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

• ve.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

Flow restrictor: narrow bore PEEK tubing Continuous in-field SPE (solid phase extraction) Pull and lock piston. Negative pressure drives the sampling Flow rate ∼ 3-6 µl/min

(∼60 ml in one or two weeks)

Inlet tube Filter

Principle of the TIMFIE sampler

Active sampling without battery or power supply

100 ml syringe

Quantitative analysis Accurate determination of extracted sample volume

Photo: Ove Jonsson

Extracted volume over time (example)

20 40 60 80 100 120 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 ACCUMULATED VOLUME (ML) SAMPLING TIME (DAYS)

Linear range 0-80 ml R2=0.999 Sample volume between 30-80 ml is preferred

3 € 17+8 € 17+8 € 8+17 € 6 € 5+4 €

Approximate costs: Start: 88-93 € Then: 7-12 €/sample

Photos: Ove Jonsson

Cut inlet tubing to a point shape to avoid stops

75 100 125 µm Inner diameters of restrictors

Consumables

TIMFIE field application (examples)

Photo: Roland Persson

Photo: Torbjörn Hansson, Grön Kompetens AB

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.

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)

 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

SPE possibilities

Photo: Ove Jonsson

Automation: Conditioning of SPE columns, 10 in parallel

Quaternary LC pump MeOH followed by H2O

Automation: Elution of SPE columns, 6 in parallel

Evaporation in water bath at 40°C and N2 flow. 50 µl DMSO as a keeper Dissolve in 3 ml ammonium acetate buffer at pH 5 Inject 0.5 ml

Methanol, acetone and methanol with 80 mM ammoniac

20 40 60 80 100 120 140

Hexytiazox Pyraklostrobin* Metrafenon Diflufenikan* Metamitron Oxadiazon BAM Indoxakarb* Bifenox* Prosulfokarb* Trifloxystrobin Metolaklor Metazaklor Isoproturon Pikoxystrobin Tiakloprid Diuron Kloridazon Etofumesat Metalaxyl Acetamiprid Hexazinon Atrazindesetyl Atrazin Terbutylazindesetyl Terbutylazin Flurtamon Simazin Alaklor Propyzamid Fludioxonil Metribuzin 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

Spiking of three different surface waters, 4 replicates, n=12

30 ml sample, error bars ±stdev, HR-P column

TIMFIE absolute recoveries pesticides LC-(+ESI)MS

• O. Jonsson et al. Environ. Sci. Technol., 2019, 53 (1), 279–286

20 40 60 80 100 120

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

% absolute recovery

TIMFIE absolute recoveries acidic pesticides LC-(-ESI)MS

WAX-column in series w ith hydrophobic polymer

TIMFIE duplicate field sampling

0,0001 0,001 0,01 0,1 1 0,0001 0,001 0,01 0,1 1

Concentration sample A (µg/l) Concentration sample B (µg/l) 9 duplicates, 156 data pairs, sample A vs sample B (µg/l ) 36 different pesticides found. Correlation (Pearson) r=0.998

0,001 0,01 0,1 1 10 0,001 0,01 0,1 1

Concentration TIMFIE sample (µg/l) Mean concentration grab sample (µg/l)

218 data pairs, grab sample concentration calculated as mean

• f sample at start and end of sampling week.

Mean value TIMFIE/grab = 1.7 (range 0.05-16.5). Correlation r=0.532

TIMFIE vs grab sampling

Grab sampling is a poor substitute for time integrated sampling

Pros

• Time integrated sample 1-2 weeks
• Whole water
• 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

Cons

• No pH adjustment
• Restricted sample volume

Summary TIMFIE sampling

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