples. The optimised method is based on sample clean-up and preconcentration by solid-phase extraction (SPE), followed by liquid chromatography electrospray ionization tandem mass spectrometry (LC-MS/MS). The method is able to detect and quantify 40 target CECs, including pharmaceuticals of different classes (analgesics, antibiotics, antihypertensives, lipid regulators, anticonvulsants, antidepressants, antiarrhythmics, beta-blockers, amongst others), hormones and lifestyle products with good reproducibility (variations below 23%), in different water matrices, and 28 CECs, in soil samples. Acceptable recoveries (65–120%) were obtained for most of the CECs in all the matrices. However in the soil samples, as complexity required a prior extraction treatment, the recovery of some analytes was affected, which reduced the number of target CECs. The achieved methodological quantification limits (0.05–5 ng/L and 0.04–1.1 ng/g levels for the water and the soil matrices, respectively) were reasonably low for most CECs. The proposed method was successfully applied to monitor CECs in a VF. The CECs detected at higher concentrations are some of the world's most widely used products (e.g. acetaminophen or caffeine and its main TP, paraxanthine). The results showed an almost 70% reduction in CEC concentrations during infiltration. The groundwater data indicated that the VF treatment operation did not affect the underlying aquifer (Cmax found in GW <1 µg/L).

Development of a Liquid Chromatography-Tandem Mass Spectrometry Method for the Simultaneous Determination of 40 Drugs of Abuse in Human Urine: Application to Real Cases.

Drugs of abuse are constantly evolving, while new synthetized substances are constantly emerging to avoid regulations. However, traditional drugs such as cocaine and amphetamine are still two of the most consumed drugs in the world. It is important, therefore, to provide suitable multiresidue methods for determining a wide range of drugs for use in toxicological and forensic analyses. The aim of this study is to develop a method for determining several families of drugs of abuse, including classic drugs, new psychoactive substances and some of their metabolites, in urine by liquid chromatography-tandem mass spectrometry. Urine is one of the most common biological matrices used in drug analysis because of its easy collection and a wide window of detection. In this study, we used solid-phase extraction to remove interferences and extract analytes from urine. Four different mixed-mode cation-exchange commercial sorbents were evaluated. The best results, in terms of apparent recoveries, were achieved with one of the strong cationic sorbents, ExtraBond SCX. The method achieved detection limits from 0.003 to 0.500 ng/mL and quantification limits from 0.050 to 1.500 ng/mL, which are suitable for determining these compounds at the usual levels found in the urine of drug users. The applicability of this method was demonstrated by analyzing real urine specimens from women following a detoxification program. Our results showed that the drug most consumed was cocaine, since it was detected in most urine specimens together with its main metabolite, benzoylecgonine. The polyconsumption of drugs from different families was also observed in some urine samples analyzed.

Carcinogenic and non-carcinogenic risk assessment induced by pesticide residues in honey of Iran based on Monte Carlo simulation

A multi-residue method was developed for 45 pesticides from different groups, encompassing the most widely used pesticides. 30 samples of honey were randomly collected from different regions of Iran and extraction was performed using validated QuEChERS method. Next, pesticide residues were identified and measured using optimized UHPLC-MS/MS and GC-MS analysis. All validation assays were performed with a blank sample. For the evaluation of linearity, matrix-matched calibration curves were prepared with spiked samples at seven concentration levels, ranging from 0.005 to 0.5 mg L−1 for pesticides in UHPLC-MS/MS and from 0.025 to 2 mg L−1 for GC-MS analysis. Recovery and precision were certified through extraction of spiked samples at concentration levels of 0.1 and 0.25 mg L−1. The limit of quantification (LOQ) was fixed as the lowest concentration level of the calibration curve, which presented adequate recovery and precision. Results indicated that the observed pesticides in honey samples were approximately 44.4% of the total studied pesticides, of which 90% belonged to the group of insecticides. Eventually, the human health risk assessment was performed for children and adult consumers based on Monte Carlo simulation. The rank order of pesticides based on HQ was lindane > diazinon > trichlorfon > permethrin for honey samples. In our study, the calculated hazard index (HI) for adults (0.18) and for children (0.57) lower than 1, suggested no potential health risks to the honey consumers. All pesticides except for lindane did not pose a cancer risk to humans, unfortunately due to lindane residue as a Persistent Organic Pollutants (POPs), CR (2.5E-5) was higher than 1.0E-6 and controlling plans should be conducted to decrease the concentration of this pesticide in Iran.

Development of a vortex oscillating clean-up column for high-throughput semi-automatic sample preparation of drug residues in fish muscle tissues

A novelty high-throughput semi-automatic sample clean-up method was developed and used for rapid analysis of 9 drug residues in fish muscle tissues combined with high-performance liquid chromatography/quadrupole-linear ion trap mass spectrometry (HPLC-QTRAP-MS/MS). The target compounds were extracted by Quick, Easy, Cheap, Effective, Rugged and Safe multiresidue (QuEChERS) method with acetonitrile. A vortex oscillating clean-up column was proposed for single step purification firstly. After centrifugation, 1 mL of acetonitrile layer was transferred into a 3 mL vortex oscillating clean-up column which packed with 150 mg C18 sorbent. The column was covered with piston, placed on a column-tube rack, vigorously agitated on a multi-tube vortex mixer. After vortex oscillation, purified extract was obtained for analysis by pushing the piston of oscillating clean-up column. The performance of the developed method was validated by analyzing 9 analytes in spiked grass carp muscle tissues. The limits of quantification (LOQs) ranged from 1.0 to 5.0 μg kg−1. The recoveries were in the range of 101–119% at the four concentration levels (2.0, 5.0, 10.0, 20.0 μg kg−1). Inter-day and intra-day relative standard deviations (RSDs) were lower than 16% for all analytes.

Determination of 38 antibiotics in raw and treated wastewater from swine farms using liquid chromatography-mass spectrometry.

The present study firstly aimed at developing a multi-residue method to identify and quantify 38 veterinary antibiotics (belonging to five different classes) not only for raw swine wastewater but also for wastewater differently treated by different units. The proposed method is based on a solid-phase extraction procedure and ultra high performance liquid chromatography with mass spectrometry. For sample preparation, the optimal loading sample volume was selected as 50mL, the pH of which was adjusted to approximately 3.0 using formic acid. Then 0.1g/L ethylenediaminetetraacetic acid disodium salt was added. The recovery rates for different types of wastewaters were in the range of 35.94-124.51% and the relative standard deviations were in the range of 0.36-14.62%. All the matrix standard curves exhibited high linearity (0.9956-0.9999). The matrix effects for the target antibiotics ranged from -61.73 to +148.75%. To ensure the practicality of the method, we performed the detection of the actually added concentration to determine method detection limits and quantitation limits. The quantitation limits of most of the target antibiotics were 0.04 μg/L, except for spiramycin (0.1 μg/L) and roxithromycin (0.2 μg/L). This optimized and validated method was applied to analyze antibiotic residues in swine water samples from four swine farms.

QuEChERS-based analytical methods developed for LC-MS/MS multiresidue determination of pesticides in representative crop fatty matrices: Olives and sunflower seeds

Oilseed crops are greatly extended all over the world. Their high fat content can interfere during pesticide multiresidue analysis through liquid chromatography-tandem mass spectrometry (LC-MS/MS). This work aimed at overcoming this issue by developing and validating two QuEChERS-based methods for LC-MS/MS determination of 42 pesticides in two fatty food matrices: olives and sunflower seeds. Optimization of the extraction method was achieved following a 26-2 fractional factorial design in a highly cost-effective way. Validation of the multi-residue methods demonstrated improved limits of detection, below the established maximum residue levels (MRLs) for almost all compounds, good precision, and trueness, in compliance with SANTE guidelines. Application of these methods to the analysis of real samples from the Iberian Peninsula showed the presence of some pesticides of relevant environmental concern, including four compounds contained in the Pesticide Action Network International list of highly hazardous pesticides, found at levels between 0.03 ng/g and 104 ng/g.

Chimpanzee exposure to pollution revealed by human biomonitoring approaches

Wildlife is increasingly exposed to environmental pollution, but data illustrating to what extent this exposure can impact health and survival of endangered species is missing. In humans, hair matrix analysis is a reliable tool for assessing cumulative exposure to organic pollutants such as pesticides but has rarely been used in other primates for this purpose. LC/MS-MS and GC/MS-MS multi-residue methods were used to screen the presence of 152 organic pollutants and their metabolites belonging to 21 different chemical families in hair samples from our closest relative, the chimpanzee. Samples were collected from 20 wild chimpanzees in Sebitoli, Kibale National Park, Uganda and 9 captive chimpanzees in the Réserve Africaine de Sigean, France. In total, 90 chemicals were detected, 60 in wild chimpanzees and 79 in captive chimpanzees. The median concentrations of detected chemicals in captive individuals were significantly higher than those in wild chimpanzees. Hair from the captive individuals at RAS was sampled a second time after 6 months in an environment of reduced exposure to these pollutants (diet of organic food, decreased use of plastic food and water containers). The number of chemicals detected in captive chimpanzees reduced from 79 to 63, and their concentrations were also significantly reduced. In the present study we report for the first time the use of hair analysis to detect organic pollutants in primate hair. We conclude that both wild and captive chimpanzees are exposed to a large range of different chemicals through their diet. Our study provides surprising and alarming evidence that besides the direct threats of poaching, deforestation and diseases, wild chimpanzees might be endangered by indirect consequences of anthropic activities. As chimpanzees are our closest relatives, our results should be considered as an alert for human health as well.

A Fully Automated Online SPE-LC-MS/MS Method for the Determination of 10 Pharmaceuticals in Wastewater Samples.

The increasing use of pharmaceuticals, their presence in the aquatic environment, and the associated toxic effects, have raised concerns in recent years. In this work, a new multi-residue analytical method was developed and validated for the determination of 10 pharmaceuticals in wastewaters using online solid-phase extraction (online SPE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS). The compounds included in the method were antineoplastics (cabazitaxel, docetaxel, doxorubicin, etoposide, irinotecan, methotrexate, paclitaxel, and topotecan), renin inhibitors (aliskiren), and antidepressants (maprotiline). The method was developed through several experiments on four online SPE cartridges, three reversed phase chromatography columns, and four combinations of mobile phase components. Under optimal conditions, very low limits of detection (LODs) of 1.30 to 10.6 ng L−1 were obtained. The method was repeatable, with relative standard deviations (RSD, %) for intraday and interday precisions ranged from 1.6 to 7.8 and from 3.3 to 13.2, respectively. Recovery values ranged from 78.4 to 111.4%, indicating the reproducibility of the method. Matrix effects were mainly presented as signal suppression, with topotecan and doxorubicin being the two most affected compounds (31.0% signal suppression). The proposed method was successfully applied to hospital effluents, detecting methotrexate (4.7–9.3 ng L−1) and maprotiline (11.2–23.1 ng L−1). Due to the shorter overall run time of 15 min, including sample preparation, and reduced sample volume (0.9 mL), this on-line SPE-LC-MS/MS method was extremely convenient and efficient in comparison to the classical off-line SPE method. The proposed method was also highly sensitive and can be used for ultratrace quantification of the studied pharmaceuticals in wastewaters, providing useful data for effective environmental monitoring.

Multi residue determination of 96 veterinary drug residues in domestic livestock and fishery products in South Korea

This study was to develop a multi-residue quantification method for determination of 96 veterinary drugs in livestock products (beef, pork, chicken, milk, egg) and fishery products (flatfish, eel, and shrimp) using liquid chromatography-tandem mass spectrometry. In addition, the purpose of this study was to verify the identification of veterinary drug residues by applying this analytical method to livestock and aquaculture animals. The coefficient of determination (r2) was more than 0.98 at the matrix-matched calibration curve. The proposed method was validated according to the CODEX guidelines (CAC/GL-71-2009), and most target compounds were found to be in acceptable quantities under the requirements of the validation guidelines. The limit of detection and limit of quantification ranged from 0.3 to 19.7 μg kg−1 and 1 to 65 μg kg−1. Samples (n = 581) were collected and analyzed to investigate the residues in target animal derived foods and 131 samples were detected (22.5%). In addition, only one rockfish sample exceeded the Korean MRL for sulfadiazine (523 μg kg−1; MRL: 100 μg kg−1) and trimethoprim (195 μg kg−1; MRL: 50 μg kg−1). The most frequently detected veterinary drugs were flumequine followed by oxytetracycline, enrofloxacin, trimethoprim, ciprofloxacin, and mebendazole. These results showed that we developed an acceptable analytical method of 96 veterinary drugs in animal derived foods and it will be useful for the safety management of veterinary drugs in livestock products, fish, and shrimp.

Development and Validation of Multi-Residue Method for Drugs Analysis in Human Feces by Liquid Chromatography-Tandem Mass Spectrometry.

The use of veterinary drugs in animal production is a common practice to secure animal and human health. However, residues of administrated drugs could be present in animal food products. Levels of drugs in food of animal origin are regulated within the European Union. In recent years, residues have been detected not only in food, but also in the environmental elements such as water or soil, meaning that humans are involuntarily exposed to these substances. This article presents a multiclass method for the analysis of various therapeutic groups of pharmaceuticals in human feces. Pharmaceuticals are extracted from feces with an acid extraction solvent, and after filtration the extract was analyzed by HPLC–MS/MS. A limit of detection of 10 ng/g was achieved for 9 pharmaceuticals, with linearity over 0.99 and repeatability and reproducibility lower than 20%. The method was satisfactorily applied in 25 feces samples of individuals that had declared not to be under medical treatment for the last two months. Results indicate the presence of six different compounds at concentration between 10 and 456 ng/g. This preliminary study showed the involuntary exposure of human gut microbiota to active substances such as pharmaceuticals