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A method using dispersive liquid-liquid microextraction (DLLME) prior to high performance liquid chromatography-diode array detection (HPLC-DAD) was developed to determine seven additives from the plastics industry (butylated hydroxytoluene, diisodecyl phthalate, irgafos 168, lawsone, quercetin, triclosan and vitamin E) in seawater samples. These compounds can reach seawater due to direct discharge from wastewater treatment plants and leaching from plastics and microplastics. The extraction was performed using 25 mL of seawater, 500 μL of 1-octanol (extraction solvent) and a stirring step instead of dispersive solvent. Additive concentrations were determined by LC-DAD on a C18 column with a mobile phase of acetonitrile and phosphoric acid aqueous solution (pH 3.5) by gradient elution. The analytical recoveries ranged from 82 to 93% for all compounds, except for lawsone (60%). Repeatability and intermediate precision were adequate with RSD < calculated values following the Horwitz equation at the concentration levels evaluated (0.06 and 0.24 mg L -1 ). All additives exhibited linear matrix calibration curves ( R 2 > 0.99). Detection limits ranged from 0.009 to 0.028 mg L -1 and quantification limits ranged from 0.027 to 0.084 mg L -1 . Finally, the application of the method to real samples verified the method as accurate and applicable to seawater.

In this work, a retention behavior based on mixed-mode reversed-phase (RP)/hydrophilic interaction liquid chromatography (HILIC) was observed for benzalkonium chloride (BAK) using a core-shell column functionalized with biphenyl groups. Although in the literature, the U-shaped retention was reported for polar compounds in mixed functionalized phases, in the present work, the behavior was dependent upon the chemical structure of the analyte with mixed functionality (ammonium group, a benzyl group and an alkyl chain) and on the high selectivity of the chromatographic column. The bimodal retention was observed for the four BAK homologues using a content of acetonitrile from 65 to 95% in the mobile phase. The data were adjusted to polynomial equations which allow for modeling and predicting the U-shaped retention. The salt concentration (50 and 100 mM), anion (formate and acetate) and cation (ammonium and triethylammonium) of the salt, pH (4 and 5) in the mobile phase were studied in order to understand their influence on the two retention modes. Significant electrostatic interactions were involved in the two retention modes, especially with a content of acetonitrile higher that 90%. Linear relationships between the retention factors of the four homologues were found in a wide range of %acetonitrile when the salt and triethylamine concentration, pH and nature of salt were changed. The differences found on the retention of the homologues, when increasing the alkyl chain length, were more significant in the RP mode due to predominant hydrophobic interactions. A pH decrease and a salt concentration increase caused a retention decrease for both modes. A decrease on of the retention was observed when acetate anion was replaced by formate anion. The different order of the polynomial equations according to the used mobile phase confirmed its relevant role in the interactions with the analytes and stationary phase. A mobile phase was selected (85% acetonitrile, pH 4 and 100 mM ammonium formate) for the BAK determination in cutaneous, otic and ophthalmic formulations with different active pharmaceutical ingredients and excipients. Low sample volume (500 μL) and short analysis time (<5 min) were some of the advantages of the proposed method. In addition, good analytical performance (R 2  > 0.999, % RSD <4.5% for intra-day precision and <5.8% for inter-day precision, and recoveries in the 92-105% range) was obtained., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Since the Directive 2013/39/EU included terbutryn to the list of priority substances of all water bodies, a previous method based on dispersive liquid-liquid micro-extraction (DLLME) for the determination of triazines in seawater has been modified. The main change consisted on the use of tandem mass spectrometry instead of diode array as detection technique. Due to the higher sensitivity of mass detector, sample volume was reduced and extraction solvent volume was optimized. The optimum extraction conditions were 5 mL of sample, 50 µL of 1-octanol and an agitation step instead of disperser solvent. The obtained analytical recoveries (73%-101% with relative standard deviations below 4%) meeting the requirements. The limits of quantification (between 0.016 and 0.021 µg L -1 ) were more than 10 times lower than the limit set by the European Directive 2013/39/EU for terbutryn (0.34 µg L -1 ). The proposed method was applied to the determination of the target compounds in seawater samples from A Coruña (Galicia, NW of Spain).

Triazines and their degradation products are transported to the aquatic environment, and once there, the probability to reach the marine environment is very high. In this paper, solid phase extraction (SPE) and extraction by matrix solid phase dispersion (MSPD) to analyse nine triazines (ametryn, atrazine, cyanazine, prometryn, propazine, simazine, simetryn, terbuthylazine and terbutryn) and eight degradation products (desethylatrazine, desethyldesisopropylatrazine, desethyl-2-hydroxyatrazine, desethylterbuthylazine, desisopropylatrazine, desisopropyl-2-hydroxyatrazine, 2-hydroxyatrazine and 2-hidroxyterbuthylazine) in seawater and marine sediments samples were used. The analysis was carried out using liquid chromatography with tandem mass spectrometry (LC-ESI-MS/MS). The methods were optimized and validated to achieve a selective and sensitive determination of the analytes from different sample, regardless of its complexity. Under the optimum conditions, the proposed methods provided adequate limits of quantification (0.05-0.45 μg L -1 and 0.23-4.26 μg kg -1 in seawater and marine sediments, respectively). Intra- and inter-day relative standard deviation were below 1.41% for all compounds. Recoveries were evaluated, and acceptable values that ranged from 87.5-99.4 and 60.9-99.7% for the seawater and sediment samples, respectively, were obtained. The proposed methods were applied to the analysis of the target compounds in seawater samples and marine sediments from a coastal area of Galicia (NW of Spain).

A fast, simple, selective and sensitive method has been developed for the determination of nine triazine herbicides (ametryn, atrazine, cyanazine, prometryn, propazine, simazine, simetryn, terbuthylazine and terbutryn) and eight degradation products (desethyl atrazine, desethyl-desisopropyl atrazine, desethyl 2-hydroxyatrazine, desethyl terbuthylazine, desisopropyl atrazine, desisopropyl 2-hydroxyatrazine, 2-hydroxyatrazine and 2-hidroxyterbuthylazine) in seawater samples. On-line solid-phase extraction coupled with ultra-pressure liquid chromatography-tandem mass spectrometry was employed for simultaneous analysis of all compounds in 11min. Validation parameters were studied through the estimation of the limits of detection and quantification, calibration curves and precision. Limits of quantification ranged from 0.023 to 0.657μgL -1 . Good linearity was obtained for all compounds with R 2 >0.99 in all cases. Furthermore, inter-day precision (0-2.1%) and intra-day precision (0-3.9%) were shown to be satisfactory. On-line solid-phase extraction recoveries in spiked unpolluted seawater sample were evaluated and acceptable values (80.3-99.8%) with adequate RSD (0.1-3.1%) were found. Finally, the proposed method was applied to the analysis of the target compounds in seawater samples collected from seawater nearby a zone of intensive horticulture of Matosinhos (Portugal). The concentrations of the herbicides were below the limit of detection in all cases., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A method based on Matrix Solid Phase Dispersion (MSPD) for determination of nine triazines in mussels has been optimised in terms of the sorbents used for extracting and cleaning-up. Two dispersing agents: C18 and florisil, and eight cleanup co-sorbents: florisil, silica, silica/alumina, Envi™ Carb, Envi-Carb-II/PSA, SAX/PSA, Envi-Carb-II /SAX/PSA and C18 were assayed. Analytes were eluted using 20 mL of ethyl acetate and 5 mL of acetonitrile and finally the extract was concentrated to dryness, re-constituted with 1 mL methanol and determined by HPLC-DAD. The best results were obtained with C18 as dispersing agent and Envi-Carb-II/SAX/PSA as clean-up co-column. Recoveries ranged between 79% and 99% and repeatability and reproducibility were below than 16% for all compounds. The linearity of the calibration curves yielded the R(2)⩾0.9993. The LOQ values ranged from 0.10 to 0.18 mg kg(-1) dried sample. Finally the method was applied to the analysis of mussel samples from Galicia (NW Spain)., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

A fast, simple, sensitive and green chemistry method using dispersive liquid-liquid microextraction (DLLME) for the simultaneous determination of seven triazine herbicides (ametryn, atrazine, cyanazine, propazine, simazine, simetryn and terbuthylazine) in estuarine seawater samples has been developed. DLLME was carried out using a small volume of seawater (25 mL) and 300 μL of 1-octanol. Herbicide concentrations were determined by liquid chromatography-diode array detection, and results were confirmed by liquid chromatography-electrospray ionisation tandem spectrometry analysis. The analytical features of the proposed method were satisfactory with repeatability < ±5% and intermediate precision < ±10%, and recoveries ranged from 81-102% for all compounds. All the triazines exhibited linear matrix calibration curves with coefficients of determination >0.999 for all the analytes except for simazine (0.9975). Limits of quantification ranged between 0.19 and 1.12 μg L(-1). The method was applied to the analysis of seawater samples from ten points susceptible to contamination by triazines from estuary of A Coruña (Galicia, NW of Spain). The levels of the seven triazines were below the LODs in the analysed samples. Use of proposed method will allow for monitoring of triazines at levels below the regulatory limits set by the European Directive 2008/105/EC of 2 and 4 μg L(-1) for atrazine and simazine, respectively.

A method using dual process columns of Matrix Solid Phase Dispersion (MSPD) and Solid Phase Extraction (SPE) has been developed for extracting and cleaning-up of nine triazine herbicides (ametryn, atrazine, cyanazine, prometryn, propazine, simazine, simetryn, terbuthylazine and terbutryn) in seaweed samples. Under optimized conditions, samples were blended with 2g of octasilyl-derivatized silica (C8) and transferred into an SPE cartridge containing ENVI-Carb II/PSA (0.5/0.5 g) as a clean up co-sorbent. Then the dispersed sample was washed with 10 mL of n-hexane and triazines were eluted with 20 mL ethyl acetate and 5 mL acetonitrile. Finally the extract was concentrated to dryness, re-constituted with 1 mL methanol:water (1:1) and injected into the HPLC-DAD system. The linearity of the calibration curves was excellent in matrix matched standards, and yielded the coefficients of determination>0.995 for all the target analytes. The recoveries ranged from 75% to 100% with relative standard deviations lower than 7%. The achieved LOQs (<10 µg kg(-1)) for all triazines under study permits to ensure proper determination at the maximum allowed residue levels set in the European Union Legislation. Samples of three seaweeds were subjected to the procedure proving the suitability of MSPD method for the analysis of triazines in different seaweeds samples., (Copyright © 2014 Elsevier B.V. All rights reserved.)

A simple method based on solid-phase extraction combined with liquid chromatography for simultaneous determination of nine triazine herbicides (ametryn, atrazine, cyanazine, prometryn, propazine, simazine, simetryn, terbuthylazine, and terbutryn) in surface water samples was developed and validated. Under optimized conditions, 50 mL of water sample was pumped through the Oasis HLB cartridge, and triazines were eluted with 3 mL acetone. Finally the extract was concentrated to dryness, reconstituted with 1 mL methanol : water (1 : 1) and injected into the HPLC-DAD system. The stability of the herbicides on the cartridges at -18 and 4°C was also evaluated, and the recoveries obtained after three weeks of storage were satisfactory for all compounds. The analytical features of the proposed method were satisfactory: repeatability and intermediate precision were <10% and recoveries in spiked river water and seawater samples were higher than 93% for all compounds studied. Limits of quantification (varied from 0.46 to 0.98 µg L⁻¹) were adequately allowing the determination of these compounds at the levels requested by the 2008/105/EC Directive. Finally, this method was applied to the analysis of 50 seawater samples from Galicia (northwest Spain).

Due to the extensive use of organochlorine pesticides (OCPs) for agricultural purposes and their high persistence and low biodegradability, they have become an important group of contaminants. Detection and quantification of pesticide residues in food, particularly fruits and vegetables, is of growing concern for producers, consumers, and governments. The most widely used pretreatment for the extraction of pesticides in plants is based on solvent extraction liquid-solid extraction (LSE). LSE can be carried out using Soxhlet, shake-flask, homogenization, sonication, and, more recently, microwave-assisted extraction, pressurized liquid extraction, and supercritical fluid extraction. Furthermore, new analytical procedures using the extraction with sorbents, such as solid-phase microextraction, stir bar sorptive extraction, and matrix solid-phase dispersion, have also been used. On the other hand, a wide range of cleanup methods (liquid-liquid extraction, solid-phase extraction, gel permeation chromatography, and dispersive solid-phase extraction; and chromatographic techniques with electron capture detector and mass spectrometry detector; and HPLC with a ultraviolet detector are reported in the literature. This article reviews the applicability, advantages, and disadvantages of various sample preparation techniques (traditional and new techniques) for the analysis of OCPs in different plants and plant materials. It covers more than 15 years of published methods in which pesticide residues have been determined in a wide range of vegetation samples (fruits, horticultural samples, medicinal plants, tree leaves, etc.) by the use of chromatographic techniques after various sample preparation steps. A great number of applications in different plant material are provided. To the best of the authors' knowledge, previously published reviews have not covered as wide and exhaustive range of vegetation matrixes as presented here. A summary of pesticide levels cited in the literature is included.

A method based on matrix solid-phase dispersion (MSPD) and SPE to determine 20 organochlorine pesticides (OCPs) in fish tissues (muscle and liver) was optimized in terms of the sorbents and elution solvents used for the analysis. The following analytical components were evaluated: ENVI-CarbTM and ENVI-18 as dispersing agents, Florisil and Florisil over alumina as cleanup adsorbents, and hexane and hexane-ethyl acetate (80 + 20) as elution solvents. The pesticides were determined by GC with electron capture detection. The best results were obtained with ENVI-Carb as a dispersing agent and an ENVI-Florisil co-column using 40 mL hexane-ethyl acetate (80 + 20) as the elution solvent. Analytical recoveries ranged between 75 and 130% except for beta-HCH in fish liver, and the RSD values were < 15% for most of the pesticides studied. Furthermore, sensitivity was sufficient (LOD of < 300 microg/kg) for all OCPs under study, in compliance with the tolerance limits of the U.S. Food and Drug Administration for OCPs in fish. The results were compared with those obtained by microwave-assisted extraction (MAE) and pressurized liquid extraction (PLE) in order to evaluate the performance of the MSPD procedure. The MPSD methodology was shown to be easy to use and fast, with a clear advantage relative to cost, because it does not need the expensive equipment required for MAE and PLE.

A novel analytical approach to determine trace levels of 20 organochlorine pesticides (OCPs) in nine vegetable matrices (lettuce, spinach, green bean, green pepper, tomato, broccoli, potato, carrot and onion) is proposed, based on stir bar sorptive extraction followed by liquid desorption and large volume injection-gas chromatography coupled to mass spectrometry using the selected-ion monitoring mode acquisition (SBSE-LD/LVI-GC-MS(SIM)). The experimental procedure consists of a previous ultrasonic extraction of the freeze-dried vegetable samples (100.0mg) with methanol (2mL) followed by centrifugation and dissolution in aqueous media prior to SBSE-LD/LVI-GC-MS(SIM) under optimised conditions. Assays were performed on 30mL aqueous samples using stir bars coated with 47microL of polydimethylsiloxane, an equilibrium time of 180min (1000rpm; 20 degrees C) and acetonitrile as back-extraction solvent, providing convenient analytical performance to monitor OCPs in vegetable matrices at the trace level. Besides the selectivity reached, the data obtained clearly demonstrate that the matrices involved have a strong effect on the recovery yields (10-110%) of the OCPs under study, in particular the green vegetables especially the leafy ones. By using the standard addition methodology, good linearity (r(2)>0.99) and convenient precisions (RSD<20%) were found for almost all cases, depending on the particular OCP and vegetable matrix involved. Furthermore enough sensitivity was also achieved (limit of detection <10microgkg(-1)) for all OCPs under study towards compliance with the European Union regulations for the maximum residue limits of pesticides in agricultural vegetables. The methodology showed to be easy of work-up, fast, almost solventless with low sample amount requirement, when compared with conventional methods of sample preparation to screen pesticides in vegetable matrices., (Copyright 2009 Elsevier B.V. All rights reserved.)

A method to determine 21 organochlorine pesticides in animal feed samples using microwave assisted extraction and solid phase extraction cleanup was optimised regarding its main parameters. After extraction with hexane-acetone (50:50), three different sorbents (alumina/ENVI-Florisil, ENVI-Carb and ENVI-Carb II/PSA) were assayed for the cleanup step. Analytes were eluted with hexane-ethyl acetate (80:20) and determined by gas chromatography and electron capture detection followed by gas chromatography-mass spectrometry. ENVI-Carb and ENVI-Carb II/PSA provided colourless eluates but fewer interferent compounds were found in ENVI-Carb II/PSA chromatograms, so this system was selected to carry out the purification of the extracts. The analytical recoveries obtained with this method were close to 100% in most cases with relative standard deviations lower than 10%. These percentages were similar to those obtained with the Soxhlet extraction procedure, which shows the method suitable for the determination of organochlorine pesticides in animal feed material. The method was also validated with the analysis of a certified reference material (CRM-115 BCR), and the results obtained were in good accordance with the certified values.

This paper describes a comparative study of 2 extraction methods, pressurized liquid extraction (PLE) and microwave-assisted extraction (MAE), for the determination of organochlorine pesticides (OCPs) in fish muscle samples. In both cases, samples were extracted with hexane-acetone (50 + 50), and the extracts were purified by solid-phase extraction using a carbon cartridge as the adsorbent. Pesticides were eluted with hexane-ethyl acetate (80 + 20) and determined by gas chromatography with electron-capture detection. Both methods demonstrated good linearity over the range studied (0.005-0.100 microg/mL). Detection limits ranged from 0.029 to 0.295 mg/kg for PLE and from 0.003 to 0.054 mg/kg for MAE. For most of the pesticides, analytical recoveries with both methods were between 80 and 120%, and the relative standard deviations were < 10%. The proposed methods were shown to be powerful techniques for the extraction of OCPs from fish muscle samples. Although good recovery rates were obtained with both extraction methods, MAE provided advantages with regard to sample handling, cost, analysis time, and solvent consumption. Acceptable validation parameters were obtained although MAE was shown to be more sensitive than PLE.

A method to determine organochlorine pesticides in horticultural samples (lettuce, tomato, spinach, potato, turnip leaf and green bean) using pressurized liquid extraction (PLE) is described and compared with microwave assisted extraction (MAE). Significant parameters affecting PLE procedure such as temperature, static extraction time and extraction solvent were optimised and discussed. Clean-up of extracts was performed by solid phase extraction (SPE) using a carbon cartridge as adsorbent. Pesticides were determined by gas chromatography and electron capture detection (GC-ECD). Analytical recoveries obtained were ca. 100% and the relative standard deviations were lower than 15% for most of the studied pesticides with the proposed methods in each analysed matrix.

The content of 21 organochlorine pesticides were studied in vegetation samples of a highly contaminated area by isomers of hexachlorocyclohexane (HCH) located close to a former industrial area in Galicia (NW Spain). Five species of plants were collected at different points of the contaminated area and the different parts of the plants were separated in order to study differences in accumulation capabilities. Samples were extracted employing microwave energy followed by a clean-up step using solid phase extraction and finally determined by GC-ECD. The results obtained show that the most abundant pesticides are HCHs isomers, being the main isomers beta-HCH and alpha-HCH in all samples whereas delta-HCH and gamma-HCH were at lower levels. Some other pesticides such as p,p'-DDT, p,p'-DDD and p,p'-DDE were also present in much lower amount in some of the samples. Several degradation products of HCH were also identified in some samples by GC-MS.

A method to determine 21 organochlorine pesticides (OCPs) in tree leaves [chestnut (Castanea sativa), hazel (Corylus avellana), oak (Quercus robur) and walnut tree (Juglans regia)] based on microwave-assisted extraction (MAE) followed by solid-phase extraction (SPE) clean-up is described. After extraction with hexane:acetone (50:50), four different sorbents (Florisil, tandem Florisil + alumina, silica and ENVI-Carb) were assayed for the clean-up step. Pesticides were eluted with 5 mL of hexane:ethyl acetate (80:20) and determined by gas chromatography and electron capture detection (GC-ECD). Carbon was the sorbent, which provided colourless eluates and chromatograms with less interferent compounds. Analytical recoveries obtained were ca. 100% for all the studied pesticides with this sorbent.

A method to determine 21 organochlorine pesticides in vegetation samples using microwave-assisted extraction (MAE) is described and compared with Soxhlet extraction. Samples were extracted with hexane-acetone (1:1, v/v) and the extracts were cleaned using solid-phase extraction with Florisil and alumine as adsorbents. Pesticides were eluted with hexane-ethyl acetate (80:20, v/v) and determined by gas chromatography and electron-capture detection. Recoveries obtained (75.5-132.7% for Soxhlet extraction and 81.5-108.4% for MAE) show that both methods are suitable for the determination of chlorinated pesticides in vegetation samples. The method using microwave energy was applied to grass samples from parks of A Coruña (N.W. Spain) and to vegetation from the contaminated industrial area of Torneiros (Pontevedra, N.W. Spain).

A high-performance liquid chromatographic method using refractive index detection for the determination of glycogen in sea urchin (Paracentrotus lividus) gonads is developed. After alkaline digestion with sodium carbonate, samples are adjusted to pH 4.6 with citric acid and incubated with amyloglucosidase to hydrolyze the glycogen. The resulting glucose is determined using a Spherisorb NH2 column as the stationary phase and an acetonitrile-water mixture (80:20, v/v) as the mobile phase. The relative standard deviation (%) was 3.57, the limit of detection was 40.1 microg/mL, and the recovery percentage was 97.2%.

"Padrón-type" peppers are a small variety of Capsicum annuum cultivated mainly in Galicia, Spain. To compare the effects of freezing and freeze-drying on the volatile components of Padrón-type peppers, preserved samples are analyzed by means of dynamic headspace sampling on an adsorbent followed by microwave desorption into a gas chromatograph equipped with a mass spectrometric detector. Sixty-five compounds are identified, including hydrocarbons, terpenes, alcohols, phenols, ethers, aldehydes, ketones, esters, pyrroles, pyrazines, and sulfurous compounds. Fresh whole, homogenized, and freeze-dried peppers have characteristic volatile-component profiles, whereas frozen peppers have a highly variable volatile-component profile.