Abstract
This work reports a fast and reliable analytical method for the screening of priority pesticides (PPs) in Ulva sp. seaweeds by gas chromatography with electron capture detection. Extraction and sample clean-up were performed in one single step by selective pressurized liquid extraction (SPLE). Several parameters affecting SPLE performance were optimized. Method performance was compared with standard Soxhlet extraction. Significant decrease of the time of analysis with better recoveries for a greater number of PPs was achieved by SPLE. Average recoveries ranged from 71 to 103 % with RSD < 10 %. Field application showed the presence of PP in the range of 3–11 ng g−1 in seaweeds collected in a coastal lagoon after a long period of heavy rains. These results suggest that Ulva sp. seaweeds tend to accumulate PPs and have the potential to be used as early alert signals of aquatic pollution especially after rains and storm events.
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American National Standard Institute (2002) ASTM: D 5812 – 96 (2002)e1: standard test method for determination of organochlorine pesticides in water by capillary column gas chromatography. ASTM International, West Conshohocken, PA
Besse JP, Geffard O, Coquery M (2012) Relevance and applicability of active biomonitoring in continental waters under the Water Framework Directive. Trends Anal Chem 36:113–127
Björklund E, Bøwadt S, Nilsson T, Mathiasson L (1999) Pressurized fluid extraction of polychlorinated biphenyls in solid environmental samples. J Chromatogr A 836:285–293
Björklund E, Sporring S, Wiberg K, Haglund P, Holst C (2006) New strategies for extraction and clean-up of persistent organic pollutants from food and feed samples using selective pressurized liquid extraction. Trends Anal Chem 25:318–325
Carafa R, Wollgast S, Canuti E, Ligthart J, Dueri S, Hanke G et al (2007) Seasonal variations of selected herbicides and related metabolites in water, sediment, seaweed and clams in the Sacca di Goro coastal lagoon (Northern Adriatic). Chemosphere 69:1625–1637
Carvalho S, Gaspar MB, Moura A, Vale C, Antunes P, Gil O et al (2006) The use of the marine biotic index AMBI in the assessment of the ecological status of the Óbidos lagoon (Portugal). Mar Pollut Bull 52:1411–1424
Eller KI, Lehotay SJ (1997) Evaluation of hydromatrix and magnesium sulfate drying agents for supercritical fluid extraction of multiple pesticides in produce. Analyst 122:429–435
EN 15662 (2008) Foods of plant origin—Determination of pesticides residues using GC-MS and/or LC-MS/MS following acetonitrile extraction/partitioning and clean-up by dispersive SPE-QuEChERS method. European Committee for Standardisation (EN), European Union, November 2008
European Commission (2000) Directive 2000/60/EC of the European Parliament and of the Council of 23 October establishing a framework for Community action in the field of water Policy. Off J Eur Commun L327:1
European Commission (2001) Decision no. 2455/2001/EC of the European of Parliament and of the Council of 20 November 2001 establishing the list of priority substances in the field of water policy and amending Directive 2000/60/EC. Off J Eur Commun L331:1
European Commission (2005) Regulation (EC) no. 396/2005 of the European Parliament and of the Council of 23 February 2005 on maximum residue levels of pesticides in or on food and feed of plant and animal origin and amending Council Directive 91/414/EEC
European Commission (2011) Document no. SANCO/12495/2011—Method validation and quality control procedures for pesticides residues analysis in food and feed
Ferreira AM, Vale C (1995) The importance of runoff to DDT and PCB inputs to the Sado Estuary and Ria Formosa. Neth J Aquat Ecol 29:211–216
García-Rodríguez D, Carro-Díaz AM, Lorenzo-Ferreira RA, Cela-Torrijos R (2010) Determination of pesticides in seaweeds by pressurized liquid extraction and programmed temperature vaporization-based large volume injection–gas chromatography–tandem mass spectrometry. J Chromatogr A 1217:2940–2949
Jayasekera R, Rossbach M (1996) Use of seaweeds for monitoring trace elements in coastal waters. Environ Geochem Health 18:63–68
Koning S, Janssen HG, Brinkman Udo ATh (2009) Modern methods of sample preparation for GC analysis. Chromatographia 69:S33–S78
Lehotay SJ, Lee CH (1997) Evaluation of a fibrous cellulose drying agent in supercritical fluid extraction and pressurized liquid extraction of diverse pesticides. J Chromatogr A 785:313–327
Li L, Li W, Qin D, Jiang S, Liu F (2009) Application of graphitized carbon black to the QuEChERS method for pesticide multiresidue analysis in spinach. J AOAC Int 92:538–547
Lorenzo RA, Pais S, Racamonde I, García-Rodríguez D, Carro AM (2012) Pesticides in seaweed: Optimization of pressurized liquid extraction and in-cell clean-up and analysis by liquid chromatography–mass spectrometry. Anal Bioanal Chem 404:173–181
Mackay D, Shiu WY, Ma KC, Lee SC (2006) Handbook of physical-chemical properties and environmental fate of organic chemicals, 2nd edn. CRC Press Taylor & Francis Group, Boca Raton
Maroli L, Pavoni B, Sfriso A, Raccanell S (1993) Concentrations of polychlorinated biphenyls and pesticides in different species of macroalgae from the Venice lagoon. Mar Pollut Bull 26:553–558
Martins M, Costa PM, Raimundo J, Vale C, Ferreira AM, Costa MH (2012) Impact of remobilized contaminants in Mytilus edulis dredging operations in a harbour area: Bioaccumulation and biomarker responses. Ecotoxicol Environ Saf 85:96–103
Nollet LML, Rathore HS (2010) Handbook of pesticides: methods of pesticide residues analysis, 1st edn. CRC Press Taylor & Francis Group, Boca Raton
Ottonello G, Ferrari A, Magi E (2014) Determination of polychlorinated biphenyls in fish: optimisation and validation of a method based on accelerated solvent extraction and gas chromatography–mass spectrometry. Food Chem 142:327–333
Pavoni B, Caliceti M, Sperni L, Sfriso A (2003) Organic micropollutants (PAHs, PCBs, pesticides) in seaweeds of the lagoon of Venice. Oceanol Acta 26:585–596
Perati P, Ullah SR (2013) Extraction of organochloride pesticides from oyster tissue using accelerated solvent extraction. In: Application Brief 152. Thermo Fischer Scientific, Sunnyvale, CA
Pereira P, Pablo H, Vale C, Rosa-Santos F, Cesário R (2009) Metal and nutrient dynamics in a eutrophic coastal lagoon (Óbidos, Portugal): the importance of observations at different time scales. Environ Monit Assess 158:405–418
Perrin DD, Armarego WLF, Perrin DR (1980) Purification of laboratory chemicals, 2nd edn. Pergamon, Oxford
Pinto MI, Sontag G, Vale C, Noronha JP (2013) Effects of ultrasonic irradiation and direct heating on extraction of priority pesticides from marine sediments. Int J Environ Anal Chem 93:1638–1659
Steene JCVD, Lambert WE (2008) Comparison of matrix effects in HPLC-MS/MS and UPLC–MS/MS analysis of nine basic pharmaceuticals in surface waters. J Am Soc Mass Spectrom 19:713–718
Stout PR, Bynum ND, Lewallen CM, Mitchell JM, Baylor MR, Ropero-Miller JD (2010) A comparison of the validity of gas chromatography–mass spectrometry and liquid chromatography-tandem mass spectrometry analysis of urine samples II: amphetamine, methamphetamine, (±)-3,4-methylenedioxyamphetamine, (±)-3,4-methylenedioxymethamphetamine, (±)-3,4-methylenedioxyethylamphetamine, phencyclidine, and (±)-11-nor-9-carboxy-Δ9-tetrahydrocannabinol. J Anal Toxicol 34:430–443
Tadeo JL (2008) Analysis of pesticides in food and environmental samples. CRC Press, Boca Raton
Tomlin CDS (1997) The pesticide manual. British Crop Protection Council, Surrey, UK
United States Environmental Protection Agency (1996) Method 3540c:1996—Soxhlet extraction. USEPA
United States Environmental Protection Agency (1996) Method 3545:1996—Pressurized fluid extraction. USEPA
United States Environmental Protection Agency (2007) Method 3620c:2007—Florisil cleanup. USEPA
Xu W, Wang X, Cai Z (2013) Analytical chemistry of the persistent organic pollutants identified in the Stockholm Convention: a review. Anal Chim Acta 790:1–13
Acknowledgments
The authors are grateful to Fundação para a Ciência e Tecnologia (Ministério do Ensino Superior e Ciência e Tecnologia) for the doctoral fellowship to M. Isabel Pinto (Grant No. SFRH/BD/76547/2011). The authors also thank Isabelina Santos and Rute Granja for their technical support in this work.
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Pinto, M.I., Micaelo, C., Vale, C. et al. Screening of Priority Pesticides in Ulva sp. Seaweeds by Selective Pressurized Solvent Extraction Before Gas Chromatography with Electron Capture Detector Analysis. Arch Environ Contam Toxicol 67, 547–556 (2014). https://doi.org/10.1007/s00244-014-0038-2
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DOI: https://doi.org/10.1007/s00244-014-0038-2