Analytical chemistry -sampling strategies Dr. Pernilla Carlsson; carlsson@recetox.muni.czf room 209, RECETOX Pernilla Carlsson, recetox, Masaryk university, AMAP, Akvr^1™ """" Outline • Why monitoring POPs? • Sampling strategies -general limitations -bioaccumulation and sampling strategy • Your hypothesis and how to address it • "Chemical tools" -chirality: environmental processes and different sources -transport processes -fate of POPs • Case study discussions Some abbreviations Persistent organic pollutants: POP. Group of banned/regulated organic contaminants Decabromodiphenyl ethane: DBDPE. Flame retardant Perfluorinated alkylated substances: PFAS. GoreTex, Teflon, Ski wax... Polybrominated diphenyl ethers: PBDE. Flame retardants. Polychlorinated biphenyls: PCB. Banned since ~1970s. Used in electrical equipment, flame retardants, additives in paintings... Short- and medium-chained chlorinated paraffins: SCCPs and MCCPs. Lubricants, flame retardants, plastizisers.. Polyuretan foam: PUF. Sampling material (air). Why monitoring? • Control of decisions => After a legislation; can we see a decreasing trend? Or; do we see unlegal usage of compounds, and where do they then come from? Why monitoring? • Trends and timelines • Trajectories-sources • New compounds and screening Why monitoring? • Understaning of transport pathways • Air: most important transport pathway for POPs 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 Seasonal Cycle — Trend x Measured Reasons for increase: Under discussion -ice free ocean, hexachlorobenzene (HCB) as byproduct during pesticide production... Ma et al. (2011), Hung et al. (2010), Kaltenborn et al. (2012) Estimates of global emissions of PCBs 80,000 70,000 60,000 50,000 40,000 30,000 20,000 10,000 0 L 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 ! 1 1 1 1 1 1 1 i 1 1 1 1 i i i l i i i i i r^^^^^^^^^^^i 1930 1940 1950 I960 Year 1970 1980 1990 2000 10,000 Concentrations (ng/g Iw) of PCB in repeated serum samples from Norwegian men 1,000 tu 0 = o u si 0 1979 1986 1994 2001 2007 Figures from Therese H. N0st (Ph.D. thesis; UiT/NILU 2014) and N0st etal, 2013: http://dx.doi.ore/10.1289 /ehp.1206317 PCB 118 PCB 153 PCB 180 Trajectories -sources Simulation start 20060107 □ Actual time 20060425. 0 10« 150 mglw£ ♦Transport of polluted air (forest/grass fires) to the Arctic Illustration slide from Torkjel Sandanger, UiT New compounds -screenings Long-range transport vs. local sources Establish baseline for future time- and spatia trends Assess biomagnification New compounds -screenings • Norway and Arctic, 2013: Screening of air, water, terrestrial and marine biota =>Few PFAS detected =>DBDPE >BDE-47 in several samples =>Short- and medium-chained chlorinated paraffins (SCCPs and MCCPs) detected in Arctic biota General issues • Amount and type of data • Seasonal distribution • Instrumentallimitationsand infrastructure • Legislation Sampling strategy biomagnification Cover the whole food web Biomagnification Log,. [PFOSL ng/g wet weight 4U • Who eats who? • Benthic/pelagic couplings? 2k Oh -2h PFOS in the eastern Canadian Arctic marine food web ^ BeJucp Marshal i-J-i GiaiKDUE quls • Bbck-legged ■.-..ilr.i Zsopbnkton J f if Shrimp 2 a 4 S 6 7 Itapht level AMAP 2009 Your hypothesis and how to address it • Clear research questions! • Data needed • Financial and time frames Your hypothesis and how to address it • An example: Does fish from the Baltic Sea contain higher concentrations of PCB and dioxins compared to fish from the Atlantic ocean?" Fish and POPs Study design: Fish -species Sampling: fishing or buying? Transport Analyses Data interpretation Literature comparison Chemical "tools" Relative distribution Degradation and metabolites Chirality Isotopes Relative distribution • PCBs: different mixtures had different ratio between congeners • Low-chlorinated PCBs: Easily undergo long-range transport. 9 Persistent Organic Pollutants Relative distribution -technical PCB mixtures Sovol fRussia) Chlorine 55.1 % Chlorofen fFolandl_Chlorine 64.4% A roc I or 1262 Chlorine 6 L9% Aroc]or]22l Chlorine 24.4% Chlorine 34.0°o uyyyyyuy oc o s o u y " (N T V) * ^ G H H * 5 40 30 20- m J 1 io- m 1 11 o- Aroclor 1242 Chlorine 43.0% r-i G H y PL) "a"1 rt1 «' a' ffl y y y u y ao Q\ O x s o z s Arochlor: USA Takasuga et al., 2006 PCB flux to the Arctic Carrizo, D.; Gustafsson, O. Distribution and Inventories of Polychlorinated Biphenyls in the Polar Mixed Layer of Seven Pan-Arctic Shelf Seas and the Interior Basins. ES&T2011. Carrizo, D.; Gustafsson, O. Pan-Arctic River Fluxes of Polychlorinated Biphenyls. £5Changed ratio in Arctic compared to technical mixture =>"Non-changed ratio": Local sources Degradation and metabolites Hydroxy-PCBs: Metabolism of PCBs to facilitate excreation of the compounds Oxychlordane: Common, stable metabolite from tra/is-/c/s-nonachlor and -chlordane DDE: Stable metabolite from DDT. Affect eggshell thickness among birds Isotopes Who eats who? Trophic positions: "place in the food web" 15N/14N=615N Illustration: Eldbj0rg Heimstad Transport processes -tracking sources tratosphere Troposphere A. VOCs, S02, CO + NOx + Sunlight + Weak/Stagnant Circulation -r—► T03 t A vs. |t T + P -> H20 vapor + HOx I Oa f T <^ " ' °" D. I P + Weak/Stagnant Circulation -> f PM C. J Photodegradation Ť Deposition (PM, POPs, Pesticides) f SM —I. f Hydrolysis K.f Vofatility Grannas et al. (2013), Jantunen et al .(2008), Kallenborn et al, (2012a), Noyes et al. (2009), Wong et al. (2011) N. f Hydrolysis-f j Sediment Biodegradation ^ p — ^ Degradation +f Persistence LT Solubility Chira lity -tracing environmental processes and sources Chiral pesticides: a-HCH, trans-, cis-, and oxychlordane Enantiomer fractions of chiral pesticides in plankton as a tool to differentiate between water masses__ Chiral pesticides => non-racemic EFs: indicate biological transformation processes Plankton non-selective metabolism, reflect EFs of pesticides in the water mass Carlsson et al, 2014 Chiral pesticides and water masses •Ice cover and a-HCH ^(hindering of) volatilisation •Chlordanes and 2011 =^>Large deviations from racemic tra/is-chlordane •Water masses and ice cover are important for the EF distribution •Impact from benthic-pelagic processes not completely understood yet Case studies of environmental pollution How? -Air sampling Active air sampler ~vaccum cleaner! PUF: Polyurethane foam (sampling media for gaseous compounds) Filter: particle associated compounds Easy to measure amount of air filtrated Sampling time: "Hours-days Need electricity Higher cost compared to passive air samplers C Air intake I El H 1 1 H "J 3 nuts Flange Polyethylene washer Filter Backing (aluminium) Silicon washer PUF plug # 1 PUF plug # 2 Picture: http://www.nilu.no/projects/ccc/manual/index.ht How? -Air sampling • Passive air sampler: • Calibration: requires extra experiments and calculations. • Long exposure time to reach equilibrium (Air-PUF). Sampling time: ^Months. Active and passive air sampler Pictures from Roland Kallenborn, NMBU Where? Where? Remote vs sources. Where? Remote vs sources... Ny-Älesund and Zeppelin station -Background concentrations! Ny-Alesund: ~40 inhabitants during the winter Zeppelin: 474 m.a.s.l. (above the inversion layer) Restricted access to the station Where? Remote vs sources... • Zeppelin: Detection of cyclic volatile methyl siloxanes (cVMS) in the air. • Active air sampling for decamethylcyclopentasiloxane (D5), hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), and dodecamethylcyclohexasiloxane (D6). • Measured D5 were in agreement with modelled predictions. Krogseth et al., 2013. Where? Remote vs sources. Environmental Science & Technology 17-Aug 6-Oct 1-Aug 1-Sep 1-Oet 1-Nov 1-Dec Date (start of sa mpl i ng| 2.5 2j0 1 5 l.D O.b 0 0 D4 J 25-NOv l7-tv$ 1.6 1.4 1.2 1 0 O.S 0 6 0.1 0? 0.0 D6 25-Nov IB ilk 6-Oct 25-Uov Date (start of sampling) K^ui* 1. Concentrations of D3, D4, Dj, and D6 in air for all samples at Zeppelin in 2011. The concentrations are shown as ranges for D3 and D4, taking into account both possible Jtider- and oyer estimation due to the storage artifacts. The concentrations for D> and D6 are the storage-cor re tied concentrations with the uncertainties as error bars. The DEHM-n^odel estimate for D> concentrations in Arctic air rroni August to December 2011 is displayed as a line. Note the different scales on the ^-aies. Krogseth et al., 2013. Monitoring and management -a case study from Svalbard Case study from Svalbard Case study from Svalbard Extensive usage of PCB in Barentsburg => local sources are present. Similar atmospheric contribution of PCB in Ny-Alesund and Barenstburg (short distances) > Clean-up Svalbard from PCBs! Pyramiden Roughly 430 kg PCB7/km2 in the soil (0-20 cm) Barentsburg Roughly 300 kg PCB7/km2 in the soil (0-20 cm) Longyearbyen Roughly 3,3 kg PCB7/km2 in the soil (0-20 cm) Remote areas of Svalbard Roughly 1,1 kg PCB7/km2 in the soil (0-20 cm) Case study from Svalbard • Routine monitoring => higher concentrations of PCB detected • High levels of PCB => management measurements -clean-up • Prevention for future => education, information, monitoring Where? -A case study from Iceland •FUNI: Small incineration plant in Isafjordur, NW Iceland •Built 1995, small throughput (~3000 tons waste/year) •Dispensation from EU regulations on dioxins in fly ash •2010: Too high levels of dioxins in sheep milk (1 sample) from the area Case study from Iceland •Lamb meat: elevated concentrations •Concentration in hay of PCDD/Fs: 0.85 pg WHO-TEQ/g •Slightly above the EU maximum limit of 0.75 pg WHO-TEQ/g Case study from Iceland Ewe =female, adult sheep Case study from Iceland •Why did it happen? •Small incinerator and too little maintainance => bad combustion process =>dioxins Case study from Iceland •Prevention for the future: maintenance of incinerators, regular surveys of PCBs, dioxins, public awareness. •This incinerator is not used anymore. Study design of your projects •Laboratory/field experiment •Analytical methods •Interpretation of data -limitations? •Time limitations? •Suggestions for larger scale project Summary -sampling strategies • Plan your work: clear hypothesis, limitations of data, seasonality, time and financial frames • Chemical "tools": stable isotopes, chirality, relative distribution • Important to link models with empirical data • Identify limitations in literature References AMAP, 2011. Snow, Water, Ice and Permafrost in the Arctic (SWIPA): Climate Change and the Cryosphere. in: AMAP (Ed.), Oslo, Norway, p. xii +538. Becker, S., Halsall, C.J., Tych, W., Kallenborn, R., Schlabach, M., Man0, S., 2012. Changing sources and environmental factors reduce the rates of decline of organochlorine pesticides in the Arctic atmosphere. Atmospheric Chemistry and Physics 12, 4033- 4044. Borgá, K., Saloranta, T.M., Ruus, A., 2010. 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