The Swedish EPA (Naturv&#229;rdsverket) (agreement 2208-13-001) and Centre for Chemical Pesticides (CKB) are gratefully acknowledged for funding this project. We thank M&#228;rit Peterson, Henrik Jernstedt, Emma Gurnell and Elin Paulsson at the OMK-lab, SLU, for skillful assistance with analytical support and supply of pesticide standards.

1. Passive Sampler Design and Preparation
<ol>
	<li>Silicone rubber sheets
	<ol>
		<li>Cut the silicone rubber sheets (600 mm x 600 mm, 0.5 mm thick) into stripes of 2.5 mm x 600 mm and 2.5 mm x 314 mm using a stainless steel cutter and connect them using a stainless steel blind rivet (3.2 mm x 10 mm) with a rivet gun to obtain a total sampler stripe size of 2.5 mm x 914 mm (surface area = 457 cm2, sorbent mass = 15.6 g, volume = 22.9 cm3).</li>
	</ol>
	</li>
	<li>Place the silico...

<ol>
	<li>Rodney, S. I., Teed, R. S., Moore, D. R. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Estimating+the+toxicity+of+pesticide+mixtures+to+aquatic+organisms:+A+review.">Estimating the toxicity of pesticide mixtures to aquatic organisms: A review.</a> Hum. Ecol. Risk Assess. 19 (6), 1557-1575 (2013).</li><li>Kreuger, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Pesticides+in+stream+water+within+an+agricultural+catchment+in+southern+Sweden,+1990-1996.">Pesticides in stream water within an agricultural catchment in southern Sweden, 1990-1996.</a> Sci. Total Environ. 216 (3), 227-251 (1998).</li><li>Carlson, J. C., Challis, J. K., Hanson, M. L., Wong, C. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Stability+of+pharmaceuticals+and+other+polar+organic+compounds+stored+on+polar+organic+chemical+integrative+samplers+and+solid-phase+extraction+cartridges.">Stability of pharmaceuticals and other polar organic compounds stored on polar organic chemical integrative samplers and solid-phase extraction cartridges.</a> Environ. Toxicol. Chem. 32 (2), 337-344 (2013).</li><li>Alvarez, D. A., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Development+of+a+passive,+in+situ,+integrative+sampler+for+hydrophilic+organic+contaminants+in+aquatic+environments.">Development of a passive, in situ, integrative sampler for hydrophilic organic contaminants in aquatic environments.</a> Environ. Toxicol. Chem. 23 (7), 1640-1648 (2004).</li><li>Vrana, B., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Passive+sampling:+An+effective+method+for+monitoring+seasonal+and+spatial+variability+of+dissolved+hydrophobic+organic+contaminants+and+metals+in+the+Danube+river.">Passive sampling: An effective method for monitoring seasonal and spatial variability of dissolved hydrophobic organic contaminants and metals in the Danube river.</a> Environ. Pollut. 184, 101-112 (2014).</li><li>Dougherty, J. A., Swarzenski, P. W., Dinicola, R. S., Reinhard, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Occurrence+of+herbicides+and+pharmaceutical+and+personal+care+products+in+surface+water+and+groundwater+around+Liberty+Bay,+Puget+Sound,+Washington.">Occurrence of herbicides and pharmaceutical and personal care products in surface water and groundwater around Liberty Bay, Puget Sound, Washington.</a> J. Environ. Qual. 39 (4), 1173-1180 (2010).</li><li>Mu&#241;oz, I., Mart&#236;nez Bueno, M. J., Ag&#252;era, A., Fern&#225;ndez-Alba, A. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Environmental+and+human+health+risk+assessment+of+organic+micro-pollutants+occurring+in+a+Spanish+marine+fish+farm.">Environmental and human health risk assessment of organic micro-pollutants occurring in a Spanish marine fish farm.</a> Environ. Pollut. 158 (5), 1809-1816 (2010).</li><li>Wille, K., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Rapid+quantification+of+pharmaceuticals+and+pesticides+in+passive+samplers+using+ultra+high+performance+liquid+chromatography+coupled+to+high+resolution+mass+spectrometry.">Rapid quantification of pharmaceuticals and pesticides in passive samplers using ultra high performance liquid chromatography coupled to high resolution mass spectrometry.</a> J. Chromatogr. A. 1218 (51), 9162-9173 (2011).</li><li>Poulier, G., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Estimates+of+pesticide+concentrations+and+fluxes+in+two+rivers+of+an+extensive+French+multi-agricultural+watershed:+application+of+the+passive+sampling+strategy.">Estimates of pesticide concentrations and fluxes in two rivers of an extensive French multi-agricultural watershed: application of the passive sampling strategy.</a> Environ. Sci. Pollut. Res. 22 (11), 8044-8057 (2015).</li><li>Moschet, C., Vermeirssen, E. L. M., Singer, H., Stamm, C., Hollender, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Evaluation+of+in-situ+calibration+of+chemcatcher+passive+samplers+for+322+micropollutants+in+agricultural+and+urban+affected+rivers.">Evaluation of in-situ calibration of chemcatcher passive samplers for 322 micropollutants in agricultural and urban affected rivers.</a> Water Res. 71, 306-317 (2015).</li><li>Petty, J. D., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=An+approach+for+assessment+of+water+quality+using+semipermeable+membrane+devices+(SPMDs)+and+bioindicator+tests.">An approach for assessment of water quality using semipermeable membrane devices (SPMDs) and bioindicator tests.</a> Chemosphere. 41 (3), 311-321 (2000).</li><li>Metcalfe, C. D., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Contaminants+in+the+coastal+karst+aquifer+system+along+the+Caribbean+coast+of+the+Yucatan+Peninsula,+Mexico.">Contaminants in the coastal karst aquifer system along the Caribbean coast of the Yucatan Peninsula, Mexico.</a> Environ. Pollut. 159 (4), 991-997 (2011).</li><li>Allan, I. J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Field+performance+of+seven+passive+sampling+devices+for+monitoring+of+hydrophobic+substances.">Field performance of seven passive sampling devices for monitoring of hydrophobic substances.</a> Environ. Sci. Technol. 43 (14), 5383-5390 (2009).</li><li>Vrana, B., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Passive+sampling+techniques+for+monitoring+pollutants+in+water.">Passive sampling techniques for monitoring pollutants in water.</a> TrAC - Trend. Anal. Chem. 24 (10), 845-868 (2005).</li><li>Allan, I. J., Harman, C., Ranneklev, S. B., Thomas, K. V., Grung, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Passive+sampling+for+target+and+nontarget+analyses+of+moderately+polar+and+nonpolar+substances+in+water.">Passive sampling for target and nontarget analyses of moderately polar and nonpolar substances in water.</a> Environ. Toxicol. Chem. 32 (8), 1718-1726 (2013).</li><li>Escher, B. I., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Evaluation+of+contaminant+removal+of+reverse+osmosis+and+advanced+oxidation+in+full-scale+operation+by+combining+passive+sampling+with+chemical+analysis+and+bioanalytical+tools.">Evaluation of contaminant removal of reverse osmosis and advanced oxidation in full-scale operation by combining passive sampling with chemical analysis and bioanalytical tools.</a> Environ. Sci. Technol. 45, 5387-5394 (2011).</li><li>Pesce, S., Morin, S., Lissalde, S., Montuelle, B., Mazzella, N. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Combining+polar+organic+chemical+integrative+samplers+(POCIS)+with+toxicity+testing+to+evaluate+pesticide+mixture+effects+on+natural+phototrophic+biofilms.">Combining polar organic chemical integrative samplers (POCIS) with toxicity testing to evaluate pesticide mixture effects on natural phototrophic biofilms.</a> Environ. Pollut. 159 (3), 735-741 (2011).</li><li>Booij, K., Smedes, F., Van Weerlee, E. M., Honkoop, P. J. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Environmental+monitoring+of+hydrophobic+organic+contaminants:+The+case+of+mussels+versus+semipermeable+membrane+devices.">Environmental monitoring of hydrophobic organic contaminants: The case of mussels versus semipermeable membrane devices.</a> Environ. Sci. Technol. 40 (12), 3893-3900 (2006).</li><li>Harman, C., Allan, I. J., Vermeirssen, E. L. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Calibration+and+use+of+the+polar+organic+chemical+integrative+sampler-a+critical+review.">Calibration and use of the polar organic chemical integrative sampler-a critical review.</a> Environ. Toxicol. Chem. 31 (12), 2724-2738 (2012).</li><li>Jonker, M. T. O., Der Heijden, S. A. V. a. n., Kotte, M., Smedes, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Quantifying+the+effects+of+temperature+and+salinity+on+partitioning+of+hydrophobic+organic+chemicals+to+silicone+rubber+passive+samplers.">Quantifying the effects of temperature and salinity on partitioning of hydrophobic organic chemicals to silicone rubber passive samplers.</a> Environ. Sci. Technol. 49 (11), 6791-6799 (2015).</li><li>Jansson, C., Kreuger, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Multiresidue+analysis+of+95+pesticides+at+low+nanogram/liter+levels+in+surface+waters+using+online+preconcentration+and+high+performance+liquid+chromatography/tandem+mass+spectrometry.">Multiresidue analysis of 95 pesticides at low nanogram/liter levels in surface waters using online preconcentration and high performance liquid chromatography/tandem mass spectrometry.</a> J. AOAC Int. 93 (6), 1732-1747 (2010).</li><li>Ahrens, L., Daneshvar, A., Lau, A. E., Kreuger, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Characterization+of+five+passive+sampling+devices+for+monitoring+of+pesticides+in+water.">Characterization of five passive sampling devices for monitoring of pesticides in water.</a> J. Chromatogr. A. 1405, 1-11 (2015).</li><li>Royston, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Approximating+the+Shapiro-Wilk+W-test+for+non-normality.">Approximating the Shapiro-Wilk W-test for non-normality.</a> Stat. Comput. 2 (3), 117-119 (1992).</li><li>Gauthier, T. D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Detecting+trends+using+Spearman's+rank+correlation+coefficient.">Detecting trends using Spearman's rank correlation coefficient.</a> Environ. Forensics. 2 (4), 359-362 (2001).</li><li>Morin, N., Mi&#232;ge, C., Coquery, M., Randon, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Chemical+calibration,+performance,+validation+and+applications+of+the+polar+organic+chemical+integrative+sampler+(POCIS)+in+aquatic+environments.">Chemical calibration, performance, validation and applications of the polar organic chemical integrative sampler (POCIS) in aquatic environments.</a> TrAC - Trend. Anal. Chem. 36, 144-175 (2012).</li><li>. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Water+Quality+-+Sampling+-+Part+23:+Guidance+on+Passive+Sampling+in+Surface+Waters.">Water Quality - Sampling - Part 23: Guidance on Passive Sampling in Surface Waters.</a> ISO 5667-23:2011. , (2011).</li><li>Morin, N., Camilleri, J., Cren-Oliv&#233;, C., Coquery, M., Mi&#232;ge, C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Determination+of+uptake+kinetics+and+sampling+rates+for+56+organic+micropollutants+using+"pharmaceutical"+POCIS.">Determination of uptake kinetics and sampling rates for 56 organic micropollutants using "pharmaceutical" POCIS.</a> Talanta. 109, 61-73 (2013).</li></ol>

For quality control, as standard procedure, laboratory blanks, limits of detection (LOD), recoveries, and repeatability were examined23. A few pesticides were detected in the blank samples at low concentration levels. LODs were set as the value of the lowest point on the calibration curve which meets the criteria of a signal to noise ratio of 3. The average LODs were 8.0 pg absolute injected on column for silicone rubber, 1.7 pg absolute for POCIS-A, 1.6 pg absolute for POCIS-B, 3.0 pg absolute for SDB-RPS dis...

Pesticides are continuously introduced to the aquatic environment and may pose a risk to aquatic organisms1. Monitoring of pesticides in the aqueous environment is typically performed using grab sampling, however, this sampling technique does not fully account for temporal variations in concentrations due to fluctuations in flow or episodic inputs (e.g., precipitation, combined sewer overflows, sewage lagoon release)2,3. Thus, monitoring methods need to be improved for a better estimation of environmental risks associated with pesticides. Passive sampling allows continuous monitoring over an extended period of time with minimal infrastructure and low contaminant concentrations4,5.
Passive samplers have been shown to be a valuable tool for the monitoring in groundwater6, fresh water7-10, wastewater11 and marine waters12. Besides monitoring purposes13,14, passive samplers have also been used for non-target analysis15, toxicology testing16,17, and as an alternative to sediment- and biomonitoring18. Passive samplers accumulate chemicals continuously from water and provide time weighted average (TWA) concentrations14. The uptake of the contaminant depends on the sampling rate (RS) and passive sampler-water partition coefficient (KPW), which depends on the passive sampler design, sampler material, physicochemical properties of the contaminant, and environmental conditions (e.g., water turbulence, temperature)13,14,19,20.
The detailed video aims to show how to calibrate and apply passive samplers for pesticides in water. The specific objectives included i) to perform preparation, extraction and instrumental analysis for 124 individual pesticides using five different types of passive samplers, including silicone rubber, polar organic chemical integrative sampler (POCIS)-A, POCIS-B, SDB-RPS and C18 disk, ii) to assess RS and KPW for the pesticides in a laboratory uptake study, and iii) to demonstrate how to select the appropriate passive sampler of the target compound of interest and how to calculate TWA concentrations for the respective passive sampler.
Reference standards and passive sampler devices
Target compounds included 124 legacy and currently used pesticides including herbicides, insecticides and fungicides (Table 1). Internal standard mixture (IS mixture) included fenoprop (2,4,5-TP), clothianidin-D3, ethion and terbuthylazine-D5. Other used chemicals included methanol (MeOH), acetonitrile (ACN), acetone (ACE), dichloromethane (DCM), cyclohexane (CH), ethyl acetate (EA), petroleum ether (PE), 2-propanol, 25% ammonia solution, acetic acid (HAc) and formic acid (FA). Five different passive sampling devices were characterized, including silicone rubber, POCIS-A and POCIS-B, SDB-RPS, and C18 disk1,21.
Table 1. Passive sampler sampling rate (R&#39;S, L day-1), sampler-water partition coefficients (K&#39;PW, L kg-1) and equations (Eq.) used for the calculation of concentrations in field samples for individual pesticidesa. (Reprinted from Journal of Chromatography A, 1405, Lutz Ahrens, Atlasi Daneshvar, Anna E. Lau, Jenny Kreuger, Characterization of five passive sampling devices for monitoring of pesticides in water, 1-11, Copyright (2015), with permission from Elsevier.)22 <a href="https://www.jove.com/files/ftp_upload/54053/Table_1.xlsx" target="_blank">Please click here to download this file.</a>

<table border="0" cellpadding="0" cellspacing="0" width="1047">
	<tbody>
		<tr height="21">
			<td height="21" style="height:21px;width:492px;">Methanol</td>
			<td style="width:164px;">Merck Millipore</td>
			<td style="width:163px;">1.06035.2500</td>
			<td style="width:228px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Acetonitrile</td>
			<td>Merck Millipore</td>
			<td>1.00029.2500&#160;</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:22px;width:492px;">Acetone</td>
			<td>Merck Millipore</td>
			<td style="width:163px;">1.00012.2500</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">2-propanol</td>
			<td>Merck Millipore</td>
			<td>1.00272.2500</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Dichloromethane</td>
			<td>Merck Millipore</td>
			<td>1.06054.2500</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Ammoniak</td>
			<td>Merck Millipore</td>
			<td>1.05428.1000</td>
			<td>Purity 25%</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Formic acid</td>
			<td style="width:164px;">Sigma-Aldrich</td>
			<td>94318-50ML-F</td>
			<td>Purity ~98%</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:22px;">Ethyl acetate&#160;</td>
			<td style="width:164px;">Sigma-Aldrich</td>
			<td>31063-2.5L</td>
			<td>for pesticide residue analysis</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:22px;">Petroleum ether&#160;</td>
			<td style="width:164px;">Sigma-Aldrich</td>
			<td>34491-4X2.5L</td>
			<td>for pesticide residue analysis</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Acetic acid&#160;</td>
			<td style="width:164px;">Sigma-Aldrich</td>
			<td>320099-500ML</td>
			<td>Purity &#8805;99.7%</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Cyclohexane&#160;</td>
			<td style="width:164px;">Fisher Chemicals</td>
			<td>C/8933/17</td>
			<td>for residue analysis</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Empty polypropylene SPE Tube with PE frits, 20 &#956;m porosity, volume 6&#160;mL</td>
			<td style="width:164px;">Supelco</td>
			<td>57026</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:492px;">Empore SPE Disks, C18, diam. 47&#160;mm</td>
			<td>Supelco</td>
			<td style="width:163px;">66883-U</td>
			<td>Passive sampler</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:492px;">Empore SPE Disks, SDB-RPS (Reversed-Phase Sulfonate), diam. 47&#160;mm</td>
			<td>Supelco</td>
			<td style="width:163px;">66886-U&#160;</td>
			<td>Passive sampler</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:492px;">POCIS-A&#160;</td>
			<td>EST</td>
			<td style="width:163px;">POCIS-HLB</td>
			<td>Passive sampler</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:492px;">POCIS-B</td>
			<td>EST</td>
			<td style="width:163px;">POCIS-Pesticide&#160;</td>
			<td>Passive sampler</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:492px;">Polyethersulfone (PES) membranes</td>
			<td>EST</td>
			<td style="width:163px;">PES</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:492px;">Silicone rubber sheet</td>
			<td style="width:164px;">Altec</td>
			<td style="width:163px;">03-65-4516</td>
			<td>Passive sampler</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:492px;">Agilent 5975C</td>
			<td style="width:164px;">Agilent Technologies</td>
			<td style="width:163px;">5975C</td>
			<td>GC-MS</td>
		</tr>
		<tr height="23">
			<td height="23" style="height:23px;width:492px;">HP-5MS UI</td>
			<td style="width:164px;">J&#38;W Scientific</td>
			<td style="width:163px;">HP-5MS</td>
			<td>Analytical column for GC-MS</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:492px;">Agilent 6460</td>
			<td style="width:164px;">Agilent Technologies</td>
			<td style="width:163px;">6460</td>
			<td>HPLC-MS/MS</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:492px;">Strata C18&#8211;E, 20 x 2 mm id and 20&#8211;25 &#956;m particle size</td>
			<td style="width:164px;">Phenomenex</td>
			<td style="width:163px;">Strata C18&#8211;E</td>
			<td style="width:228px;">Online SPE column for LC-MS/MS</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:492px;">Strata X, 20 x 2 mm id and 20&#8211;25 &#956;m particle size</td>
			<td style="width:164px;">Phenomenex</td>
			<td style="width:163px;">Strata X</td>
			<td style="width:228px;">Online SPE column for LC-MS/MS</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:492px;">Zorbax Eclipse Plus C18</td>
			<td style="width:164px;">Agilent Technologies</td>
			<td style="width:163px;">Zorbax Eclipse Plus C18</td>
			<td>Analytical column for LC-MS/MS</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:492px;">Isolute phase separator, 25 mL</td>
			<td style="width:164px;">Biotage</td>
			<td style="width:163px;">120-1907-E</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:492px;">Stainless steel blind rivet, 3.2x10 mm</td>
			<td style="width:164px;">Ejot &#38; Avdel</td>
			<td style="width:163px;">951222</td>
			<td></td>
		</tr>
	</tbody>
</table>

characterization and application of passive samplers for monitoring of pesticides in water

Five different water passive samplers were calibrated under laboratory conditions for measurement of 124 legacy and current used pesticides. This study provides a protocol for the passive sampler preparation, calibration, extraction method and instrumental analysis. Sampling rates (RS) and passive sampler-water partition coefficients (KPW) were calculated for silicone rubber, polar organic chemical integrative sampler POCIS-A, POCIS-B, SDB-RPS and C18 disk. The uptake of the selected compounds depended on their physicochemical properties, i.e., silicone rubber showed a better uptake for more hydrophobic compounds (log octanol-water partition coefficient (KOW) &#62; 5.3), whereas POCIS-A, POCIS-B and SDB-RPS disk were more suitable for hydrophilic compounds (log KOW &#60; 0.70).

Five different passive sampler techniques were compared for the uptake of 124 legacy and current used pesticides including silicone rubber (Figure 1), and POCIS A, POCIS B, SDB-RPS and C18 disk (Figure 2). The performance of the extraction method and instrumental analysis was optimized. The outcome of the laboratory uptake experiments can be used to calculate the R&#39;S and log K&#39;PW values (T...

Watch this Scientific Journal Video about Characterization and Application of Passive Samplers for Monitoring of Pesticides in Water at JoVE.com

Characterization and Application of Passive Samplers for Monitoring of Pesticides in Water

A protocol about the characterization and application of five different passive sampling devices is presented.

Five different water passive samplers were calibrated under laboratory conditions for measurement of 124 legacy and current used pesticides. This study ...

The overall goal of this procedure is to demonstrate preparation, extraction, and analysis of pesticides using five different passive sampling devices and to show how to calibrate them in the laboratory for field application. Passive sampling is a promising tool to answer quick questions for measuring pesticides, continuously at low concentration levels to improve for example, environmental risk assessments. The main advantage of passive sampling is that it's a simple time-integrated method for measuring a broad range of pesticides in aqueous environment.This method is a valuable tool for monitoring of pesticides in water. It can also be used for non-target analyzers, toxicity testing, and as an alternative for sediment and biomonitoring. Following this procedure, sampling rates and passive sampler water partitioning coefficients can be calculated based on the uptake profile for individual pesticides.Cut silicone rubber sheets into stripes of 2.5 millimeters by 600 millimeters and 2.5 millimeters by 214 millimeters using a stainless steel cutter. Connect them using a stainless steel blind rivet with a rivet gun to obtain a total sampler stripe size of 2.5 millimeters by 914 millimeters. After cleaning the silicone rubbers by socket extraction as described in the text protocol attach a silicone rubber stripe to a stainless steel spider sampler holder by wrapping the silicone rubber stripe around the rods on the holder.Attach each end of the silicone rubber stripe to a rod on the holder to the loop at the end of the silicone rubber stripe. For POCIS A place 220 milligrams of HLB bulk sorbent between 2 9.0 centimeters by 9.0 centimeters square PES membranes. For POCIS B, place 220 milligrams of a sorbent mixture between two PES membranes.Compress the sorbent and the two PES membranes between two stainless steel rings manually, and secure onto a stainless steel sample holder. Next, place the SDBRPC and C18 disks between two PES membranes. Similarly compress the disks and two PES membranes between two stainless steel rings manually and secure onto a stainless steel sample holder.Fill the three tanks with natural water. Perform all experiments at a constant water temperature and under turbulent water conditions using two electric pumps attached to the tank wall on each side. Also perform the experiments in the dark to minimize the effect of photo-degradation.Next spike each glass container with a pesticide standard mixture containing 124 pesticides using a glass syringe. Conduct the uptake study in rectangular 95 liter glass containers. Designate tank one for silicone rubber, tank two for POCIS A, POCIS B.And tank three for SDB-RPS disk C18 disk.Take out the passive samplers manually from the tanks at time intervals of 5, 11, 20, and 26 days to determine the sampling rates of the pesticides. In addition, monitor the concentrations of the pesticides in each tank by collecting 100 milliliter water samples at day 0, 5, 11, 20, and 26. Prior to extraction, dry the silicone rubber stripe under a stream of high purity nitrogen gas.For gas chromotography mass spectrometry analysis, carry out the solid liquid extraction using sockslet extraction. After placing the silicone rubber into the sockslet extractor add 250 milliliters petroleum ether and acetone and 3 boiling stones into the round bottom flask. Spike the silicone rubber with 100 microliters of an internal standard mixture using a pipet.Then add 50 milliliters of petroleum acetone into the sockslet extractor. Switch on the heater and run the sockslet extraction for 19 hours and then switch off the heater. Concentrate the extracts by rotory evaporation followed by gentle nitrogen blowdown to one milliliter.Exchange the solvent to 90 to 10 cyclohexane to acetone by adding 3 times 1 milliliter of cyclohexane acetone during the nitrogen blowdown to 1 milliliter. For liquid chromotography tandem mass spectrometry analysis the silicone rubber is extracted with 300 milliliters of methanol. Exchange the solvent to a acetonitrile by adding one milliliter of acetonitrile during the nitrogen blowdown to one milliliter.Open the POCIS sampler carefully and transfer the sorbent with ultra-pure water using a funnel into a pre-cleaned empty polypropylene solid face extraction cartridge containing two polyethylene frets. Dry the sorbent by vacuum to remove water. Prior to elution, spike the sorbent with 100 microliters of an internal standard mixture using a pipet.Elude the POCIS A and POCIS B cartridges using 1.5 milliliters of methanol followed by 8 milliliters of 80 to 20 dychloromethane to methanol for LCMSMS analysis. Concentrate the extracts to 1 milliliter by gentle nitrogen blowdown before exchanging the solvent to acetonitrile by adding 1 milliliter of acetonitrile during the nitrogen blowdown to 1 milliliter. For gas chromotography mass spectrometry analysis POCIS A and B is eluded using 5 milliliters of ethyl acetate and the solvent is exchanged to 90 to 10 cyclohexane to acetone by adding 3 times 1 milliliter of cyclohexane to acetone during the nitrogen blowdown to 1 milliliter.Transfer individual disks of SDB-RPS and C18 into a glass beaker and dry them under nitrogen gas. Spike the disks with 100 microliters of an internal standard mixture using a pipet. Sonicate the disks two times in a glass beaker at room temperature.First with five milliliters of ethyl acetate for ten minutes and then with three milliliters of ethyl acetate for ten minutes. Transfer both extracts into one glass tube before concentrating them to two milliliters by gentle nitrogen blowdown. Split the samples into two one millimeter fractions for GCMS and LCMSMS analysis.In one fraction concentrate the extracts to 0.5 milliliters by gentle nitrogen blowdown and then exchange the solvent to cyclohexane and acetone for GCMS analysis. For LCMSMS analysis concentrate the extracts to 0.5 milliliters by gentle nitrogen blowdown and exchange the solvent to acetonitrile. Shown here are exemplary results for the uptake of acetamiprid in silicone rubber in nanograms showing a linear uptake from day 0 to 20 and then a curvilinear uptake from day 20 to 26.This plot shows exemplary results for the uptake of dimethoate in silicone rubber in nanograms. Showing a linear uptake from day 0 to 10 and then an equilibrium after day 10. The five tested passive samplers were capable of accumulating pesticides with a wide range of different octenol water partition coefficients showing that silicone rubber is more suitable for hydrophobic compounds, whereas more polar compounds were better taken up by POCIS A, POCIS B, and SDB-RPS disk.After watching this video you should have a good understanding how to prepare, extract, and analysis pesticides using five different passive sampling devices and how to calibrate them in the laboratory. While attempting this procedure it's important to remember that this study was performed under static conditions while future uptake study should consider using follow-through exposure or in calibration. The usage of performance compounds, which are spiked to the passive sampler before deployment can be used to calculate n-zeto sampling rates and allow for more accurate estimates of time-rate average concentration.Please don't forget, working with organic solvents acets and basics can be extremely hazardous and precautions like lab coat, gloves, eye protection, should be taken while performing this procedure.

Characterization and Application of Passive Samplers for Monitoring of Pesticides in Water

Abstract