(v)) Analytical chemistry -Monitoring and sampling strategies Outline - monitoring of POPs • Why? History, control, time trends, new and emerging compounds How? EMEP, NORMAN and CLRTAP Sampling devices, time series, air quality • Where? Remote vs sources History of POPs 1979 1983 1984- 1998- 2003 2004- 2009- 2011—2014 The CLRTAP entered in for untnes v 1979 Geneva Convention on Transboundary Air pollution, (CLRTAP) The 1998 Aarhus protocol entered into force The 1998 Aarhus Protocol under the CLRTAPn EMEP was was implemended, entered into force in 1988 The Stockholm Convention (SC) entered into force, 12 legacy POPs. Annex A: (elimination), Annex B: (restriction) Annex C: (unintentionally produced). 1 Technical endosulfan listed under the SC 7 new substances under the The 1998 Aarhus Protocol, 9 new substances under theSC The 1998 Aarhus Protocol is ratified by 33 parties and signed by 36 SC signed by 152 countries Figure: Kine Halse, NILU/NMBU PhD thesis 2014 Global Action on POPs • International Treaty on POPs: Stockholm Convention on Persistent Organic Pollutants (www.pops.int) •Stockholm Convention aims at eliminating these chemicals from 2004 •Outlawed nine of the "dirty dozen'' Persistent, bioaccumulative, toxic; PBT P: Tha|fnfe > 6months in soil and sediment, > 2 months in water B: log Kow >5. Kow =partitioning coefficient for octanohwater T: toxic -most often chronic effects for POPs •POPs: Can also undergo long-range transport (LRT) •Thaifiife - 2 days in air and/or monitoring in remote areas •Several atmospheric monitoring stations in the Arctic! Huna et al.. 201 0 • Long-term Monitoring Stations a Satellite Stations 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 Increased concentrations of HCB in air at Zeppelin station. Reasons: Under discussion -ice free ocean, HCB as byproduct during pesticide production... Ma et al. (2011), Hung et al. (2010), Kallenborn et al. (2012) 80,000 Estimates of global emissions of PCBs 70,000 60,000 50,000 40,000 30,000 20,000 10,000 0 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 1 i 1 1 1 1 1 1 11 1 1 1 1 1 1 "^^^^^^^^^^1 10,000 Concentrations f S 1,000 (ng/g Iw) of PCB in J a repeated serum ! n inn samples from | o Norwegian men i 1979 11 j 1 H 1986 1994 CZl 2001 1-1 2007 Figures from Therese H. N0st (Ph.D. thesis; UiT/NILU 2014) and N0st etal, 2013: http://dx.doi.org/10.1289 /ehp.1206317 PCB 118 PCB 153 PCB 180 Trajectories -sources Simulation start 20060407 □ Actual time 20060425. 0 0 50 10* ISO 200 mg/m2 ♦Transport of polluted air (forest/grass fires) to the Arctic ♦Foto: Ann-Christine Engvall, Stockholms Universitet Illustration slide from Torkjel Sandanger, UiT New compounds -screenings • Long-range transport vs. local sources • Establish baseline for future time- and spatial 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 CLRTAP, EMEP, NORMAN, • Convention on Long-range Transboundary Air Pollution: CLRTAP • European Monitoring and Evaluation Programme: EMEP • NORMAN: Scientific network for investigations of emerging compounds CLRTAP, E M E P, NORMAN Main components 2010 Monitoring network Pietu re: http://www. ni lu. no/projects/ccc/network/i ndex. htm I CLRTAP, E M E P, NORMAN EMEP is a scientifically based and policy driven program and provides support to the CLRTAP on: a Atmospheric monitoring and modelling; a Emission inventories and emission projections; n Integrated assessment modelling; a Hemispheric transport of air pollution CLRTAP, EM EP, NORMAN • 2005: The NORMAN Network started with support from EU • 2009: NORMAN lives on! The network includes reference laboratories and research centers related to monitoring and biomonitoring of emerging environmental substances • RECETOX is part of NORMAN CLRTAP, EM EP, NORMAN The NORMAN mission: Enhance exchange information Encourage validation of analytical methods and monitoring tools Ensure that knowledge of emerging pollutants is maintained and developed CLRTAP, EMEP, NORMAN • Emerging substances: Not always new! • Emerging substances Have been detected in the environment, but are currently not included in routine monitoring programmes at EU level. The fate, behaviour and (eco)toxicological effects of the substances are not well understood. CLRTAP, EMEP, NORMAN • Examples of emerging substances: Non-regulated PFAS (although PFOS is on the list), dicofol (replacement for DDT), pharmaceuticals, siloxanes (in your deodorant), «unknown» compounds 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 1 Air intake I > 3 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 Aluminum tube (3 m long) Sample holder ■•■'.'Air Flow control High volume pump Pictures from Roland Kallenborn, NMBU Where? Remote vs sources. Arctic: Remote, not many local sources! Europe: Tracking the sources, tracking the route of contaminants Cities: Control of emissions, air quality 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 I 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 3-5 3.0 T 2.0 B I"* u S 1.0 0 5 0.0 D3 17-Aug ü-Ol:: 25-Nüv 2.5 2.0 1 5 l.D 0 0 D4 1 17-Aug e-oa 25-NOv I I 1-Aug 1-Sep 1-Oct 1-Nov 1-Dec Date (start of sampling! 1.6 1.4 1.1 1 0 0.S 0 6 0.4 0 7 0.0 D6 |B'I fei 17-Aug 6-Oet i5-Nov Date (start of sampling) Figure 1L Concentrations of D3, D4, D> and D6 in air for all samples at Zeppelin in Zul 1. The concentrations are shown as ranges for D3 and D4, taking into accountboth possible under- and over estimation due to the storage artifacts. The concentrations for Ds and D6 are the storage-corrected concentrations with the jncertainties as error bars* The DEHM-model estimate for Dj concentrations in Arctic air from August to December 2011 is displayed as a line. Note the different scales on the jj-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. Summary monitoring Why? EMEP, NORMAN, CLRTAP -Control over emissions -Detection of new, emerging substances Where? How? -Conventions and organisations for air monitoring -Remote areas =>background information, confirmation of stability- -Source areas => Control of emissions, part of the trajectory information -Air monitoring: volatile/semivolatile compounds, particle associated compounds. Active vs passive sampling. Monitoring of biota/human for ecotoxicological reasons. References Halldorsson X Audunsson G, Guicharnaud R, Dyrmundsson 0, Hansson S, Hreinsson K. 2012. Contamination of livestock due to the operation of a small waste incinerator: A case incident in skutulsfjordur, iceland, in 2010. Acta Veterinaria Scandinavica 54:S4. Hung, H., Kaltenborn, R., Breivik, K., Su, Y.S., Brorstrom-Lunden, E., Olafsdottir, K., Thorlacius, J.M., Leppanen, S., Bossi, R., Skov, H., Mano, S., Patton, G.W., Stern, G., Sverko, E., Fellin, P., 2010. Atmospheric monitoring of organic pollutants in the Arctic under the Arctic Monitoring and Assessment Programme (AMAP): 1993-2006. Sei. Total Environ. 408, 2854-2873. Kaltenborn, R., Reiersen, L.O., Olseng, CD., 2012. Long-term atmospheric monitoring of persistent organic pollutants (POPs) in the Arctic: a versatile tool for regulators and environmental science studies. Atmospheric Pollution Research 3, 485-493. Krogseth, I. S.; Kierkegaard, A.; McLachlan, M. S.; Breivik, K.; Hansen, K. M.; Schlabach, M., Occurrence and Seasonality of Cyclic Volatile Methyl Siloxanes in Arctic Air. Environ. Sei. Technol. 2013, 47, 502-509. Ma, J., Hung, H., Tian, C, Kaltenborn, R., 2011. "Revolatilization of persistent organic pollutants in the Arctic induced by climate change." Nature Clim. Change 1(5): 255-260. N0st T.H, Breivik K, Fuskevag O.M, Nieboer E, Ödland JO, Sandanger TM. 2013. Persistent organic pollutants in norwegian men from 1979 to 2007: Intraindividual changes, age-period-cohort effects, and model predictions. Environmental Health Perspectives 121:1292-1298. PCB clean-up project; Governor of Svalbard, www.sysselmannen.no Additional information -EMEP, NORMAN, CLRTAP • More info: http://www.unece.org/env/lrtap/welcome.htrril http://ebas.nilu.no/ (EMEP air monitoring data), www.norman-network.net • CLRTAP is a convention via United Nations Economic Commission for Europe (UNECE) • Geneva: 1960s: Sulphur emissions continental Europe -acidification Scandinavian lakes. • 1972-77: Several studies about transport of air pollutants. => International cooperation • Ministrial high-level meeting for these acute problems in Geneva nov 1979. => Signature of the Convention on Long-range Transboundary Air Pollution (CLRTAP) by 34 Governments and the European Community (EC). This was the first international legally binding instrument to deal with problems of air pollution on a regional basis • CLRTAP: In force 1983 • Aarhus protocol: Regional protocol, P not necessary (PAHs on the list). • Stockholm conv: Global protocol. By September 2014, the SC has been signed by 152 countries and include 179 parties and have a global action monitoring plan (GMP). Additional information • EMEP: Scientifically based and policy driven programme under the CLRTAP for international co-operation to solve transboundary air pollution problems. • Some of the monitored compounds: Surface ozone, particles (PM10; particulate matter <10u.m), nitrogen and sulphur compounds, PAHs, dioxins, PCBs, HCH, Hg, Cd, Pb (Mercury, cadmium and lead). Additional information • The NORMAN mission: • Enhance the exchange of information and collection of data on emerging environmental substances. • Encourage the validation and harmonisation of common measurement methods and monitoring tools so that the demands of risk assessors can be better met. • Ensure that knowledge of emerging pollutants is maintained and developed by stimulating coordinated, interdisciplinary projects on problem-oriented research and knowledge transfer to address identified needs.