Karakterisering og anvendelse af passive samplere for Overvågning af pesticider i vand
Summary
A protocol about the characterization and application of five different passive sampling devices is presented.
Abstract
Fem forskellige vand passive samplere blev kalibreret under laboratorieforhold til måling af 124 arv og aktuelle brugte pesticider. Denne undersøgelse giver en protokol for den passive sampler forberedelse, kalibrering, ekstraktion metode og instrumentel analyse. Sampling satser (R S) og passive sampler-vand fordelingskoefficienter (K PW) blev beregnet for silikonegummi, polært organisk kemisk integrativ sampler POCIS-A, POCIS-B, SDB-RPS og C 18 disk. Optagelsen af de udvalgte forbindelser afhang af deres fysisk-kemiske egenskaber, dvs. viste silikonegummi en bedre optagelse for flere hydrofobe forbindelser (log oktanol-vand fordelingskoefficienten (K OW)> 5.3), hvorimod POCIS-A, POCIS-B og SDB- RPS disk var mere egnet til hydrofile forbindelser (log K OW <0,70).
Introduction
Pesticider løbende introduceret til vandmiljøet og kan udgøre en risiko for vandorganismer 1. Overvågning af pesticider i det vandige miljø udføres typisk ved hjælp af grab prøveudtagning, men denne sampling teknik ikke fuldt ud højde for tidsmæssige variationer i koncentrationer på grund af udsving i flow eller episodiske input (f.eks, nedbør, overløb, spildevand lagune release) 2 3. Således overvågningsmetoder skal forbedres for en bedre vurdering af miljørisici forbundet med pesticider. Passiv prøvetagning giver kontinuerlig overvågning over en længere periode med minimal infrastruktur og lave forureningskoncentrationer 4,5.
Passive samplere har vist sig at være et værdifuldt værktøj til overvågning i grundvandet 6, frisk vand 7-10, spildevand 11 og havområder 12. Udover overvågningsformål <sup> 13,14, har passive samplere også blevet anvendt til ikke-target-analyse 15, toksikologi test 16,17, og som et alternativ til sediment og bioovervågning 18. Passive samplere ophobes kemikalier kontinuerligt fra vand og give tidsvægtet gennemsnit (TWA) koncentrationer 14. Optagelsen af det forurenende afhænger samplingfrekvens (R S) og passiv sampler-vand fordelingskoefficienten (K PW), som afhænger af den passive sampler design, sampler materiale, fysisk-kemiske egenskaber forureningsstoffet, og miljømæssige forhold (f.eks, vand turbulens, temperatur) 13,14,19,20.
Den detaljerede video har til formål at vise, hvordan man kalibrere og anvende passive prøvetagere for pesticider i vand. De specifikke mål omfattede i) at udføre forberedelse, udvinding og instrumentel analyse for 124 individuelle pesticider anvender fem forskellige typer af passiv SamplERS, herunder silikonegummi, polært organisk kemisk integrativ sampler (POCIS) -A, POCIS-B, SDB-RPS og C18 disk, ii) at vurdere R S og K PW for pesticider i et laboratorium uptake undersøgelse, og iii) at vise, hvordan du vælger den passende passive sampler af målforbindelsen af interesse og hvordan man beregner TWA koncentrationer for det respektive passive sampler.
Referencestandarder og passive sampler enheder
Målforbindelser omfattede 124 arv og i øjeblikket anvendes pesticider, herunder herbicider, insekticider og fungicider (tabel 1). Intern standard blanding (IS blanding) inkluderet fenoprop (2,4,5-TP), clothianidin-D3, ethion og terbuthylazin-D 5. Andre anvendte kemikalier inkluderet methanol (MeOH), acetonitril (ACN), acetone (ACE), dichlormethan (DCM), cyclohexan (CH), ethylacetat (EA), petroleum ethende (PE), 2-propanol, 25% ammoniakopløsning, eddikesyre (HAc) og myresyre (FA). Fem forskellige passive sampling anordninger blev karakteriseret, herunder silikonegummi, POCIS-A og POCIS-B, SDB-RPS, og C 18 disk 1,21.
Tabel 1. Passiv sampler sampling rate (R 'S, L dag -1), sampler-vand fordelingskoefficienter (K' PW, L kg -1) og ligninger (ligning.), Der anvendes til beregning af koncentrationer i marken prøver til individuel pesticider a. (Gengivet fra Journal of Chromatography A, 1405, Lutz Ahrens, Atlasi Daneshvar, Anna E. Lau, Jenny Kreuger, Karakterisering af fem passive sampling udstyr til overvågning af pesticider i vand, 1-11, Copyright (2015), med tilladelse fra Elsevier .) 22 klik her for at downloade denne fil.
Protocol
Representative Results
Discussion
For kvalitetskontrol, som standardprocedure, laboratorie emner, detektionsgrænser (LOD), inddrivelser og repeterbarhed blev undersøgt 23. Enkelte pesticider blev påvist i de blindprøver ved lave koncentrationsniveauer. Bestemmelsesgrænseværdier blev sat som værdien af det laveste punkt på kalibreringskurven, der opfylder kriterierne for et signal til støj-forhold på 3. De gennemsnitlige bestemmelsesgrænseværdier var 8,0 pg absolut injiceret på søjlen for silikonegummi, 1,7 pg absolut for P…
Declarações
The authors have nothing to disclose.
Acknowledgements
The Swedish EPA (Naturvårdsverket) (agreement 2208-13-001) and Centre for Chemical Pesticides (CKB) are gratefully acknowledged for funding this project. We thank Märit Peterson, Henrik Jernstedt, Emma Gurnell and Elin Paulsson at the OMK-lab, SLU, for skillful assistance with analytical support and supply of pesticide standards.
Materials
| Methanol | Merck Millipore | 1.06035.2500 | |
| Acetonitrile | Merck Millipore | 1.00029.2500 | |
| Acetone | Merck Millipore | 1.00012.2500 | |
| 2-propanol | Merck Millipore | 1.00272.2500 | |
| Dichloromethane | Merck Millipore | 1.06054.2500 | |
| Ammoniak | Merck Millipore | 1.05428.1000 | Purity 25% |
| Formic acid | Sigma-Aldrich | 94318-50ML-F | Purity ~98% |
| Ethyl acetate | Sigma-Aldrich | 31063-2.5L | for pesticide residue analysis |
| Petroleum ether | Sigma-Aldrich | 34491-4X2.5L | for pesticide residue analysis |
| Acetic acid | Sigma-Aldrich | 320099-500ML | Purity ≥99.7% |
| Cyclohexane | Fisher Chemicals | C/8933/17 | for residue analysis |
| Empty polypropylene SPE Tube with PE frits, 20 μm porosity, volume 6 mL | Supelco | 57026 | |
| Empore SPE Disks, C18, diam. 47 mm | Supelco | 66883-U | Passive sampler |
| Empore SPE Disks, SDB-RPS (Reversed-Phase Sulfonate), diam. 47 mm | Supelco | 66886-U | Passive sampler |
| POCIS-A | EST | POCIS-HLB | Passive sampler |
| POCIS-B | EST | POCIS-Pesticide | Passive sampler |
| Polyethersulfone (PES) membranes | EST | PES | |
| Silicone rubber sheet | Altec | 03-65-4516 | Passive sampler |
| Agilent 5975C | Agilent Technologies | 5975C | GC-MS |
| HP-5MS UI | J&W Scientific | HP-5MS | Analytical column for GC-MS |
| Agilent 6460 | Agilent Technologies | 6460 | HPLC-MS/MS |
| Strata C18–E, 20 x 2 mm id and 20–25 μm particle size | Phenomenex | Strata C18–E | Online SPE column for LC-MS/MS |
| Strata X, 20 x 2 mm id and 20–25 μm particle size | Phenomenex | Strata X | Online SPE column for LC-MS/MS |
| Zorbax Eclipse Plus C18 | Agilent Technologies | Zorbax Eclipse Plus C18 | Analytical column for LC-MS/MS |
| Isolute phase separator, 25 mL | Biotage | 120-1907-E | |
| Stainless steel blind rivet, 3.2×10 mm | Ejot & Avdel | 951222 |
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