TIMFIE sampler - A new time-integrating, active, low -tech sampling - PowerPoint PPT Presentation

TIMFIE sampler - A new time-integrating, active, low -tech sampling device for quantitative monitoring of pesticides in w hole w ater Time-Integrating, Micro Flow, In-line Extraction Ove Jonsson Swedish University of Agricultural Sciences (SLU) Department of Aquatic Sciences and Assessment ove.jonsson@slu.se

Pesticide fate From: Water 2017 , 9 (7), 451 • Pesticide concentration in surface water will vary significantly over time • Average concentrations? Time proportional sampling. • Maximum concentrations? Event driven sampling. • Grab sampling will not answer these questions

Principle of the TIMFIE sampler Active sampling Flow restrictor: without battery or narrow bore PEEK tubing power supply 100 ml Continuous in-field SPE syringe (solid phase extraction) Filter Flow rate ∼ 3-6 µl/min Pull and lock piston. ( ∼ 60 ml in one or two weeks) Inlet Negative pressure tube drives the sampling

Quantitative analysis Accurate determination of extracted sample volume Photo: Ove Jonsson

Extracted volume over time (example) 120 100 ACCUMULATED VOLUME (ML) Linear range 0-80 ml R 2 =0.999 80 Sample volume 60 between 30-80 ml is preferred 40 20 0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 SAMPLING TIME (DAYS)

Consumables Inner diameters of restrictors 75 100 125 µm 17+8 € 6 € 5+4 € 8+17 € 3 € 17+8 € Approximate costs: Start: 88-93 € Then: 7-12 €/sample Photos: Ove Jonsson Cut inlet tubing to a point shape to avoid stops

TIMFIE field application (examples) Photo: Roland Persson

Two weeks sampling Changes in water level Know your sampling site! Photo: Torbjörn Hansson, Grön Kompetens AB

Winter sampling (Sweden) entire sampler below surface to avoid freezing. TIMFIE mounted on a fishing-rod. Photo: Torbjörn Hansson, Grön Kompetens AB

Hiding the TIMFIE in a small stream (storm w ater) Syringe is hidden here Flow restrictor under stones SPE under this stone… …and inlet tube here… Inlet tube

Storm w ater w ells in urban areas Glyphosate and other urban used pesticide Dam to increase water height (Jeans leg with sand)

SPE possibilities  Closed flow system, small format  Stack cartridges in series to extract different compound classes  Minimized solvent consumption  Simple, inexpensive shipping and storage  Rational internal standard addition Chromafix HR-P, HR-XAW and HR-XCW polymeric columns from Macherey-Nagel Photo: Ove Jonsson

Automation: Conditioning of SPE columns, 10 in parallel MeOH followed by H 2 O Quaternary LC pump

Automation: Elution of SPE columns, 6 in parallel Methanol, acetone and methanol with 80 mM ammoniac Evaporation in water bath at 40°C and N 2 flow. 50 µl DMSO as a keeper Dissolve in 3 ml ammonium acetate buffer at pH 5 Inject 0.5 ml

100 120 140 20 40 60 80 0 Hexytiazox TIMFIE absolute recoveries pesticides LC-(+ESI)MS Pyraklostrobin* Metrafenon Diflufenikan* Metamitron Oxadiazon BAM Indoxakarb* Bifenox* Prosulfokarb* Trifloxystrobin Metolaklor Metazaklor Isoproturon Pikoxystrobin Tiakloprid Spiking of three different surface waters, 4 replicates, n=12 Diuron Kloridazon Etofumesat Metalaxyl Acetamiprid Hexazinon Atrazindesetyl Atrazin 30 ml sample, error bars ± stdev, HR-P column Terbutylazindesetyl Terbutylazin Flurtamon Simazin Alaklor Propyzamid Fludioxonil Metribuzin O. Jonsson et al. Environ. Sci. Technol., 2019 , 53 (1), 279–286 Triallat Azoxystrobin Amisulbrom* Boskalid Quinoxyfen* Atrazindesisopropyl Siltiofam Klotianidin Pendimetalin Cyflufenamid Klomazon Cyprodinil* Cyanazin Linuron Mandipropamid Terbutryn Cybutryn Pirimikarb Karfentrazonetyl Metabenztiazuron Klorfenvinfos Tiametoxam Bitertanol Fenpropimorf* Pymetrozin Propikonazol Imidakloprid Dimetoat Fuberidazol Flusilazol Tolklofosmetyl* Flutriafol Penkonazol Epoxikonazol Difenokonazol Protiokonazol-destio Flufenacet Cyazofamid Fluopikolid Tritikonazol Fenpropidin* Florasulam* Spiroxamin* Fenmedifam Prokloraz* Metiokarb Tribenuronmetyl

% absolute recovery WAX-column in series w ith hydrophobic polymer TIMFIE absolute recoveries acidic pesticides LC-(-ESI)MS 100 120 20 40 60 80 0 2,4-D Bentazon Bifenox-syra Diflufenikan Diklorprop Flonicamid Florasulam Fluazinam Fludioxonil Flupyrsulfuronmetyl Fluroxipyr Jodsulfuronmetyl Karfentrazonsyra Klopyralid MCPA Mekoprop Mesosulfuronmetyl Metsulfuronmetyl Pikloram Propoxykarbazon Pyroxsulam Sulfosulfuron Tifensulfuronmetyl Triflusulfuronmetyl Trinexapak-syra

TIMFIE duplicate field sampling 1 9 duplicates, 156 data pairs, sample A vs sample B (µg/l ) 36 different pesticides found. Correlation (Pearson) r=0.998 Concentration sample A (µg/l) 0,1 0,01 0,001 0,0001 0,0001 0,001 0,01 0,1 1 Concentration sample B (µg/l)

TIMFIE vs grab sampling 10 218 data pairs, grab sample concentration calculated as mean of sample at start and end of sampling week. Mean value TIMFIE/grab = 1.7 (range 0.05-16.5). Correlation r=0.532 Concentration TIMFIE sample (µg/l) 1 0,1 0,01 Grab sampling is a poor substitute for time integrated sampling 0,001 0,001 0,01 0,1 1 Mean concentration grab sample (µg/l)

Summary TIMFIE sampling Pros Cons • Time integrated sample 1-2 weeks • No pH adjustment • Whole water • Restricted sample volume • Quantitative • Pre-concentration • Validation process according to established procedures • Flexible, different SPE materials Translate current SPE methods to TIMFIE conditions • Small format, flexible application • Transport and storage • Inexpensive • Use syringe water for further analysis

Acknow ledgement Swedish EPA and the Centre for Chemical Pesticides for financial support Colleagues at the Swedish University of Agricultural Sciences (SLU): Elin Paulsson, Henrik Jernstedt and Jenny Kreuger

Thank you for your time! Photo: Therese Nanos