High sensitive multiresidue analysis of pharmaceuticals and antifungals in surface water using U-HPLC-Q-Exactive Orbitrap HRMS. Application to the Danube river basin on the Romanian territory.

The occurrence of 67 pharmaceutical and antifungal residues in the Danube river on the Romanian territory was studied by using solid-phase extraction (SPE) and LC-Q Exactive Orbitrap high resolution MS in both full scan (FS) MS and targeted MS/MS modes. A single-laboratory validation procedure was carried out for the determination of 67 compounds in FSMS mode evaluating selectivity, sensitivity, linearity, precision and accuracy. The method showed satisfactory analytical performance.

Simultaneous determination of seven gestagens in kidney fats by Ultra Performance Convergence Chromatography tandem mass spectrometry.

An ultra-performance convergence chromatography (UPC2) system coupled tandem mass spectrometry was successfully utilised to analyse chlormadinone acetate, delmadinone acetate, fluorogestone acetate, medroxyprogesterone acetate, megestrol acetate, melengestrol acetate, chlortestasterone acetate in bovine and porcine kidney fat. This novel approach obtained an improved resolution in comparison to previously reported chromatographic methods combined with MS detector in a shorter analytical time. All the acetylgestagen compounds were well separated on a ACQUITY UPC(2) HSS C18 column (3.

Carry-over of veterinary drugs from medicated to non-medicated feeds in commercial feed manufacturing plants.

Different compound feeds have to be manufactured in the same production line. As a consequence, traces of the first produced feed may remain in the production and get mixed with the next feed batches. This "carry-over" is unavoidable, and so non-medicated feed can be contaminated with veterinary drugs like antibiotics added to the previous batch of medicated feed.

Comprehensive analysis of ß-lactam antibiotics including penicillins, cephalosporins, and carbapenems in poultry muscle using liquid chromatography coupled to tandem mass spectrometry.

A comprehensive method for the quantitative residue analysis of trace levels of 22 ß-lactam antibiotics, including penicillins, cephalosporins, and carbapenems, in poultry muscle by liquid chromatography in combination with tandem mass spectrometric detection is reported. The samples analyzed for ß-lactam residues are hydrolyzed using piperidine in order to improve compound stability and to include the total residue content of the cephalosporin ceftifour. The reaction procedure was optimized using a full experimental design.

Uptake of oxytetracycline, sulfamethoxazole and ketoconazole from fertilised soils by plants.

This study was performed to investigate the potential for a set of two antibiotics and one antifungal compound to be taken up from the soil by plants. Plants are used for animal or human consumption, and so the measured concentrations in the plant material will be used to model potential human exposure to these compounds. The uptake by two types of plants (grass and watercress) from two types of soil was studied.

Application of EU guidelines for the validation of screening methods for veterinary drugs.

Commission Decision (CD) 2002/657/EC describes detailed rules for method validation within the framework of residue monitoring programmes. The approach described in this CD is based on criteria. For (qualitative) screening methods, the most important criteria is that the CCβ has to be below any regulatory limit.

Ultrasonic or accelerated solvent extraction followed by U-HPLC-high mass accuracy MS for screening of pharmaceuticals and fungicides in soil and plant samples.

Different veterinary pharmaceuticals are used in agricultural livestock becoming a source of environment contamination. Furthermore, no regulation exists for the concentration limits of pharmaceuticals in soil or water. Monitoring programs for environment contamination with pharmaceuticals are needed, requiring new sensitive and selective screening methods.

Quantitative trace analysis of a broad range of antiviral drugs in poultry muscle using column-switch liquid chromatography coupled to tandem mass spectrometry.

A liquid chromatography-tandem mass spectrometry method for the analysis of seven antiviral drugs, zanamivir, ribavirin, oseltamivir, oseltamivir carboxylate, amantadine, rimantadine and arbidol, in poultry muscle is reported. The antiviral drugs were extracted from the homogenized poultry muscle sample using methanol. The extract was purified using tandem solid-phase extraction combining a cation exchange cartridge and a phenylboronic acid cartridge.

Determination of the stability of antibiotics in matrix and reference solutions using a straightforward procedure applying mass spectrometric detection.

The stability of an antibiotic is a very important characteristic, especially in the field of antibiotic residue analysis. During method development or validation, the stability of the antibiotic has to be demonstrated no matter if the method is used for screening, confirmation, qualitative or quantitative analysis. A procedure for testing the stability of antibiotics in solutions and food samples using LC-MS/MS is described.

Feasibility of desorption electrospray ionization mass spectrometry for rapid screening of anabolic steroid esters in hair.

Hormone and veterinary drug screening and forensics can benefit from the recent developments in desorption electrospray ionization (DESI) mass spectrometry (MS). In this work the feasibility of DESI application for the rapid screening of intact esters of anabolic steroids in bovine hair has been studied. Using a linear ion trap both full scan and data-dependent collision induced dissociation MS(n) spectra were acquired in minutes for testosterone cypionate, testosterone decanoate and estradiol benzoate standard solutions deposited on a glass or PTFE surface.

Influence of anabolic combinations of an androgen plus an estrogen on biochemical pathways in bovine uterine endometrium and ovary.

The application of anabolic steroids in food producing animals is forbidden in the EU since 1988, but the abuse of such drugs is a potential problem. The existing test systems are based on known compounds and can be eluded by newly emerging substances. The examination of physiological effects of anabolic hormones on different tissues to indirectly detect misuse might overcome this problem.

Fully automated screening of veterinary drugs in milk by turbulent flow chromatography and tandem mass spectrometry.

There is an increasing interest in screening methods for quick and sensitive analysis of various classes of veterinary drugs with limited sample pre-treatment. Turbulent flow chromatography in combination with tandem mass spectrometry has been applied for the first time as an efficient screening method in routine analysis of milk samples. Eight veterinary drugs, belonging to seven different classes were selected for this study.

Generic sample preparation combined with high-resolution liquid chromatography-time-of-flight mass spectrometry for unification of urine screening in doping-control laboratories.

A unification of doping-control screening procedures of prohibited small molecule substances--including stimulants, narcotics, steroids, beta2-agonists and diuretics--is highly urgent in order to free resources for new classes such as banned proteins. Conceptually this may be achieved by the use of a combination of one gas chromatography-time-of-flight mass spectrometry method and one liquid chromatography-time-of-flight mass spectrometry method. In this work a quantitative screening method using high-resolution liquid chromatography in combination with accurate-mass time-of-flight mass spectrometry was developed and validated for determination of glucocorticosteroids, beta2-agonists, thiazide diuretics, and narcotics and stimulants in urine.

Detectability of testosterone esters and estradiol benzoate in bovine hair and plasma following pour-on treatment.

The abuse of synthetic esters of natural steroids such as testosterone and estradiol in cattle fattening and sports is hard to detect via routine urine testing. The esters are rapidly hydrolysed in vivo into substances which are also endogenously present in urine. An interesting alternative can be provided by the analysis of the administered synthetic steroids themselves, i.

Effect of sample pre-treatment on the determination of steroid esters in hair of bovine calves.

The effect of three sample pre-treatment steps, washing, cutting and grinding on the determination of steroid esters in hair is studied. The study is performed by using hair samples obtained after pour-on application of steroid esters to bovine calves. After sample pre-treatment the hair is treated with a mild reducing agent [tris(2-carboxyethyl)phosphine hydrochloride] to extract the steroid esters.

Multi-residue screening of veterinary drugs in egg, fish and meat using high-resolution liquid chromatography accurate mass time-of-flight mass spectrometry.

The last 2 years multi-compound methods are gaining ground as screening methods. In this study a high-resolution liquid chromatography combined with time-of-flight mass spectrometry (HRLC-ToF-MS) is tested for the screening of about 100 veterinary drugs in three matrices, meat, fish and egg. While the results are satisfactory for 70-90% of the veterinary drugs, a more efficient sample preparation or extract purification is required for quantitative analysis of all analytes in more difficult matrices like egg.

Full-scan accurate mass selectivity of ultra-performance liquid chromatography combined with time-of-flight and orbitrap mass spectrometry in hormone and veterinary drug residue analysis.

The applicability of ultra-performance liquid chromatography (UPLC) combined with full-scan accurate mass time-of-flight (TOF) and Orbitrap mass spectrometry (MS) to the analysis of hormone and veterinary drug residues was evaluated. Extracts from blank bovine hair were fortified with 14 steroid esters. UPLC-Orbitrap MS performed at a resolving power of 60,000 (FWHM) enabled the detection and accurate mass measurement (<3 ppm error) of all 14 steroid esters at low ng/g concentration level, despite the complex matrix background.

Toward a generic extraction method for simultaneous determination of pesticides, mycotoxins, plant toxins, and veterinary drugs in feed and food matrixes.

A fast and straightforward generic procedure for the simultaneous extraction of various classes of pesticides, mycotoxins, plant toxins, and veterinary drugs in various matrixes has been developed, for subsequent analysis by liquid chromatography with mass spectrometric detection. As a first step, four existing multianalyte procedures and three newly proposed methods were compared for a test set of 172 pesticides, mycotoxins, and plant toxins spiked to a feed matrix. The new procedures, which basically involved extraction/dilution of the sample with water and an acidified organic solvent (methanol, acetonitrile, or acetone), were most promising.

Comprehensive screening and quantification of veterinary drugs in milk using UPLC-ToF-MS.

Ultra-performance liquid chromatography combined with time-of-flight mass spectrometry (UPLC-ToF-MS) has been used for screening and quantification of more than 100 veterinary drugs in milk. The veterinary drugs represent different classes including benzimidazoles, macrolides, penicillins, quinolones, sulphonamides, pyrimidines, tetracylines, nitroimidazoles, tranquillizers, ionophores, amphenicols and non-steroidal anti-inflammatory agents (NSAIDs). After protein precipitation, centrifugation and solid-phase extraction (SPE), the extracts were analysed by UPLC-ToF-MS.

Multiresidue analysis of beta-agonists in bovine and porcine urine, feed and hair using liquid chromatography electrospray ionisation tandem mass spectrometry.

The use of beta-agonists as growth promoters in cattle breeding is forbidden in many countries for reasons of fair trade and consumer protection. In recent years the use of liquid chromatography (LC) tandem mass spectrometry (MS/MS) has been shown to be the method of choice for the control of beta-agonists. In this study an LC-MS/MS multiresidue analysis method is presented for trace analysis of 22 beta-agonists.

Analytical strategies for residue analysis of veterinary drugs and growth-promoting agents in food-producing animals--a review.

After a brief introduction into the field of veterinary drugs and growth-promoting agents, the most important EU regulations and directives for the inspection of food-producing animals and animal products regarding the residue control of these substances are presented and discussed. Main attention in the review is on the methods of analysis in use today for the most important classes of veterinary drugs and growth-promoting agents viz. anthelmintics, antibiotics, coccidiostats, hormones, beta-agonists and tranquillizers.

Determination of cannabinoids in cannabis products using liquid chromatography-ion trap mass spectrometry.

A method was developed and validated for the simultaneous determination of five cannabinoids, viz. cannabidiol (CBD), cannabidiol acid (CBD-COOH), cannabinol (CBN), delta9-tetrahydrocannabinol (THC), and 3'-carboxy-delta9-all-trans-tetrahydrocannabinol (THC-COOH) in cannabis products. The cannabinoids were extracted from the grinded cannabis samples with a mixture of methanol-chloroform and analysed using liquid chromatography with ion-trap-mass-spectrometry (LC-IT-MSn).

Liquid chromatography with triple-quadrupole and quadrupole-time-of-flight mass spectrometry for the determination of micro-constituents - a comparison.

The potential of liquid chromatography with triple-quadrupole mass spectrometry (LC-QqQ MS) was compared to that of quadrupole time-of-flight mass spectrometry (LC-Q-ToF MS) for the determination of microconstituents. Three applications were studied: (1) the ng/l quantification of five human drugs in surface water and waste-water effluents; (2) the quantification and confirmation of three corticosteroids in bovine urine at concentrations of 1-100 microg/l, and; (3) the confirmation of nicotine in rat plasma. In all cases, the criteria of the EU Commission Decision 2002/657/EC were followed (for confirmation analysis two MS/MS ions were monitored, and the ratio of their abundances were calculated and compared with those of standards).

Application of the revised EU criteria for the confirmation of anabolic steroids in meat using GC-MS.

The EU criteria for the confirmation of the presence of illegal compounds in biological matrices were recently revised. The old and the revised criteria were applied to relative ion intensities obtained for five anabolic steroids (methylboldenone, methyltestosterone, ethynylestradiol, beta-boldenone and beta-nortestosterone) in meat (cow, pig, turkey) and fish at concentrations ranging from 0.5 to 5.

Determination of nicotine and cotinine in rat plasma by liquid chromatography-tandem mass spectrometry.

A method was developed for the efficient determination of nicotine and cotinine in rat plasma samples originating from nicotine exposure studies. Nicotine and cotinine were extracted from plasma samples with dichloromethane and concentrated to minimum volume with nitrogen stream. The volatility of nicotine was prevented by the addition of hydrochloric acid to the organic solvent during evaporation.