•Spatial and temporal distribution of currently used pesticides in the Guadalquivir River Basin.•Organophosphorus>triazines>carbamates are the most commonly detected.•Transformation products were ...found at higher concentrations than parent pesticides.•WWTP are an important source of pesticide to the environment.•Low accumulation levels in sediments and biota.
The occurrence of 50 currently used pesticides and their transformation products in surface and waste waters, sediment and fish in the Guadalquivir River Basin was determined in 2010 and 2011. After selective sample extraction, pesticides were identified and quantified by liquid chromatography coupled to tandem mass spectrometry (LC–MS/MS). The contamination profile in water and sediments is marked by the presence of organophosphorus and triazines. Transformation products were even at higher concentrations than parent pesticides. A wider range of pesticides was present in water than in sediments but none of them were detected in fish. The mean concentrations ranged from 0.2 to 13.0ng/L in water and from 0.1 to 13.2ng/g d.w. in sediment. The spatial distribution of most pesticides was consistent with the agricultural activities of the area or their urban applications. The waste water treatment plant effluents that impact the river are minor sources for few pesticides but for most of them run-off would be the most important contribution. The temporal distribution showed differences between both sampling campaigns related to the river flow. The low-flow produced a pesticide concentration effect, generating higher levels in water and accumulation in sediments. This forecasts a hazard in future scenarios if the current situation of the climate change and water scarcity evolves to more critical conditions highlighting the need of these monitoring studies.
•Pressurized liquid extraction (PLE) is green, economic, rapid and high throughput.•PLE provides recoveries in the same range as, or greater than, other methods.•Pressurized hot-water extraction can ...extract polar and even non-polar analytes.•In-cell clean-up is feasible and advantageous in choosing sorbents properly.•The newest equipment is compatible with strong acids and bases removing in-cell lipids.
Pressurized liquid extraction (PLE) is an automated technique that uses elevated temperature and pressure to achieve exhaustive extraction from solid matrices, so reducing solvent consumption and enhancing sample throughput when compared with traditional procedures. Hence, it can be considered an environment-friendly technique, generating small volumes of waste and reducing costs and time. This review focuses on application of this green technique to the analysis of organic contaminants in food and environmental matrices for monitoring purposes. We examine fundamentals and key aspects of the development of a PLE method, including pressurized hot-water extraction, together with some relevant applications in food and the environment. We pay special attention to methods, including clean-up in one step in the extraction cell or on-line clean-up coupled to the extraction cell. We also compare PLE with other techniques (e.g., Soxhlet, microwave-assisted extraction, and supercritical fluid extraction).
•Overview of analytical methodologies and sample preparation.•Trend is to develop and to apply automatic techniques and multi-class methods.•High-resolution, full-scan analysis and UHPLC have ...increased in popularity.•Future development should extend analysis to dozens of multiclass compounds.•Future development should also keep acceptable recoveries and sensitivity.
We review the current methods developed for the analysis of legal and illegal drugs (LIDs) and their metabolites in environmental samples. We discuss the advantages and the pitfalls of multi-class methods with emphasis on new strategies for sample preparation and recent technical developments. Finally, we present the applicability of these methods to the analysis of LIDs in protected environmental areas.
This study is focused on the occurrence of 17 pharmaceuticals in waters (34 samples), sediments (16 samples) and soils (23 samples, at two different depths) in a typical Mediterranean coastal wetland ...(Pego–Oliva marsh, Spain). Soil and sediment samples were extracted by pressurized liquid extraction (PLE). Aqueous extracts from PLE and water samples were concentrated by solid-phase extraction (SPE) and determined by liquid-chromatography tandem mass spectrometry (LC–MS/MS). Pharmaceuticals were detected in concentrations up to 112ng/L in water samples, up to 15.1ng/g sediments and up to 8.4ng/g in soil. In surface waters, ibuprofen and codeine were the compounds more frequently detected (up to 59ng/L and 63ng/L, respectively). Ground and tap water samples analyzed were also contaminated with pharmaceuticals. The 94% of sediments and the 80% of agricultural soils were polluted (mostly by carbamazepine and acetaminophen). Diffusion of codeine and fluoroquinolones to deeper soil horizons was observed. Possible relationships between variables were established by Pearson correlations and principal components analysis (PCA). An environmental risk assessment based on the available long-term data was performed. Results showed actual risk for the lowest trophic level, and for fishes, due to the presence of fluoroquinolones and ibuprofen. Nevertheless, the presence of pharmaceuticals in the environment is not limited only to an ecological problem since contamination also affects drinking water, being a potential risk to human health.
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► We studied the occurrence of 17 pharmaceuticals in water, sediments and soils of a Mediterranean wetland. ► The 100% of waters, 94% of sediments and 96 % of agricultural soils were polluted. ► The most frequent pharmaceuticals were codeine and ibuprofen in water and carbamazepine and acetaminophen in soil/sediment. ► Diffusion of codeine and fluoroquinolones to deeper soil horizons, was observed. ► Risk for the lower trophic levels and fishes was established.
The present work describes the development of a sensitive analytical method based on pressurized liquid extraction (PLE) and pre-concentration by solid-phase extraction (SPE), followed by liquid ...chromatography–electrospray tandem mass spectrometry (LC–ESI-MS/MS) for the determination of seventeen pharmaceuticals in soils and sediments. The method is based on sample homogenisation using Na
2–EDTA washed sand and extraction with water at 90
°C. Special emphasis was placed on the optimization of the extraction procedure to develop a green method that reduces, at a maximum, the use of organic solvents in order to eliminate matrix components during the clean-up. The proposed method was linear in a concentration range from 0.3 to 333
ng
g
−1, with correlation coefficients higher than 0.993. Method detection (MDLs) and quantification (MQLs) limits ranged from 0.1 to 6.8
ng
g
−1 and from 0.25 to 23
ng
g
−1, respectively. Absolute recoveries were analyte dependent, varying between 50% and 105% at the MQL level, except for fenofibrate (40%) and diclofenac (34%). The intra-day and inter-day precision was given by RSD values from 0.7% to 7.9% and from 1.6% to 14.5%, respectively. Acetaminophen, carbamazepine, ciprofloxacin, clofibric acid, codeine, diazepam, fenofibrate, metropolol, ofloxacin and propanolol were detected at concentrations from MDL to 35.62
ng
g
−1 in soils and sediments from marsh areas. Due to the low recoveries, results for fenofibrate and diclofenac can only be considered as semi-quantitative. The method was fully suitable for the other 15 pharmaceuticals.
The enantiomeric and diastereomeric profiling of chiral pharmaceuticals (ephedrine, norephedrine, atenolol and venlafaxine) and illicit drugs (amphetamine, methamphetamine, ...3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxy-N-methylamphetamine (MDMA) and 3,4-methylenedioxy-N-ethylamphetamine (MDEA)) was undertaken over a period of fourteen consecutive days in three wastewater treatment plants (WWTPs) in the city of Valencia, Spain. Degradation efficiency of WWTPs was found to be compound and enantiomer dependent. Selective enantiomer enrichment was observed for several target analytes. Amphetamine and MDMA were enriched with R(−)-enantiomers. 1S,2S(+)-pseudoephedrine was found to be more readily degradable during activated sludge treatment than its diastereomer 1R,2S(−)-ephedrine. Atenolol underwent enrichment with either S(−)- or R(+)-enantiomer in different WWTPs. This unexpected enantiomeric variation in the stereoselective degradation of atenolol could be attributed to different processes utilized during activated sludge treatment. The application of (enantiomeric) profiling of wastewater revealed usage patterns of chiral drugs in the Valencia region.
•Enantiomeric profiling of chiral drugs was undertaken at three WWTPs.•Degradation efficiency of WWTPs was compound and enantiomer dependent.•Atenolol was enriched with either S(−)- or R(+)-enantiomer in different WWTPs.•Amphetamine and MDMA were enriched with R(−)-enantiomers•1S,2S(+)-pseudoephedrine was more readily degradable than its diastereomer
The feasibility of different extraction procedures was tested and compared for the determination of 12 organophosphorus and carbamates insecticides in honey samples. In this sense, once the samples ...were pre-treated – essentially dissolved in hot water by stirring – and before they could be analyzed by liquid chromatography–ion trap-second stage mass spectrometry (LC–MS
2), four different approaches were studied for the extraction step: QuEChERS, solid-phase extraction (SPE), pressurized liquid extraction (PLE) and solid-phase microextraction (SPME). The main aim of this work was to maximise the sensitivity of pesticides and to minimise the presence of interfering compounds in the extract. All pesticides were linear in the range from CC
β
to 1000× CC
β
for the four extraction methods (three orders of magnitude). Detection capabilities (CC
β
) were 0.024–1.155
mg
kg
−1 with QuEChERS, 0.010–0.646
mg
kg
−1 with SPE, 0.007–0.595
mg
kg
−1 with PLE, and 0.001–0.060
mg
kg
−1 with SPME. All the target compounds could be recovered by any of the methods, at a CC
β
fortification level ranged from 28 to 90% for the SPME. In comparison, the PLE method was the most efficient extraction method with recoveries from 82 to 104%. It was followed by the QuEChERS method with recoveries between 78 and 101% and the SPE method with recoveries between 72 and 100%. The repeatability expressed as relative standard deviation (RSDs) was below 20% for all the pesticides by any of the tested extraction methods. Results obtained applying the four extraction techniques to real honey samples are analogous.
The distribution of 17 pharmaceuticals between water and the solid phase (sediments and soils) was studied by utilizing solid-phase extraction (SPE) and liquid chromatography–tandem mass spectrometry ...(LC-MS/MS). Two extraction procedures for soils and sediments, prior to the SPE, one based on pressurized liquid extraction (PLE) with hot water and the other on methanol/water ultrasonic extraction, were compared. Absolute recoveries were 71.2–99.3% relative standard deviation (RSD) <21.4%) for water, and the method detection limits (MDLs) ranged from 0.3 to 10 ng L
−1
. Recoveries were 35.4–105.3% (RSDs <19.1%) and 42.1–97.8% (RSDs <14%) for soil and sediment samples, respectively, using PLE and 20.2–86.5% (RSDs <25.1%) and 30.3–97.4% (RSDs <19.1%) using ultrasonic extraction. Fifteen of the 17 pharmaceuticals were present in the L’Albufera water at concentrations up to 17 μg L
−1
. Oxytetracycline and tetracycline were not detected. In sediments, only tetracycline, norfloxacin and diclofenac were not found. The other studied pharmaceuticals were present in the range from less than the method quantification limit (MQL) to 35.83 ng g
−1
. Among the 17 target compounds, ofloxacin, ciprofloxacin, norfloxacin, trimethoprim, clofibric acid and diclofenac were not detected in soil samples. The average concentrations ranged from less than the MQL for ibuprofen to 34.91 ng g
−1
for tetracycline. These results indicate that pharmaceuticals could survive the wastewater treatment processes, which could lead to their dissemination in water environments.
A simple and robust method using solid-phase extraction (SPE) and liquid chromatography tandem mass spectrometry (LC-MS/MS) for the simultaneous determination of 14 drugs of abuse and their ...metabolites (cocainics, amphetamine-like compounds, cannabinoids, and opiates) in surface waters has been developed. Seven SPE adsorbents (Oasis HLB, Oasis MCX, Oasis Wax, Supelselect HLB, Strata-X, Strata-XCW), amount of sorbent bed, water volume, and pH were investigated. The highest recoveries, as well as the simplest protocol, were obtained for Oasis HLB cartridges (6 mL/200 mg) using 250 mL of water. The proposed method was linear in a concentration range from 0.03-6 to 300-60,000 ng/L depending on the compound, with correlation coefficients higher than 0.998. Matrix effects have been studied in surface water samples, and several isotope-labeled internal standards have been evaluated as a way to compensate the signal suppression observed. Limits of detection (LODs) and quantification (LOQs) ranged from 0.01 to 1.54 ng/L and from 0.03 to 5.13 ng/L, respectively. Recoveries were 71-102% at the LOQ level and 77-104 at 50 ng/L. The intra-day and intermediate precisions were from 1% to 8% and from 2% to 11%, respectively. The present work reports for the first time the occurrence of drugs of abuse residues in surface water samples from the Natural Park of L'Albufera (Valencia, Spain). Codeine, cocaine, benzoylecgonine, ecgonine methylester, amphetamine, 3,4-methylendioxy methamphetamine, morphine, and methadone were quantified with median values of 11.10, 0.02, 5.59, 0.08, 0.21, 0.75 and 0.14 ng/L respectively, and 11-nor-9-carboxy-Δ9-tetrahydrocannabinol was detected in one sample at levels <LOQ.
An optimized extraction and cleanup method for the analysis of chlortetracycline (CTC), doxycycline (DC), oxytetracycline (OTC) and tetracycline (TC) in soil is presented. Soil extraction in a ...pressurized liquid extraction system, followed by extract clean up using solid-phase extraction (SPE) and tetracycline determination by liquid chromatography tandem mass spectrometry (LC-MS/MS) provided appropriate efficiency and reproducibility. Different dispersing agents and solvents for soil extraction and several SPE cartridges for cleanup were compared. The best extraction results were obtained using ethylenediamine tetraacetic acid-treated sand as dispersing agent, and water at 70 °C. The most effective cleanup was obtained using Strata-XTM sorbent in combination with a strong anion exchange cartridge. Recoveries ranged from 71% to 96% and precision, as indicated by the relative standard deviations, was within the range of 8-15%. The limits of quantification (LOQs) by using LC-MS/MS, based on signal-to-noise ratio (S/N) of 10, ranged from 1 μg kg⁻¹ for TC to 5 μg kg⁻¹ for CTC. These results pointed out that this technique is appropriate to determine tetracyclines in soils. Analysis of 100 samples taken in the Valencian Community revealed that, in soil, up to 5 μg kg⁻¹ CTC, 15 μg kg⁻¹ OTC, 18 μg kg⁻¹ TC, and 12 μg kg⁻¹ DC could be detected. Detection of the analytes in several samples, which typify great part of the Spanish agricultural soils, should be outlined as most important result of this study.
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