Evaluation of the sorption/desorption processes of pesticides in biodegradable mulch films used in agriculture.

Microplastics from mulch films can be a source of chemical contamination to agricultural soils. In this context, biodegradable films have been widely positioned as a greener choice. However, their sorption/desorption capabilities, in contrast to the conventional plastic types remain understudied. It is for this reason that objective evaluation of their interactions with residual agricultural contaminants becomes important. Our findings reveal that polyethylene (PE) mulch films retained lower amounts of pesticide residues and demonstrated a higher desorption/release [median desorption = 71.86 µg/L or about 50%], while polybutylene adipate terephthalate (PBAT) mulch films retained higher amounts of pesticide residues onto their surface and demonstrated a much lower desorption [median desorption = 24.27 µg/L or about 17%] after a spraying event. A higher ambient temperature had no significant effect on final desorption amounts in both PE [median = 65.27 µg/L at 20 °C and 74.23 µg/L at 40 °C] and PBAT [median = 24.26 µg/L at 20 °C and 24.78 µg/L at 40 °C] mulch films. However, it did favour a faster desorption pace in PE films. Desorption in PBAT and PE plastic types was correlated with the log Kow value [Spearman's correlation: 0.857 and 0.837 respectively, p < 0.05]. However, only a moderate correlation with pKa was observed in PBAT [Spearman's correlation: 0.478, p < 0.05], while none for PE plastic type. Sorption of pesticides onto biodegradable PBAT microplastics were best explained by Elovich [R2: 0.937-0.959] and pseudo-second order kinetics [R2: 0.942-0.987], suggesting the presence of chemisorption. Furthermore, Weber Morris plots suggested the presence of a multi-step process and Boyd plots indicated that film diffusion or chemical bond formation was the rate-limiting step governing this phenomenon.

Quantification of nanoplastic uptake and distribution in the root, stem and leaves of the edible herb Lepidum sativum.

This study confirms the uptake, translocation and bioaccumulation of 100 nm polystyrene nanoplastics in the root, stem and leaves of the plant Lepidum sativum at exposure concentrations ranging from environmentally realistic 10 µg/L up to a high of 100 mg/L. Accumulation in plant tissues was characterised by aggregation in the intercellular spaces and heterogeneous distribution. Nanoplastic presence was confirmed in the root tips, root surface and stele, lateral roots, root hairs, stem vascular bundles, leaf veins and mesophyll, as well as leaf epidermis including stomatal sites. Quantification results show that majority of the particles were retained in the root and accumulation in stem and leaves was only 13 to 18 % of the median value in roots. There was a reduction of 38.89 ± 9.62 % in the germination rate, 55 % in plant fresh weight, as well as in root weight (> 80 %), root length (> 60 %), shoot weight (51 to 78 %) and number of lateral roots (> 28 %) at exposure concentrations at and above 50 mg/L. However, lower, environmentally probable exposure concentrations did not affect the plant health significantly. Our results highlight the urgent need for further exploration of this issue from the point of view of food safety and security. STATEMENT OF ENVIRONMENTAL IMPLICATION: Micro and nanoplastics have been reported in agricultural environments across the globe and reports regarding their hazardous effects over agricultural and plant health call for an urgent exploration of this issue. This work demonstrates the uptake, bioaccumulation and distribution of nanoplastics in an edible plant at an environmentally realistic concentration and raises serious concerns regarding the possible implications for food safety and security. It presents a novel approach which addresses the quantification of nanoplastic accumulation in plant tissues and helps identify the mechanism and trends behind this phenomenon which has been a challenge up until now.

Method optimisation for large scope pesticide multiresidue analysis in bee pollen: A pilot monitoring study.

Pesticide contamination in emerging foods and supplements is currently a topic of great interest. This study focused on the evaluation of pesticide residues in commercial bee pollen samples to evaluate the risk associated with their consumption. To this end, an automated clean-up method for the pesticide extracts of bee pollen was developed. An LC-MS/MS and a GC-MS/MS method were validated for the analysis of 353 pesticides in 80 bee pollen samples purchased from different countries. The results showed the presence of 77 different pesticide residues in bee pollen, including plant protection chemicals and veterinary treatments. 85 % of the samples were contaminated with pesticides and no relevant differences were found between conventional and organic samples. Pesticide concentrations exceeding the imposed MRL were found in 40 % of the samples, but the risk assessment showed that consumers are not exposed to an unacceptable risk when consuming the evaluated bee pollen.

Comparison of APIStrip passive sampling with conventional sample techniques for the control of acaricide residues in honey bee hives.

Western honey bees are very sensitive bioindicators for studying environmental conditions, hence frequently included in many investigations. However, it is very common in both research studies and health surveillance programs to sample different components of the colony, including adult bees, brood and their food reserves. These practices are undoubtedly aggressive for the colony as a whole, and may affect its normal functioning and even compromise its viability. APIStrip-based passive sampling allows long-term monitoring of residues without affecting the colony in any way. In this study, we compared the effectiveness in the control of acaricide residues by using passive and conventional sampling, where the residue levels of the acaricides coumaphos, tau-fluvalinate and amitraz were evaluated. Conventional and APIStrip-based sampling differ in methods for evaluating bee exposure to residues. APIStrip is less invasive than conventional sampling, offers more efficient measurement of environmental contaminants, and can be stored at room temperature, saving costs and minimizing operator error.

Acceptance by Honey Bees of Wax Decontaminated through an Extraction Process with Methanol.

Honey bees face serious threats. These include the presence of the Varroa destructor mite in hives, which requires the use of acaricides to control. The constant recycling of old wax exacerbates the problem, and results in the accumulation of residues in the beeswax, which is a problem for the viability of the colony. The same happens with the accumulation of phytosanitary residues. In a previous study, we implemented an efficient wax decontamination method using a batch methanol extraction method. The present study evaluates the acceptance of the decontaminated wax by the bees for comb building, brood, honey and pollen containment. The results show a slight delay in the start of comb building and small changes were observed in the pharmacopoeia of the decontaminated wax compared to the original commercial wax. The slight delay in the acceptance of the decontaminated wax could be due to the loss of some components, such as honey residues, which usually appear in the wax. The addition of bee-attractive substances to the manufacturing process could help to mitigate the delay. The results suggest that the use of decontaminated wax is a good alternative to reduce the concentration of residues in hives.

Exploring sorption of pesticides and PAHs in microplastics derived from plastic mulch films used in modern agriculture.

The sorption and vector effect of microplastics on the transfer of pesticides and polycyclic aromatic hydrocarbons (PAHs), as well as its impact on agriculture remain largely unexplored. This comparative study is first to investigate the sorption behavior of different pesticides and PAHs at environmentally realistic concentrations by model microplastics and microplastics derived from polyethylene mulch films. Sorption was found to be up to 90% higher in the case of microplastics derived from mulch films as opposed to pure polyethylene microspheres. For microplastics from mulch films, the sorption percentages for pesticides in media containing CaCl2 were reported to be: pyridate (75.68% and 52.44%), fenazaquin (48.54% and 32.02%), pyridaben (45.04% and 56.70%), bifenthrin (74.27% and 25.88%), etofenprox (82.16% and 54.16%) and pyridalyl (97.00% and 29.74%) at 5 µg/L and 200 µg/L pesticide concentration levels respectively. For PAHs, the sorption amounts were: naphthalene (22.03% and 48.00%), fluorene (38.99% and 39.00%), anthracene (64.62% and 68.02%) and pyrene (75.65% and 86.38%) at 5 µg/L and 200 µg/L PAH concentration levels respectively. Sorption was influenced by the octanol-water partition coefficient (log Kow) and ionic strength. Kinetics of the process in the case of sorption of pesticides were best explained by pseudo-first order kinetic model (R2 between 0.90 and 0.98) while the best fitting isotherm model was Dubinin-Radushkevich (R2 between 0.92 and 0.99). Results suggest the presence of surface level physi-sorption through a micropore volume filling mechanism and the role of hydrophobic and electrostatic forces. Pesticide desorption data in polyethylene mulch films indicate that pesticides with high log Kow were almost completely retained in mulch films, while those with lower log Kow were desorbed rapidly into the surrounding media. Our study highlights the role of microplastics from plastic mulch films as vectors for pesticide and PAH transport at environmentally realistic concentrations and the factors that influence it.

Coumaphos residue transfer to honey bee brood (Apis mellifera) in realistic scenarios.

Coumaphos is a veterinary treatment administered for the control of Varroa destructor in honey bee colonies. The detection of its residues, however, has been frequently reported in beeswax. This study is pioneer to investigate whether the honey bee brood is exposed to coumaphos via contact or by ingestion of food resources due to a residue transfer inside the bee hive. This field study addresses two scenarios: 1) after its administration according to the posology using strips inside the bee hives and, 2) placing contaminated wax containing coumaphos at 10 mg/Kg into the bee hives (simulating the use of recycled wax). In bee bread, the average concentrations of residues (mean ± s.d.) were 246.66 ± 772.29 ng/g and 192.55 ± 320.19 ng/g in scenario 1 and 2, respectively. In honey, residue concentration was 1.98 ± 5.41 ng/g and 1.93 ± 6.59 ng/g. In scenario 2, exposure has led to residue detection in all larval stages at concentrations ranging from 51.93 to 383.42 ng/g (larvae), 42.20-58.54 ng/g (prepupae), 18.35-26.24 ng/g (pupae) to 21.92-35.92 ng/g (born bee). This study shows that there is a high risk for the bee brood (larvae) by ingestion of bee bread when the residue concentration is >251.31 ng/g. Residue levels in larvae or in prepupae >42.20 ng/g give rise to a moderate risk.

Determination of Regulated and Emerging Mycotoxins in Organic and Conventional Gluten-Free Flours by LC-MS/MS.

Gluten-free cereal products have grown in popularity in recent years as they are perceived as "healthier" alternatives and can be safely consumed by celiac patients, and people with gluten intolerance or wheat allergies. Molds that produce mycotoxins contaminate cereal crops, posing a threat to global food security. Maximum levels have been set for certain mycotoxins in cereal flours; however, little is known about the levels of emerging mycotoxins in these flours. The aim of this study was to develop an efficient, sensitive, and selective method for the detection of four emerging (beauvericin and enniatins A1, B, and B1) and three regulated (aflatoxin B1, zearalenone, and deoxynivalenol) mycotoxins in gluten-free flours. Ultrasound-assisted matrix solid-phase dispersion was used in the extraction of these mycotoxins from flour samples. The validated method was utilized for the LC-MS/MS analysis of conventional and organic wholegrain oat and rice flours. Six of the seven target mycotoxins were detected in these samples. Multi-mycotoxin contamination was found in all flour types, particularly in conventional wholegrain oat flour. Despite the low detection frequency in rice flour, one sample was found to contain zearalenone at a concentration of 83.2 µg/kg, which was higher than the level set by the European Commission for cereal flours. The emerging mycotoxins had the highest detection frequencies; enniatin B was present in 53% of the samples at a maximum concentration of 56 µg/kg, followed by enniatin B1 and beauvericin, which were detected in 46% of the samples, and at levels reaching 21 µg/kg and 10 µg/kg, respectively. These results highlight the need to improve the current knowledge and regulations on the presence of mycotoxins, particularly emerging ones, in gluten-free flours and cereal-based products.

Microbial Decontamination of Bee Pollen by Direct Ozone Exposure.

The bee pollen is a complete and healthy food with important nutritional properties. Usually, bee pollen is consumed dehydrated, but it is possible to market it as fresh frozen pollen, favoring the maintenance of its properties and greatly increasing its palatability, compared to dried pollen. However, fresh frozen pollen maintains a high microbiological load that can include some pathogenic genus to human health. In this work, ozonation combined with drying is applied to reduce the microbiological load. The lowest timing exposure to ozone (30 min) was chosen together with hot-air drying during 15 min to evaluate the shelf-life of treated bee-pollen under cold storage (4 °C), and initial reductions of 3, 1.5, and 1.7 log cycles were obtained for Enterobacteriaceae, mesophilic aerobes, and molds and yeasts counting, respectively. Six weeks after treatment the microbial load was held at a lower level than initially observed in fresh bee-pollen. In addition, ozone treatment did not have a negative impact on the polyphenols evaluated. Likewise, the sensory profile of the bee pollen under different treatments was studied. For all these assays the results have been favorable, so we can say that ozonation of fresh pollen is safe for human consumption, which maintains its polyphenols composition and organoleptically is better valued than dried pollen.

Impact of Varroa destructor and associated pathologies on the colony collapse disorder affecting honey bees.

Varroa mite is the major threat to the western honey bee, Apis mellifera, and the cause of significant economic losses in the apiculture industry. Varroa destructor feeds on brood and adult bees being responsible for vectoring virus infections and other diseases. This study analyses the role of Varroa and other associated pathogens, such as viruses or the fungus Nosema ceranae, and their relationships regarding the viability of the bee colony. It has been carried out during one beekeeping season, with the subspecies A. m. iberiensis, commonly used in the apiculture industry of Spain. Our study shows a significant relationship between the presence of Varroa destructor and viral infection by deformed wing virus and acute bee paralysis virus. Nosema ceranae behaved as an opportunistic pathogen. In addition, this study explored a potential naturally occurring subset of peptides, responsible for the humoral immunity of the bees. The expression of the antimicrobial peptides abaecin and melittin showed a significant relationship with the levels of Varroa mite and the deformed wing virus.

Exploring the Extracellular Macromolecular Composition of Crude Extracts of Penicillium rubens Strain 212 for Elucidation Its Mode of Action as a Biocontrol Agent.

Penicillium rubens strain 212 (PO212) acts as an inducer of systemic resistance in tomato plants. The effect of crude extracellular extracts of PO212 on the soil-borne pathogen Fusarium oxysporum f. sp. lycopersici has been evaluated. Evidence of the involvement of soluble, thermo-labile, and proteinase-inactivated macromolecules present in PO212 crude extracts in the control of Fusarium vascular disease in tomato plants was found. Proteomic techniques and the availability of the access to the PO212 genome database have allowed the identification of glycosyl hydrolases, oxidases, and peptidases in these extracellular extracts. Furthermore, a bioassay-guided fractionation of PO212 crude extracellular extracts using an integrated membrane/solid phase extraction process was set up. This method enabled the separation of a PO212 crude extracellular extract of seven days of growth into four fractions of different molecular sizes and polarities: high molecular mass protein fraction >5 kDa, middle molecular mass protein fraction 5-1 kDa, low molecular mass metabolite fraction, and nutrients from culture medium (mainly glucose and minerals). The high and middle molecular mass protein fractions retained disease control activity in a way similar to that of the control extracts. Proteomic techniques have allowed the identification of nine putatively secreted proteins in the high molecular mass protein fraction matching those identified in the total crude extracts. Therefore, these enzymes are considered to be potentially responsible of the crude extracellular extract-induced resistance in tomato plants against F. oxysporum f. sp. lycopersici. Further studies are required to establish which of the identified proteins participate in the PO212's action mode as a biocontrol agent.

The toxic unit approach as a risk indicator in honey bees surveillance programmes: A case of study in Apis mellifera iberiensis.

The influence of genetic diversity and exposure to xenobiotics on the prevalence of pathogens was studied within the context of a voluntary epidemiological study in Spanish apiaries of Apis mellifera iberiensis, carried out during the spring season of years 2014 and 2015. As such, the evolutionary lineages of the honey bee colonies were identified, a multiresidue analysis of xenobiotics was carried out in beebread and worker bee samples, and the Toxic Unit (TUm) was estimated for each sampled apiary. The relationship between lineages and the most prevalent pathogens (Nosema ceranae, Varroa destructor, trypanosomatids, Black Queen Cell Virus; and Deformed Wing Virus) was analysed with contingency tables, and the possible relationships between TUm and the prevalence of these pathogens were studied by using a factor analysis. The statistical analysis supported the associations between V. destructor and Deformed Wing Virus (DWV), and between N. ceranae and Black Queen Cell Virus (BQCV), but the association between these pathogens and trypanosomatids was not observed. TUm values varied between 5.5 × 10-6 and 3.65 × 10-1. When TUm < 3.35 × 10-4, it was mainly determined by coumaphos, tau-fluvalinate and/or chlorfenvinphos. At higher values, other insecticides also contributed to TUm, although a clear predominance was not seen up to TUm ≥ 1.83 × 10-2, when it was mainly defined by acrinathrin, spinosad and/or imidacloprid. The possible cumulative effect from the joint action of xenobiotics was >10% in the 63% of the cases. The prevalence of pathogens did not appear to be influenced by the distribution of evolutionary lineages and, while the prevalence of V. destructor was not found to be determined by TUm, there was a trend towards an increasing prevalence of N. ceranae when TUm ≥ 23 10-4. This study is an example of using TUm approach beyond the field of the ecotoxicology.

Quantitative determination of poly(amidoamine) dendrimers in urine by liquid chromatography/electrospray ionization hybrid quadrupole linear ion trap mass spectrometry.

RATIONALE: Dendrimer nanocarriers have become of increasing interest in the field of biomedicine for their drug delivery potential. Surface modifications and optimized nanosize control are the strategies being followed to enhance drug delivery efficacy and renal clearance, especially for dendrimers of a lower generation number. The aim of this study was the development and performance evaluation of an analytical method for the quantitative determination of polyamidoamine (PAMAM) dendrimers in urine. METHODS: PAMAM dendrimers (generations G0 to G3) were analyzed using liquid chromatography/electrospray ionization hybrid quadrupole linear ion trap mass spectrometry (LC/ESI-QqLIT-MS). Quantitative analysis was performed in selected reaction monitoring (SRM) mode. To confer a higher degree of confidence on the identification of PAMAM dendrimers, an SRM scan and collision-induced dissociation (CID), as a dependent scan, were performed in one single run using the information-dependent acquisition (IDA) mode. RESULTS: The LC/ESI-QqLIT-MS method, in SRM mode, allowed quantitative determination in urine matrix with good repeatability and reproducibility (relative standard deviation (R.S.D.) from 2 to 15%), linearity (R >0.99) over the concentration range (6∙10-4 to 5∙10-2 mmol.L-1 ), and sensitivity within the micromolar range. The detection limit values were above 1∙10-4 mmol.L-1 in both solvent and urine, for the generations studied. CONCLUSIONS: The developed method has demonstrated a capability for the identification and quantification of PAMAM dendrimer nanoparticles in a complex liquid matrix. The use of an LC/ESI-QqLIT-MS system, of modest m/z range and unit resolution, offers an alternative in the analysis of lower generation PAMAM dendrimers between mass analyzers of higher resolution and the conventional LC-UV method that is commonly applied for dendrimer quantification, but which lacks sufficient identification capacity. Copyright © 2013 John Wiley & Sons, Ltd.

Identification and quantification of poly(amidoamine) PAMAM dendrimers of generations 0 to 3 by liquid chromatography/hybrid quadrupole time-of-flight mass spectrometry in aqueous medium.

RATIONALE: Poly(amidoamine) PAMAM dendrimers are highly water soluble and are used as flexible scaffolding or nanocontainers to conjugate, complex or encapsulate therapeutic drugs to overcome intrinsically weak characteristics such as solubilization in aqueous medium. To provide a reliable method for the quantitation of PAMAM dendrimers in aqueous medium, we report here a validation study which was developed in a complex wastewater matrix to evaluate the matrix effect in the electrospray ionization (ESI) source. METHODS: PAMAM dendrimers (generations G0 to G3) were identified and quantitated in aqueous medium using liquid chromatography interfaced to a hybrid quadrupole/time-of-flight mass analyzer. This approach used the high resolving power of isotopic clusters and mass accuracy of the instrument, with especial attention to the tandem mass spectrometric (MS/MS) capabilities. The formation of multiply charged ions of PAMAM dendrimers in the ESI source and their later fragmentation allowed fragmentation paths to be determined and structural assignments to be made. RESULTS: The analytical strategy allowed dendrimer identification with a high degree of confidence obtained by accurate mass and high resolution with mass errors below 5 ppm and 10 ppm in MS and MS/MS modes. The parameters of validation in spiked matrix were: limits of quantification in the range of 0.12 to 1.25 µM depending on the generation, linearity (R >0.996), repeatability (R.S.D. <6.7%) and reproducibility (R.S.D. <10.8%). CONCLUSIONS: Accurate mass measurement, elemental composition, and charge state assignment through the resolution of isotopic clusters of product and precursor ions, confers enhanced confidence on PAMAM dendrimer characterization. This selectivity provided high discriminating capacity of PAMAM dendrimers against matrix interferences. Because of the reliable and reproducible quantitation by LC/ESI-QTOF-MS, analysis of PAMAM dendrimers in an aqueous matrix is feasible.

Determination of malachite green residues in fish using molecularly imprinted solid-phase extraction followed by liquid chromatography-linear ion trap mass spectrometry.

This paper describes the development of an analytical procedure to determine malachite green (MG) residues in salmon samples using molecularly imprinted polymers (MIPs) as the extraction and clean-up material, followed by liquid chromatography-linear ion trap mass spectrometry (LC-QqQLIT-MS/MS). MG and two structurally related compounds, crystal violet (CV) and brilliant green (BG) were employed for the selectivity test. The imprinted polymers exhibited high binding affinity for MG, while CV and BG showed less binding capacity: 47% and 34%, respectively. The recovery values of MG in salmon samples fortified with leucomalachite green (LMG) were determined by measuring the amount of MG in the sample, after carrying out the oxidation reaction with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), which converts the LMG back into chromic-form. The average recovery of MG in spiked salmon muscle over the concentration range 1-100 ng g(-1) was 98% with a relative standard deviation value (R.S.D.) below 12%. The method detection limits (MDLs) obtained for MG, CV, BG and their leuco-metabolites were in the range of 3-20 ng kg(-1) (ppt).

Evaluation of various liquid chromatography-quadrupole-linear ion trap-mass spectrometry operation modes applied to the analysis of organic pollutants in wastewaters.

The LC-MS/MS analysis of a group of 14 organic pollutants in wastewater--including pharmaceuticals (analgesics/anti-inflammatories, lipid regulators and diuretics), pesticides (diuron) and disinfectants (chlorophene)--has been carried out using a hybrid triple quadrupole-linear ion trap-mass spectrometer (QqLIT). In order to take advantage of the capabilities of the QqLIT system, two methods have been developed and compared, based on the application of different operation modes. One of them uses selected reaction monitoring (SRM), which is the standard mode for quantitative LC-MS/MS analysis. The other is based on the use of an information dependent acquisition scan function (IDA), which allows the combination of a SRM acting as the survey scan and an enhanced product ion scan (EPI) as dependent scan within the same analysis. Performance of both methods was compared, especially in terms of their limits of detection and identification capability. The advantages and limitations of both techniques are discussed. Finally, the two methodologies developed were applied to real samples for evaluation of effluent wastewater in a treatment plant on the south-eastern Mediterranean coast of Spain. The presence of most of the target compounds was detected at mean concentrations ranging from 50 ng/L (mefenamic acid) to 3373 ng/L (hydrochlorothiazide).

Application of passive sampling devices for screening of micro-pollutants in marine aquaculture using LC-MS/MS.

Knowledge on the presence of micro-pollutants, in particular emerging contaminants, such as pharmaceuticals, biocides or some pesticides, in semi-enclosed coastal areas, where fish farms are installed, is very limited. This article shows data on the presence of micro-pollutants over 1 year monitoring campaign carried out in a fish farm placed on the Mediterranean Sea. With this work, the results of the development of an analytical procedure which, makes use of passive sampling techniques (with polar organic chemical integrative samplers, POCIS, pharmaceutical configuration) and of the LC-QLIT-MS system, are presented. The development of the analytical procedure entail laboratory-based calibration with the samplers POCIS, for calculating uptake rates and sampling rates of compounds representative of a wide range of polarity (4.56>or=logK(ow)>or=-0.12). The uptake of the target compounds in the sampler POCIS, follows a linear pattern for most compounds, and sampling rates varied from 0.001 to 0.319l/d. The calibration experiments have shown that POCIS pharmaceutical configuration could be used for sampling other non-target compounds, such as pesticides and biocides with a logK(ow)

Application of liquid chromatography/quadrupole-linear Ion trap mass spectrometry and time-of-flight mass spectrometry to the determination of pharmaceuticals and related contaminants in wastewater.

This paper describes an enhanced liquid chromatography-mass spectrometry (LC-MS) strategy for the analysis of a selected group of 56 organic pollutants in wastewater. This group comprises 38 pharmaceuticals and 10 of their most frequent metabolites, 6 pesticides, and 2 disinfectants. The LC-MS methodology applied is based in the use of a hybrid triple-quadrupole linear ion trap mass spectrometer (QTRAP) in combination with time-of-flight mass spectrometry (TOF-MS). The join application of both techniques provided very good results in terms of accurate quantification and unequivocal confirmation. Quantification was performed by LC-QTRAP-MS operating under selected reaction monitoring (SRM) mode in both positive and negative electrospray ionization. Unequivocal identification was provided by the acquisition of three SRM transitions per compound in most of the cases and by LC-TOF-MS analysis, which allows obtaining accurate mass measurements of the identified compounds with errors lower than 2 ppm. Additionally, the use of TOF-MS permits retrospective analysis, since the full spectrum is recorded at all times with a high sensitivity. Thus, review of recorded chromatograms looking for new compounds or transformation products suspected to be present in the samples is feasible allowing one to increase the scope of the method along the monitoring program. The analytical performance of the quantitative LC-QTRAP-MS method was evaluated in effluent wastewater samples. Linearity of response over 3 orders of magnitude was demonstrated for most compounds (R(2) > 0.99). Method limits of detection were between 0.04 and 50 ng L(-1). Finally, the methodology was successfully applied to a monitoring study intended to characterize wastewater effluents of six sewage treatment plants in Spain. The presence of most of compounds was detected at concentrations ranging from 9 ng L(-1) (atrazine) to 15 microg L(-1) (paraxanthine).

Liquid chromatography-tandem mass spectrometry for the analysis of pharmaceutical residues in environmental samples: a review.

Pharmaceutical residues are environmental contaminants of recent concern and the requirements for analytical methods are mainly dictated by low concentrations found in aqueous and solid environmental samples. In the current article, a review of the liquid chromatography-tandem mass spectrometry (LC-MS/MS) based methods published so far for the determination of pharmaceuticals in the environment is presented. Pharmaceuticals included in this review are antibiotics, non-steroidal anti-inflammatory drugs, beta-blockers, lipid regulating agents and psychiatric drugs. Advanced aspects of current LC-MS/MS methodology, including sample preparation and matrix effects, are discussed.