Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | , 5 , and Chemistry 11 , H. Hung and Physics Discussions Atmospheric 5 , T. Meyer 9,10 , T. Harner 4 , C. Halsall 3 , R. W. Macdonald 16924 16923 8 ´ a ´ anov , K. J. Hageman 2 , J. Kl 7,8 ´ an , C. Bogdal , P. Kl 1 6 11 Fisheries and Oceans Canada, Institute of Ocean Sciences, Sidney, BritishDepartment Columbia, of Physical and Environmental Sciences, University of Toronto Scarborough, ¨ urich, Switzerland This discussion paper is/has beenand under Physics review (ACP). for Please the refer journal to Atmospheric the Chemistry corresponding final paper in ACP if available. Department of Chemistry, Villanova University, Villanova,Institute PA, for 19085, Chemical USA and Bioengineering, ETH Zurich, Wolfgang-Pauli-Strasse 10,Department 8093 of Chemistry, University ofLancaster Otago, Dunedin, Environment Centre, 9010 Centre New Zealand for Chemicals Management, Lancaster University, Environment Canada, Science and Technology Branch,Department Toronto, of Ontario, M3H Chemistry, Biotechnology 5T4, and Canada Food Science, Norwegian University ofDepartment Life of Chemistry, Faculty of Science, Masaryk University, Kamenice 5,RECETOX, 625 Faculty 00 of Brno, Science, Masaryk University, Kamenice 3, 625 00Department Brno, Czech of Environment and Geography, Centre for Earth Observation Science, 10 V8L 4B2, Canada 11 1265 Military Trail, Toronto, ON, M1C 1A4, Canada Received: 26 June 2012 – Accepted: 29Correspondence June to: 2012 A. – M. Published: Grannas 10 ([email protected]) July 2012 Published by Copernicus Publications on behalf of the European Geosciences Union. F. Wania 1 2 Z 3 4 Lancaster, LA1 4YQ,5 UK 6 Sciences, Christian Magnus7 Falsen vei 1, Postbox 5003, 1432, Norway Czech Republic 8 Republic 9 University of Manitoba, Winnipeg, Manitoba, R3T 2N2, Canada The role of the globalfate cryosphere of in organic the contaminants A. M. Grannas Atmos. Chem. Phys. Discuss., 12, 16923–17000,www.atmos-chem-phys-discuss.net/12/16923/2012/ 2012 doi:10.5194/acpd-12-16923-2012 © Author(s) 2012. CC Attribution 3.0 License. R. Kallenborn Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | ´ e et al., 16926 16925 ects is highly dependent on snowpack physical properties such as ff cient scavenger of atmospheric organic pollutants while a seasonal snowpack, ecting cryospheric processes and properties. Arctic sea ice extent is decreasing ffi ff Climate change may significantly impact the nature and extent of the cryosphere, The global cryosphere is defined as the part of the Earth’s surface where water is contaminants to surrounding ecosystems (Blais et al., 2001a; Bogdal et al., 2010). et al., 2007). Thevital cryospheric parts environments of in regional Polar ecosystemscryosphere regions (McConnell, on is 2006; Earth also Slaymaker are and presentregions. Kelly, considered 2007). Each in component The high of altitude, theand cryosphere boreal fate plays of and a contaminants mid-latitude unique and role (including is in discussed urban) the in global turn transport thus in a Sect. 3. at an alarming rate (Perovich,rapid 2011; AMAP, wastage 2011a), and (Sharp glaciers, et also al., now undergoing 2011; Hanna et al., 2011), may deliver previously stored nature of these e density, specific surface area, air permeability2008, 2012). and The thermal cryosphere conductivity is (Domin sheets also hold a critical nearly component 80 ofice % the can of global play the water an cycle. world’s Ice important freshwater. role It in has surface been atmospheric shown chemistry that processes snow (Grannas and present in solid form.ice It caps, thus ice sheets, includes andcial sea the component ice, frozen of lake geosphere the ice, (permafrost).ergy Earth The river balance cryosphere system ice, of is for snowpack, the a several glaciers, moisture cru- key Earth from reasons. due warm It to is locations sensiblesurfaces. important to Snow and and cold in latent ice the locations, heat play and en- important involvedrespect roles the in to in heat, high the decoupling moisture albedo transport the and surface-air of of contaminant interface snow fluxes. with In and the ice case of snow, the quantitative and mountain regions (e.g.ecosystem snow, sea health, ice, this glaciers) workthe or has role the not of impact yet the of beeninformation global contaminants placed available cryosphere on about in in specific the contaminant elementscontaminant context fate. of fate Here of the in we cryosphere understanding cold into seek environments. a to global synthesize picture the of al., 2008). While much recent work has been on individual compartments within Polar Grannas et al., 2007),and changing contaminant contaminant-environment fate interactions during with snowmelt climate change (Meyer (Couillard and et Wania, 2008), to global and localBlais cold-trapping, et is al., of 1998;tion particular Daly of and concern elevated Wania, (Wania concentrations 2005;far and of Wania from Mackay, organic and 1993; contaminant contaminants Westgate, 2008). in sourcethe The polar role regions observa- and of has mountain snow lednumber areas and of to ice reviews much in discuss work contaminant(Wania various et transport aimed aspects al., and at of 1998b; fate Herbert the characterizing sonal during et snowpack cryosphere (Halsall, al., the in 2004), 2006), last photochemistry contaminant including decade. in contaminant cycling snow A interaction (Domine with and sea- Shepson, 2002; It is now widely recognizedpose that organic severe contaminants risk are to globallyof distributed contaminants wildlife and has and may been humanFinizio well et health documented al., (AMAP, 1998; and 2009a).Scheringer, Bard, characterized The 2009). 1999; (Wania Accumulation global Wania, of et 2003; transport contaminants al., Gouin in 1998a; Polar et regions al., and 2004; mountains, Harner due et al., 2006; cryospheric compartments impact contaminanttions cycling and feedbacks and also fate. occurceptible A within to variety the perturbations of cryospheric due system, interac- state to most of of climate knowledge which regarding change. are thethe In sus- transport global this and cryosphere article, processing with we an of emphasis organic review on contaminants the the in current role of a changing1 climate. Introduction The cryosphere is an important componentis of an global e organic contaminant cycles.sea Snow ice, glaciers and icedays caps to are millennia. contaminant Important reservoirs physical on and time chemical scales processes ranging occurring from in the various Abstract 5 5 25 15 20 10 20 25 15 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | - ff ectiveness. The first ff ers a perspective on the inter- ff orts, changing policies and monitor- ff 16928 16927 orts ff The Arctic Monitoring and Assessment Programme (AMAP) is an international orga- The POPs Protocol of the Convention on Long-Range Transboundary Air Pollution The Stockholm Convention on persistent organic pollutants (POPs) came into force on POPs was published in 2009 (AMAP,2009a) and a special report on “The Greenland Force on Hemispheric Transportport of of Air the Task Pollutants. Forceresults The on for 2010 Hemispheric POPs in Transport POPs of the Assessmenteling Air cryosphere the Re- and Pollutants fate the included and important monitoring transport(UNECE, role 2010). of of this POPs, compartment including in the mod- delivery of POPsnization to of the circumpolar food countries chain establishedissues in of 1991. POPs AMAP. Results arement of one reports of Arctic several to monitoring priority inform and on research the status are of integrated the in Arctic assess- environment. The latest assessment nomic Commission for Europethrough the region. European Under Monitoring theand and transport CLRTAP, monitoring Evaluation and fate Programme is modeling and isCentre carried carried work – out out on through East emissions The and Meteorological Synthesizing and several Modelling, working the groups, Task namely Force the on Task Integrated Force Assessment on and Measurements Modelling and the Task in air, their cycling betweenpreviously trapped the POPs cryosphere due to and climateitoring air, change. and The data report re-release need also (from to emphasized thatto ice/snow) be mon- distinguish of integrated changes with that multi-media arehistorical models due to releases and regulatory and emissions actions chemical information from cycling changes (UNEP, 2009). associated with (CLRTAP), established in 1998Convention (UNECE, but 1998), addresses is the complementary concerns to of the countries Stockholm within the United Nations Eco- in 2004 andthe is Stockholm the Convention is largestneeds the international of Global Article Convention 16 Monitoring of on Plan theglobal Convention, (GMP) POPs. monitoring dealing which with report A measuring addresses targeting its key POPs the e 2009 in component and air recognized and of the human milk/blood importance was of completed the in cryosphere on levels and trends of POPs climate change and increaseddevelopment, and human mining activity of resources. including transport/shipping, industrial hazardous chemicals is addressedagreements at and the programs. In international manypolar level cases and/or through these alpine various policies recognize regions treaties, fate the where of uniqueness toxic the of chemicals cryosphere and ultimately playsAs their new a delivery contaminants to key are the role food includeding chain, in in including priorities the reduction humans. will e cycling in and the part scientific community. dictate Looking the to the measurementgagement future, and to we can process address foresee changes studies the to undertaken need these for by political once en- pristine regions that are associated with latitudes and considers the potential impacts of climate-change in each compartment. 2 Current policy and monitoring e The importance of the cryosphere in the context of organic contaminants and other nant transport and cycling: thecarbon hydrologic cycle, cycle. the Cryosphere-dominated cryospheric environments cycle,to and are change the thus organic of exceptionally the vulnerable feedback physical mechanisms. environment Contaminant because cycles, suchronmental as system change integrated of may parts cold influence regions, of areclimate-related all this similarly environmental three prone complex change to envi- change (Macdonald asmann et a et al., result al., of 2012; 2000, expected Guglielmo 2003a, etactions al., between b, contaminants 2012). 2005; and This the Ho review various o cryospheric compartments at a range of presents a great challenge.range Not of physical only and areature chemical these dependent, properties fate but of processesscenarios. contaminants the controlled As that cryosphere by discussed are itself a in stronglymajor wide is temper- a feedback systems recent highly in detailed variable complex review cold under ecosystems (AMAP, 2011a), climate that there have change relevance are to three contami- Predicting the impact of climate change on contaminant fate within the cryosphere 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | orts have been established ff erent possible fates, which will be discussed ff 16930 16929 orts will need to consider the cycling and fate of chemically diverse ff ect atmospheric transport. In both Arctic and Antarctic regions long-term atmo- ff A number of global and regional long-term monitoring e The Antarctic Treaty entered into force in 1961. The purpose of the treaty is to protect The sensitivity of alpine regions to organic contaminants is dealt with through a vari- in the following sub-sections. However, here wethe discuss atmosphere the to transport the of chemicals Earth’s from surface via snowfall. 3.1 The role of snowfall inFalling contaminant snow delivery plays an to important surfaces rolecontaminants in in the cold transport environments. The and enhanced ultimateto partitioning distribution surfaces of of at organic gas-phase cold chemicals temperatures, combinedresults with in the snow large surface being areasthe an of atmosphere excellent snowflakes, (Lei scavenger and of Wania,falling semi-volatile snow 2004). are organic Chemicals then chemicals that subject from reach to the several di Earth’s surface with toring has been initiated moreIncorporation recently, in commencing in snowpack 2007 and (Kallenbornas ice et melting creates al., of temporary 2012). the reservoirs reservoirscesses of progresses, that contaminants, redistribution contribute occurs. but to Thediscussed contaminant wide in cycling variety further and of detail pro- fate in are Sect. summarized 3.1–3.9. in Fig. 1, and al., 1976; Tanabe et1992, al., 1997, 1983; 1998) Oehme and and numerousport partitioning Mano, routes. processes 1983; Long-term can Oehme, atmospheric occurspatial 1991, along monitoring and Barrie these provides temporal et trans- a trends, al., may critical and a also activity to to identify estimate spheric the monitoring manner programs in are which2010; presently Ma climate et established change al., (Su 2011;have et Kallenborn been et al., monitored al., for 2008; 2012). the Hung Specifically, past in et two the al., decades, Arctic, whereas legacy in POPs the Antarctic similar moni- Once emitted to the atmosphere,cal, organic chemical contaminants and can biological undergo processes a thatvironment. variety Long-range in of atmospheric combination physi- transport make is up the theirobserved main fate global mechanism in distribution that the of results en- contaminants in (Peterle, the 1969; Peel, 1975; Risebrough et 3 Impacts of the cryosphere on contaminant fate Committee for Alpine Research. within the above mentioned treaties,records agreements of and contaminant levels. programs With to theand measure list monitoring long-term of e contaminants expanding,analytes. future research This willcritical present to sampling understanding and thecontaminants. analytical In local, challenges. Sect. regional Process 3, androle we studies of global discuss are the in fate global more of cryosphere specific in historic terms contaminant and transport, these dynamics processes emerging and and variability. the cently published a thorough reporthighlights changes on to Antarctic the Climate cryosphere Change of (ATME, this 2010), continent. which ety of regional and multinationalthe programs, Protection including of the International the Commission Alps for and the Alpine Convention and the International Scientific 1992); freshwater contamination (Lockhart etdiets al., (Kinloch 1992), et and al., risks/ 1992). benefits of northern the Antarctic environment from negative anthropogenictive influence. measures Among that other have been protec- adoptedProtection, under adopted this in treaty, the 1991, ProtocolAntarctic on commits environment Environmental and Parties prohibits to all activities theexcept relating for comprehensive to scientific Antarctic protection research. mineral of resources, The the Scientific Committee on Antarctic Research has re- ern Contaminants Program (NCP),since which the reports late through 1980s. AMAP,of has Some data been of operating collected theoccurrence, early by work various and under Arctic pathways NCP of programscontamination synthesized (Muir into contaminants a et five (Barrie wide al., reviews et 1992); variety dealing terrestrial al., ecosystem with 1992); contamination sources, marine (Thomas et ecosystem al., Ice Sheet in a Changing Climate” (AMAP, 2009b) was prepared. The Canadian North- 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | er- er- ff ff et al., ff erent tempera- ff cients, temperature ffi erent physicochemical 85 % from rain. Snow is ff > 16932 16931 -dioxins and dibenzofurans (PCDD/Fs) to a Northern cients (Roth et al., 2004), and scavenging ratios have ´ e et al., 2007a), models have been developed for es- p ffi erent temperatures, as shown for polycyclic aromatic hy- ff ecting the transport behavior and distribution of organic contam- ff cient than rain in scavenging water soluble organic species (Lei and ffi ect of temperature on snow-air partitioning was considered as well (i.e. the ff ect is apparent when sampling snowpack along elevational gradients in moun- ff erent chemicals and at di The degree to which contaminants are delivered from the atmosphere to the Earth’s Due to the temperature-dependence of snow-air partition coe The pathways via which organic contaminants enter snowpack include vapor scav- Snowfall scavenges a wide array of contaminants with di Organic contaminants have been measured in freshly fallen snow collected in di ff amounts of contaminant deposition along an elevational gradient in western Canada dients in mountains are sometimes, butthat not the always, found. geographic Hageman distribution et of al.national (2010) contaminants parks found in in snowpack in North eightonly America if alpine could the and e be Arctic explainedconcentrations by at local contaminant the sources muchsource but contribution colder alone). arctic sites were higher thansurfaces by expected falling based snow on dependswell on as both the the amount contaminant of concentrations snow in snow that as falls. Blais et al. (1998) showed that the increasing plays an important roleThis in e determining the degreetains (Blais to et which al., 1998; snowlated Arellano scavenging vapor et occurs. al., and 2011). particle Wania scavengingtures and ratios to Westgate for demonstrate (2008) why both used increasing snow calcu- contaminant and concentrations rain along elevational at gra- di By measuring pesticides inshowed both that summer the rain total andatrazine, annual carbaryl, winter wet and snowfall, deposition dacthal Mast of inactually et the the less al. relatively Rocky e (2007) water-soluble Mountains pesticides, was Wania, 2004). Thus, both modelingtance and of measurement snowfall in studies a indicateinants that in the the impor- environment depends heavily on chemical properties and the location. portance of snowfall in deliveringicantly contaminants between to mountain remote regions alpine intion regions of Europe. varied polychlorinated More signif- than dibenzo- twoSwedish watershed thirds occurred of during months the with totalwith average temperatures deposi- the below freezing, highest values observed during months with snowfall (Bergknut et al., 2011). physicochemical properties. Carrera et al. (2001) used field data to show that the im- al., 2007) and varies significantly between specific contaminants, depending on their atmosphere before deposition (Waniadetected et in snowpack al., both 1999a).vapor- low- and However, and particle-bound Carrera high-molecular phases et weight in theal. al. PAHs, atmosphere, which (2011) (2001) respectively. observed reside Likewise, Schrlau a in et wide the water. range of particle-bound fractions of chemicals in snow melt enging by snow, particledeposition, scavenging and by scavengingent snow, by pathways dry spring has gaseous rain. been deposition, investigated The via dry relative modeling particle importance (Daly and of Wania, these 2004; Stocker di et di drocarbons (PAHs) and PCBs via(Wania calculations et for vapor al., and 1999a; particlephases Lei scavenging and when ratios Wania, snow 2004). isused Because melted to chemicals directly for redistribute determine analysis, between how measurements snowpack-entrapped in chemicals were melted distributed snow in cannot the be timating snow-air partition coe been determined for a numberand of Eisenreich, volatile 1998; and Starokozhev semi-volatile et organic al., compounds 2009). (Franz properties. This occursdominantly because in (a) the atmospheric relatively gasand volatile phase (b) can contaminants partition contaminants that into withis reside or lower onto trapped pre- volatility snowflake by surfaces sorb falling to snow. atmospheric The particulate degree matter of that scavenging, and its mechanism, varies for ent parts of themid-latitude world, mountains including (McConnell et at al.,(Herbert an 1998; et urban Zabik al., site and 2005a, in Seiber,ies b), 1993), Europe have in and (Czucwa measured the in the et Arctic 1995; sorption Antarctica al., Roth of (Cincinelli 1988), et organic et in contaminants al., al., to 2004; 2005). snow Domin Lab-based and stud- ice (Ho 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | ect ff er con- ectively ff ff cult to find un- erent mountain ected by climate ff ffi ff erent regions. In re- cult to segregate the ff ffi erent type of spatial comparison, Usenko et ff 16934 16933 cient transport medium for semi-volatile organic ffi ect the global fate of organic contaminants (Macdon- ff ect) and increasing amounts of snowfall with elevation. Annual ff decade) and longer-term (multi-decadal) accumulation history of POPs and other ected cold glaciers, particularly in temperate mountain regions. Eichler et al. (2001) Utilization of firn and ice cores in the Arctic is providing insight into the recent Because snow can serve as an e ff < Alps) at 4200 m a.s.l. and analyzed inorganic tracers. A significant deviation of the fluorinated alkylated acids) (Younggirello et et al., al., 2007; Hermanson 2010;to et Meyer provide al., et accurate 2005, al., depositionalprocesses 2010; 2012). fluxes that Rug- for Contaminant can a accumulation occur.mate given In in from year order ice Alpine due to is icewater to reconstruct unlikely cores, the past were glaciers post-depositional atmospheric selected, having pollutionever, because negligible due and influence meltwater cli- to by disturbs recenta percolating climate the melt- warming annual itdrilled layer becomes an structure. more ice How- and core more from di the accumulation area of the glacier Grenzgletscher (Swiss variability and climate change. Asrelative emissions importance decrease, and the these secondary are sources strongly grow in controlled by climate. ( organic contaminants (e.g. currently used pesticides, brominated flame retardants, per- dichlorodiphenyltrichloroethane (DDT) and hexachlorcyclohexanefrom (HCH) Mt. in Everest ice cores the (the Rocky Tibetan Mountains in Plateau), Northclimate Mt. America. variations These Muztagata associations and (in suggest organicrelative linkages the contaminant between extent eastern distribution. of It the Pamirs)the is influence and of di deposition climate of variation/change contaminantsthat from to deposition emission at ice changes given on andfactors sites snow (winds, is temperatures, cores, a secondary product but sources) of the that both are records the strongly clearly a strength show of emissions and other et al., 2010); Colleest Gnifetti (Wang in et the al.,Canada Swiss/Italian (Gregor 2008); et Alps al., Lys (Gabrieli 1995). Using Glacier,correlations et literature-reported between Italy al., data, climate Wang (Villa 2010); et variation al. Mt. et patternslation, (2010b) Ever- (including found al., the the Siberia 2006) El High and Nino-Southern pattern Oscil- Ellesmere and Island, the North Atlantic Oscillation) and deposition of including Svalbard, Norway (Isaksson et al., 2003; Ruggirello et al., 2010; Hermanson is possible to examine contaminantganic records contaminants have preserved been in measured ice in cores. ice Anthropogenic cores collected or- in a variety of locations (UNEP/AMAP, 2011). However, there is aof lack of changing direct snow observed in evidence termsof of of the aging both e and quality, e.g. compaction changing etc.,inant specific and surface transport quantity area and or due timing to fate.endeavors. climate This change is on certainly organic an contam- area for3.2 future research and Preservation of monitoring contaminant deposition recordsIn in geographic ice locations cores where snow is converted to firn, and eventual permanent ice, it siderably around the globecreasing with (e.g. 20 increasing % (e.g. reductiongions with 40 from % increased mean) snow increase trends precipitation, fromsurface deposition occurring media of mean) in organic would and contaminants di increase; from de- cipitation, and air in to organic regions contaminants with can and be during atmospherically times of transported low more or e no pre- contributed significantly to the higherments relative on contaminant that concentrations side in of lake the sedi- divide. contaminants, this mechanism of contaminantchanges delivery due to to the climate surfaceby change. is a A susceptible change to changing in climateald the may et extent a of al., snowChange 2003a, cover (IPCC, b; brought 2007) Stocker about projected that et precipitation al., in 2007). a changing The climate Intergovernmental will Panel di on Climate to the temperature e precipitation trends along elevationalsystems gradients (Wania vary and significantly Westgate, in 2008),tration which di partly trends explains in why mountains contaminantal. concen- vary. (2007) In showed a that di increased snowfall on the east side of the Rocky Mountains was due to both increasing contaminant concentrations in snow with elevation (due 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | A (1) C [m] IA orts in K ff orts and ff cient (MTC). ffi ´ e and Shepson, erence between the air above ff orts under UNEP. 16936 16935 ff ect global atmospheric chemistry (Domin ff cient to the snow grain surface from the gas phase values for numerous organic chemicals and provided a linear ffi erent field programs (polar regions and alpine) may provide a ff IA K can be calculated using: are the specific surface area, and density of the snow. Roth et ciently removes gaseous substance from the snowpack, while the 100 (2) ] is the chemical concentration at the snow grain surface and · 2 SA ffi ρ − ρ K · erences in sources and contaminant transport patterns. The valuable ff and A -ratio from the expected seawater ratio of 1.16 provided evidence for the SSA cient [mol m · + ffi ] is the snow pore vapor concentration. The dimensionless bulk snow/air par- I /C IA 3 I SSA C − K C wind ventilation = = -to-Na In previous studies that describe snow-atmosphere exchange, the chemical flux has The gaseous mass transfer between snow and the atmosphere is in most cases − SA IA been calculated as thethe product snow of the and concentration the di snow pore space, and an overall mass transfer coe tition coe K where al. (2004) measured free energy relationship that cangas be phase used for to numerous estimate organics. the chemical partitioning into the K where [mol m atmosphere (Meyer and Wania, 2011b).gases in Chemicals the in pore space, dry orand snow sorbed clean to are snow snow, either grain prevalent surfaces present in andspace as particulate subarctic and matter. and In snow dry arctic grain2011b). regions surfaces during The are winter, distribution important only betweentioning the for those properties, pore mass two snowpack transport phases properties and depends (Meyerequilibrium temperature. on and sorption The the Wania, temperature-dependent coe chemical’s parti- can be expressed as: orption from snow grainand surfaces, Wania, in 2011b). order to maintain partitioning equilibriumlimited (Meyer by chemical transportchemical within partitions the into snow the pore pore space space, the (interstitial larger air). is The its more potential a for exchange with the associated chemical loss in the snow pore space is rapidly compensated for by des- volatilize from the snow inwind notable ventilation amounts e (Meyer and Wania, 2011b). In such cases 2004), which may even2002; a Grannas et al.,thermodynamically 2007). by Losses a of lossface chemicals of area storage from capacity (Cabanes the in et snowpackwind ageing al., may ventilation snow (Colbeck, be 2003) with 1989; driven and Albert diminishing and possiblyhas sur- Shultz, higher been 2002; Albert observed temperature, et and empirically al.,Burniston kinetically in 2002). et Such the by loss al., field (Herbert 2007)2004; et and Hansen al., et also 2005b; al., reproducednants Finizio 2006; by such et Stocker simulation as al., et tri- models 2006; al., and (Daly 2007). tetrachlorinated and Even PCBs semi-volatile Wania, as organic well as contami- three- and four-ring PAHs can The porous naturenently of or snow seasonally as coveredchemicals well by between snow as snow provides the and for the extent a overlying of substantial atmosphere exchange the (Wania of et global organic al., area 1998b; Halsall, that is perma- ographical di time-series provided by firnthe and Arctic and ice elsewhere, cores particularly could withwhich respect longer complement to term air newer, emerging measurements monitoring contaminants inthe for e air tying are together lacking. of Coordinationuseful di of endeavor coring for global e monitoring e 3.3 The exchange of organic chemicals between snow and the atmosphere by transport of soluble chemical speciesglacier. with Today, the the percolating relevance meltwater of movingcontaminants within percolating within this temperate meltwater ice for is theies hardly known. conservation do Nonetheless, provide of the few an organic existingIce/firn excellent stud- cores assessment taken of in relative the contaminant Norwegian accumulation and history. Canadian Arctic provide information on ge- Cl 5 5 20 25 15 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | ´ e et and air is trapped. As pressure in- in the Arctic. A case study by Meyer ff SA K 16938 16937 ´ e et al., 2007b), shallower depths (Sturm et al., 1995), and lower ects of chemical partitioning and snow properties, the MTCs are two ff in watersheds erent snow layers within one snowpack (Albert et al., 2000). Polar and subarctic snow covers have the largest spatial and temporal extension. It is also important to note that artificial ventilation of snowpack can be induced by Snow permeability strongly influences snow-atmosphere exchange, and depends ff can serve as an invaluableextreme record of environments, past seasonal atmospheric snowmelt composition. In occurs, all and but the this most can significantly impact 3.4 The role of seasonal snowmelt in modifying organic contaminantSnow behavior (and associatedposited contaminants) to the can surface.and experience In persistently at various cold higher processes climates,time, depths snow interstitial once will form air continue between de- firn snow to grainsthe as accumulate can snowpack, be it exchanged until with is the thecreases, compressed atmosphere pores firn above eventually by is close eventually the compressed o into snow ice, above. and this During ice this (and the air trapped within) lease from a subarctic snowpack,combining whereas the in the e Arctic netto deposition three would occur. orders By ofthan magnitudes under still larger wind under conditions. the influence of moderately strong winds Compared to subarctic snow, arcticsurface snow areas usually (Domin exhibits higher densitiespermeability and (Albert specific and Shultz,dian 2002), Wind and Energy is Atlas, exposed 2003)The to as latter well higher results as wind in lower speeds aand temperatures (Cana- Wania (Taillandier generally et (2011b) much revealed al., higher that 2006). byconditions assuming typical snowpack properties for and subarctic environmental and arctic regions, PCB-28 would experience a net re- permeability in snow as thedient proportionality and factor the between flow the velocity bulkpack (Albert snow can and pressure change Perron, gra- by 2000). two Permeabilityal., in orders 2008). a of Snow seasonal magnitude permeability snow- over can thedi also course vary of by almost the one winter order (Domin of magnitude between of air transmissibility (Albert et al., 2000). Adopting Darcy’s Law, we can describe the commonly applied in the past to estimate permeability, it only correlates poorly in terms certain chemical measurement techniques. Measurementing methods of that interstitial rely on airflow pump- from rates the on snowpack theand for mixing order of chemical of concentrations analysis/detection of litersal., analyte often 2002). per from As require various minute, such, depths measured which in interstitialthe the air causes true, snowpack chemical local advection-dominated (Albert concentrations may concentration et flow not at represent a given point in amainly snowpack. on snow layering and snow microstructure. Although snow density has been pressure variations induced by windsurface turbulence and roughness “form features drag” (Albert pressuresurface around and roughness snow Hawley, features 2002). that At aretably more increase Summit, the pronounced Greenland, rate in snow of winter(Albert chemical than transport and summer Hawley, in 2002). can snow, assuming no- similar wind conditions time scales, such asrequires the a diurnal more chemical preciseHawley exchange MTC (2002) induced parameterization. and by Albert Albert photolytic andby et investigating reactions, Shultz chemical al. (2002), transport (2002) Albert withintilation filled snow and induced was some by found of wind to ventilation. thecause Wind substantially associated advective ven- enhance chemical knowledge the transport gap al., snow-atmosphere even 2002). at exchange The snow and intensity depths can ability of of wind and several ventilation meters snow depends (Albert surface on et roughness the wind features. speed, Wind snow ventilation perme- in snow is caused by MTC was set as aet constant al., (Wania, 2007), 1997; whereas Halsall, inable 2004; (Daly other Herbert and studies Wania, et it 2004; al., wasshould Hansen 2006; treated et be Stocker as al., appropriate a 2006). when Such wind investigatingriods parameterizations chemical speed of of exchange dependent weeks the processes vari- MTC or over months. time However, pe- the description of processes occurring on shorter The latter parameter is associated with relatively high uncertainty. In some studies the 5 5 25 15 20 10 25 20 10 15 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | 16940 16939 associated with the spring freshet during snowmelt can result in ff ects of contaminants on aquatic species depends on the contami- ff A seasonal snow cover functionsfor atmospherically as deposited a contaminants recipient (for periods andwhich ranging temporary disappears up to storage during 10 reservoir months), melt and therefore releases the stored contaminants in Contaminants are typically not releasedmelt from snow water packs concentrations, with temporally butfractions. uniform they can be enriched in early or late melt water a relatively short period of time. The high run-o the mobilization of particle-bound contaminants in soils and sediments. – – – Falling snow can influence contaminant input to a watershed by modifying the rate of bility to change than is the case in warmer regions. vulnerable stage of development. Onethe particular role of motivation a for seeking seasonalto snow to anticipate cover understand how in climate contaminantnants change amplification (Macdonald is may et to impact al., achieve 2003a). aquatic the Whereascontaminant organism rising behavior ability exposure in temperatures a may to only watershed, contami- slightly smallchanges modify temperature in changes the can characteristics precipitate of large ice a cover) seasonal and snow its coverpathways melt (e.g. consequent duration, (e.g. to depth, the rate surface melting of of melting). seasonal In snow other cover create words, a changes greater in vulnera- contaminant These features of acontaminant seasonally amplification, snow i.e. covered watershed result can inof essentially long-term contaminants contribute average in and/or to water peak(Meyer that concentrations and are Wania, higher 2008).highest than contaminant Furthermore, they loads to would the occur be in melt early in spring, of the when a organisms absence are seasonal at of a snow snow particularly cover causes watershed, but mostly by modifyingwater. the This extent is and timing because: of concentration peaks in the partly because it may influence the long-term average retention of contaminants in a atmospheric deposition, as discussed in Sect. 3.1. A seasonal snow cover is of interest deposition to watershed surfaces. However,the water retention concentrations capacity will of alsothat the depend finds its watershed, on way namely into the thetaminant water fraction properties, compartment of such (Bergknut et the as al.,properties contaminant partitioning 2011). will input In behavior influence addition and this to retention degradability, con- teorological many capacity, including and watershed relief, hydrological soil characteristics. properties, Watershed andbe retention me- subject will to almost high certainly temporalthe variability extent on and a timing number of of concentration time peaks scales, and and thereby thus also will toxicity. impact centration variability, especially as itfluctuating relates concentrations to can seasonal be biological moreal., cycles. toxic 2011). Specifically, than The average specific concentrationscoincide (Ashauer timing with et of time concentration periods peaksconcentrations is of strongly crucial, depend particular on namely organism a whetheruse susceptibility contaminant’s they input and or to emission food a of uptake. watershed, the i.e. Water either contaminant the within the watershed or the rate of atmospheric 3.4.1 The role of seasonal snowIn in contaminant high amplification latitudes orcontaminants. Seasonal altitudes, snow snow can influencesas act both as a watershed a contaminant temporary input sourceof reservoir and to for detrimental retention a contaminants e of and watershednants’ during toxicity, its the concentration, snowmelt andaverage period. the concentration The period in of likelihood exposure. water Not relevant only in is this the long-term context, but also the short-term con- the Arctic and atend lower elevations of in summer alpine (e.g. regions,snow Armstrong, the season 2001), snow (Olsen but melts et warming completely al.,contaminants is in by 2011 leading the the and context to references of a therein). seasonal shortening Here snowmelt we of cycles. discuss the the fate of the local and regional hydrology, nutrient cycles and contaminant fate. For much of 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | ff ff in an urban ff occurred by over- during time periods ff ff occurring during snowmelt is occurs more uniformly. There rates, which in turn were con- ff ff ff with very high, albeit short run-o ff , PAH transport in the river during the ff conditions that favor infiltration to soils -HCH in stream water in the year when γ ff 16942 16941 occurring on the surface than below the ground. (ii) Very high run-o ff ` ere et al. (2006) noted that organic contaminant concentrations in early atmospherically deposited contaminants cient storage reservoir for all organic species. As discussed in Sect. 3.3, more ffi , likely due to the mobilization of contaminated particles under high flow conditions Incidentally, dilution of compounds by the high run-o There is field evidence of the contaminant amplification potential of a seasonal snow Generally, only the photochemically stable and less volatile organic contaminants ff Non-atmospheric watershed sources may become diluted by melt water containing high flow conditionslow were flow. as Because of much thespring as 10 freshet two times was higher orders three run-o et of orders al., of magnitude 2011a). magnitude higher Alsoparticle-bound, higher the than had than flow peak during during concentrations of normal duringo long the flow chain period (Meyer perfluoroalkyl of maximum acids,(Meyer snowmelt believed et run- al., to 2011b). be largely also possible, namely for compounds that do not have primarily atmospheric origin. trations of the pesticidesthe chlorothalonil snowpack and was thickerland and flow when rather a than highersnowmelt proportion subsurface was flow. of found PAH run-o totrolled transport correlate by in the strongly this intensity with of urban run-o melting watershed (Meyer et during al., 2011a). Concentrations of PAHs during the more hydrophobic compounds wereal. highly (2011) concentrated in noted melt that water.of as Bergknut much et the as PCDD/Fs 71 %snowmelt from of induced a the spring annual Boreal flood, exportthat a catchment of percentage the in PCBs exceeding spring and Northern considerably freshet 79 thepercentage % Sweden makes for contribution of the occurred to contaminant that the export during was annualter the attributed flow reaching to significant of streams amounts water through ofarea melt (52 overland during % wa- flow. two to Comparing subsequent 66 years, snowmelt %). Meyer run-o et The al. higher (2011a) observed higher peak concen- ceptions may be urbanthose watersheds during that the experience spring intense freshet rain (Zhao events and that Gray, 1999). resemble cover. Lafreni melt water from a remote alpine area were much higher than in the snowpack, and even of a seasonal snowpack, but so are the annually averaged water concentrations. Ex- fore expect that not only are the maximum water concentrations higher in the presence rate maxima is lower thanare in two a reasons watershed for whereare run-o this: expected to (i) increase Whereascompounds contaminant run-o retention sorbing within to the soilby watershed, organic passage in through matter, particular the overland for ground.when flow the Snowmelt is ground generates is less high often run-o likely stillportion frozen of to and run-o thus be largely “filtered” impermeable,rates resulting as in may occur a during higher snowmelttransport result and in thus greatly in enhanced the potential mobility for of solid particle-sorbed phase substances. Overall, we may there- will still be presentEmpirically, it to has a not large yetretention been extent of established in these whether a organic theence contaminants seasonal annually of is averaged snow a enhanced watershed cover seasonal or snowin at diminished cover. a the However, through watershed we onset the experiencing may of pres- surmise highly episodic melt. that contaminant run-o retention an e volatile substances are readily losttaminants by evaporation may back also to be thehigh atmosphere. degraded Some thermodynamic within con- forcing, the contaminants snow,in as may locations not discussed where in be freezing Sect. rain ablemore frequently has 3.9. to in sealed Despite escape a the warming the surface, climatea snowpack (e.g. an higher Post occurrence et proportion which al., of 2009), appears the and contaminant in these may special enter cases the water cycle during the freshet. Organic contaminant deposition withlow and temperatures, to which cause snow semi-volatile is chemicalsto enhanced to transition mostly atmospheric from because the particles gas of phase and the ice surfaces (Lei and Wania, 2004). Snow cover is not 3.4.2 Snow cover as a recipient and temporary storage reservoir for 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | ¨ ondorf and ect. An example of ff 90 %) to the liquid water > 16944 16943 ` ere et al. (2006) noted the strongest enrichment ` ere et al., 2006). Particle sorption is not the only reason for contaminant enrichment in late melt water A peculiar release behavior with maximum melt water concentration in the middle of Some substances’ sorption behavior is such that they are only partially particle- The opposite behavior was observed for particle bound organic substances in the the melt period (typeroalkyl 5, acids Table (Plassmann 1) et was al., observed 2011). for This intermediate release profile chain could length only perfluo- be explained by fractions. A late release issorb also strongly observed to for the somewhat snowend water grain of soluble surface, the substances but melt instead that period,late of concentrations stage in being of the melting released when melt only theis water at snow diminishing tend surface the and to area disappearing very gradually and (type increase thuschain 3, the in Table perfluoroalkyl snow’s 1). a sorptive Such acids capacity behavior (Plassmann wasas observed et chlorpyrifos for al., (Meyer long and 2011) Wania, and 2011a). predicted for pesticides such strongly dependent on snowpack properties,2009a, such as b; the Meyer particle and content Wania,tent, (Meyer 2011a). et even For al., quite example, in hydrophobic(Lafreni snow contaminants with are very enriched low in particle early con- melt water fractions Table 1). Examples of contaminantsal., behaving 2009a), this the way longer are chainal., the semifluorinated 2010), larger and alkanes mercury PAHs used (Meyer (Mann in et et skiwaxes al., (Plassmann 2011). et sorbed in snow. Theirelution of release the from fraction meltingrelease dissolved of snow in particles is water from and thendominates a the not characterized second snowpack only by late (type depends an peak 4, on early associated Table the 1). with contaminant’s Which the partitioning one properties, of but these is peaks also in early melt water samples for HCHs. controlled melting experiments.peated Because freeze-thaw cycles, snow, often in acts as particularretained a in particle if the filter, particle-sorbed melting it snowpack substances to are has be released undergone only at re- the very end of the melt (type 2, was also observed in the field: Lafreni (Meyer et al., 2009a). Preferential enrichment of water soluble organic contaminants organics, which are estimatedphase to present partition in a predominantlysurements melting ( in snowpack, the closely melt resembled watersize of electrical (Meyer organic et conductivity contaminants, al., mea- exclusion 2009a, frommore the b). complete ice than Because matrix that of can of the be inorganicperiments, assumed ions larger the to first (Kammerer molecular quarter be and even Lee, of the 1969).total melt In load water laboratory of contained ex- as water much solubleter as chemicals, three fraction such quarters had as of concentrations the the in pesticide excess atrazine. of The five first times melt the wa- average snow concentration layer at the snowthe grain snowpack, surface. most When of latephenomenon the melt of ions water early have forms elutionganic already and (type contaminants been percolates 1 during eluted. through inhomogeneous studies A Table snow mechanistically involving 1) that similar artificially was wasHerrmann, observed subjected generated 1987; to for and Meyer controlled water contaminated et melt soluble al., conditions or- (Sch 2006, 2009a). In fact, elution curves of water soluble 3.4.3 Fractionated release of contaminants fromSnow melting can snow contribute to contaminantalso amplification on not the only at scaletablished the for of watershed quite scale, the some but snowpackions time (Johannessen itself that and early (Meyer Henriksen, melt and 1978;explained water Tsiouris Wania, by fractions et a 2008). are al., melt It 1985). enrichedthat water Mechanistically, in had this have front inorganic is been been percolating excluded down es- from a the snowpack ice and matrix dissolving and the are, ions thus, present within a liquid-like bound and the remobilizationthis of phenomenon solids is counteracts the this concentrationscreek, dilution of which short e dipped chain duringbehavior perfluoroalkyl the of acids spring long in freshet chain an (Meyer perfluoroalkyl urban et acids al., mentioned above. 2011b), in contrast to the low concentrations of such contaminants, at least as long as these are not particle 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | erent ff . In cases where melt ff , as was illustrated by the case of the ff erences in the elution behavior of di ff 16946 16945 erent extents in the timing of concentration peaks in the re- cient to explain the di ff ffi rates during snowmelt. In other words, highest water concentrations for such ff The contaminant enrichment in melt water observed at the base of the snowpack Both laboratory experiments and model calculations have been used to explore what All five types of elution behavior in Table 1 could be reproduced with, and thereby that sediment concentrations aremovement increasing of the in glacier glacier-fed (Fig. lakes 2a closely and following b), the while in non-glacial lakes concentrations are during 1950–1970, a periodal., 2001b). with The greater authors warned contaminationincrease that by enhanced the glacial organochlorines melt release (Blais due ofbecome to et climate a contaminants change local may to secondary freshwater.et source al., Melting for 2009); mountain measurements POPs glaciers oforganochlorine (Blais a have pesticides, et large revealed al., range a of 1998;tions remarkable POPs, AMAP, in re-increase 2005; including pro-glacial lakes of PCBs, Bogdal directly PCDD/Fs sediment fed(Fig. by and concentra- 2). melt A water from comparison rapidly between melting sediment adjacent trends glaciers in vicinal Swiss Alpine lakes confirmed 2010b; Bogdal et al., 2010).ticularly High susceptible altitude to environments, rapid which(Blais are climate et believed change, to al., provide be 2001b; cryospherichave par- shown Batterbee reservoirs that et a of glacier-fed al., tributary POPs wasalpine 2009; the lake Schmid dominant in source et of the most al., Canadianof POPs Rocky 2011). to the Mountains. a glacier Blais sub- They melt et have discharging also al. into found (2001a) this that lake at originated least from 10 % the ice that was deposited ice covered lakes and oceans ismay melting, be the more timing relevant of in release understanding from the the timing snowpack of base 3.5 concentration peaks in the Fate of water. contaminants in meltingSimilar glaciers to Arctic environments, the scavengingported and deposition POPs of by atmospherically snow trans- plays(Finizio an et important al., role delivering 2006; POPs Vighi, to alpine 2006; environments Thies et al., 2007; Kang et al., 2009; Wang et al., of little relevance forceiving the rivers, timing because of it concentrationrun-o peaks is of overwhelmed such bysubstances substances the would in likely high occur the particle during re- water the loads directly period enters caused of water highest by bodies, run-o such high as occurs during glacial melt or when snow on The enrichment of particle-bound substances in the late melt water fractions is likely pesticide chlorothalonil in an urban stream discussed earlier (Meyer et al., 2011a). with hydraulic barriers and in2009b; snowpacks Meyer that and are Wania, subject 2011a).enrichment to The bottom of filtering melt of type (Meyer particles 2facetted et by snow al., (Table the grains 1) snow, as and was well therefore as enhanced by in the formation dense ofmay snow dirt be consisting cones (Meyer reflected of et toceiving fine al., 2009b). water di and bodies. Induring the snowmelt case the of concentrationtent observed the of in water ground receiving soluble infiltration waters contaminants depends and that on peak surface the early run-o ex- snowpack and melt characteristicsrichment have in the melt largest water influence (Meyertion on et of the water al., contaminant soluble 2009b; compounds en- Meyerdeep (type and and 1, Wania, aged Table 1) 2011a). snowpack was The that found early is to elu- melting be most rapidly, while pronounced it in is attenuated in layered snow mechanistically explained by, amelting snowpack of melt several horizontal modelmelt snow that water layers (Meyer simulates and and theequilibrium Wania, the sequential partitioning 2011a; resulting Plassmann between downward etparticulate the percolation al., matter, of various 2011). melt snowpack The water,considerations phases model are air-filled su (snow assumes pore grain space),chemicals surface, suggesting (Meyer and that Wania, thermodynamic 2011a). declining during the snowmeltmay be period, related for to reasons the2011). that changing Also are ionic the composition currently of releaseenced still the by of unclear, melt the mercury but water ionic (Plassmann from strength2011). et of a al., the melting water snowpack used was to make found the to artificial be snow influ- (Mann et al., assuming that the strength of sorption of the compounds to the snow grain surface is 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | ect E2; ff + ected by ff -HCH and α E1 / E1 = 0.5) but with the = -HCH in sea water to α -HCH advected by long-range -HCH inventory in the Beaufort α α -HCH (the only chiral HCH) in air -HCH, due to abandonment of use α α 16948 16947 ective barrier to evaporation of POPs from sea- ff ´ elie penguins from the Western Antarctic Peninsula (Geisz et al., even distribution for both enantiomers where EF = -HCH could be degraded in the Beaufort Sea by 2020. -HCH in the air had racemic enantiomeric composition (EF α α -HCH concentrations between 1993 and 2007 and they anticipate that the α sea-ice ´ cko et al. (2012) evaluated the evolution of the ect (e.g. Li et al., 2004). Measurements made as early as 1993 (Jantunen and Bidle- Pu Concentrations of POPs in the Arctic atmosphere during the past ten years have Locally the release of POPs during the glacial melting season may represent a rel- Coupling of a dynamic chemical fate model for PCBs, DDTs, and PCDD/Fs based on -HCH input/output routes. Degradation processes could explain the decrease in ob- ff product of various industrial chemical processes. Atmospheric increases of HCB are Sea and found thating between via ocean 1986 currents, and whileα 1993, gas exchange, the river inventories inflow and increasedserved ice due export to were negligible load- majority of varied regionally but are generally trendingto downward (Hung this et al., is 2010). An hexachlorobenzene exception (HCB), a former pesticide and still an unintended by- winter values, and the(Fig. EF 3). changed Changes towards involatilize the EF and signature upon mix of icetransport, the breakup with resulting allow surrounding nearly in non-racemic the waters racemic potential togas atmospheric use exchange chiral due signatures to to loss track of changes in ice air-water cover in the ocean. flux direction of HCHs from netMeasurements deposition of in the the 1980s enantiomer toand net compositions surface volatilization of seawater in in the Arctic 1990s. Canadathat (Jantunen more et open al., water 2008; Wong isJantunen et allowing et al., for 2011) al. more show volatilization (2008)coverage, from and the ocean Wong reservoir. etracemic Both al. mixture (2011) showedloss that of during ice winter/spring cover ice in spring, the concentrations in the air rose considerably from the oration of semi-volatile contaminantsother formerly volatile trapped POPs below the (e.g.e sea hexachlorobenzene, ice. HCB) are sensitiveman, to 1996) this showed that temperature atmosphericby declines China and in India (e.g. Li and Macdonald, 2005), resulted in a reversal of the air-sea observed over the western Arctic Ocean in recent years, will lead to increased evap- sient reservoir and transporting mechanismdonald for anthropogenic et contaminants (e.g. al., Mac- 2005). In addition, significantly reduced ice cover in late summer, as 3.6 Contaminant occurrence and processing in the sea-ice snowpack and The year-round ice covermargin of of the the Polar Southern oceans Ocean)water (central is to an Arctic the e Ocean atmosphere. and Seature ice the cover (i.e. southern responds thermodynamic directly processes to of averagewinds freezing ambient (i.e. and tempera- dynamic melting) forcing, and Screen is and strongly Simmonds, 2010). a Sea ice cover itself is a tran- evant source of toxicbiota. Melting compounds glaciers to have also sensitiveposure been mountain to hypothesized DDT ecosystems as of a and Ad 2008). source may for the a continuing ex- al., 2010). It couldacceleration be of shown the that since releasewould the of also 1990s, POPs have climate resulted stored change into in has a climate Alpine release resulted warming, glaciers. of in POPs A contaminants an water. are steady-state but The released at release climate earlier a of and much chemicalsaccelerate more slower may at concentrated be rate. the by further Due same glacial boosted rate melt lost if in about glacier the 12 melting % future. continues of Between to caused their 1999 a ice and volume volume, 2008, loss whereas of the the 3.5 extraordinarily Swiss % warm glaciers (Farinotti summer et of al., 2003 2009). decades ago (Fig. 2c; Schmid et al., 2011). historical use and emissionmodel scenarios enabled for further these confirmation POPs ofthe with this interconnection a glacier between transient hypothesis contaminant-, glacial and glacier-, provided ice insight and flow into climate-dynamics (Bogdal et following a decreasing trend expected by emission reduction measures taken a few 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | N ◦ culties such as gaining access at the ffi 16950 16949 ects of low-latitude emissions and seasonality in the data (since Arctic ice melt is An additional concern is that contaminants stored in the winter snowpack over ice Relatively few studies have examined the occurrence of organic contaminants in Overall, the downward trends of organochlorine air concentrations are due to the re- ff will in turn yield relatively contaminated melt water (see Sect. 3.4) which will collect in eventually reaching the marginal ice zonesSea (MIZ) (Gustafsson of et the al., Western 2005) Arcticthe where and locations they the of are Barents ice released formation whenby and the climate melting, ice change, and melts. therefore, in Changes may the have in from types the and capacity the to amounts alter Arctic. of the ice Althoughof export induced of sea we contaminants ice, have the reasonablenant transport loads estimates of carried of by particulates the thatpathway contained ice for volumetric within (Macdonald most transport et sea POPs al., remains ice, 2005), poorly and the quantified. some magnitude of contami- this transport ity of river-mouths ofWhite major Sea rivers flowing on into thetransport the northwest elsewhere Arctic over coast a Ocean, of period thecontaminated of Russia, Bering sediments 15 and Strait, yr. from The the in the modeltransported East the results with Siberian support Faroe-Shetland the rivers the Channel concept (Melnikov ice to that et into al., the 2003) Central may Arctic be Ocean over a period of several years, right time of thedynamic year. However, nature given the by extensive whichin areas covered snow organic by and contaminants sea-ice be andare can the transported warranted. associate The and/or with transport releasedcess and of within during accumulate sea the periods ice global of across cryosphere,movement the of as melt, contaminants Arctic part sea contained Ocean of ice within1995; the is or studies Lange freshwater an deposited and cycle important upon Pfirman, and the pro- 1998). possibly2007) ice Simulations for have (Pfirman of specifically the et investigated contaminant al., the transport potential by for ice contaminants (Pavlov, located in the vicin- found that concentrations offace most air POPs temperatures and were negatively positivelyat correlated correlated significance with levels sea-ice with of extent summer 90 from % sur- 2000 or to more. 2009, the sea ice system, largely due to logistical di most significant and POPs input from southerly sources is lowest in summer). They e sured at Zeppelin andArctic Alert environmental sinks to (ice/snow, revealice land evidence retreat. and of They water) hypothesized remobilization that due theatmospheric of to overall POPs POPs downward Arctic trends trapped warming caused observed in and in byand measured sea decreasing environmental emissions, degradation changing mayatmospheric POPs. have locations By masked of statistically any sources residuals removing climate showed the increasing change declining tendencies time influence whenet trends, on Arctic the al., sea-ice underlying 2007). retreat spedwere The up almost statistical (Stroeve entirely detrending performed and using correlation summertime analysis datasets of in Ma order et to minimize al. the (2011) which has become iceis free a consequence in of thewater the past (Slubowska-Wodengen, significantly 2007; 6–7 increased Nilsen yr. inflow et Thehas al., of reduced 2008). been warm, Although ice observed surface dramatic North-Atlantic in cover iceis retreat other in unique. parts Fram Ma et of Strait al. the (2011) Arctic, further a analyzed permanently the ice-free time series state of at POPs 80 in Arctic air mea- Zeppelin. Becker et al.consider (2012) several hypotheses discuss for this the behavior.inated recent Revolatilization soils from upturn previously and contam- in vegetationBarber HCB may et concentrations influence al., and 2005), atmospheric asticides. concentrations The well (Bailey, as fungicides, 2001; chlorothalonil the presence andhave been of quintozene, shown and HCB to the impurities contain arachnicide, insible HCB tetradifon, currently use as used of impurities pes- (Gouin HCB-contaminatedduction et in pesticides, al., sea these 2008). ice Besides increases cover the on may pos- the be west related coast to of Spitsbergen, a where re- Zeppelin is located, similar increasing trend in HCBof was Alert also (Wang observed et at al., the 2010a). Canadian High Arctic station duction of use/production of thesethe compounds. change It in is the currently downward trend unclear of what HCB has atmospheric caused concentrations since 2003 near observed since 2003 at the Zeppelin (Svalbard) mountain research station (Fig. 4). A 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | C ◦ 98 % -HCH) ∼ γ -HCH, in- α - and α 0.05) indicating -HCH, which in air p < α ) a significant positive re- 5–10, 40 %, compared to 14 = < n –C perfluorocarboxylic acids (PF- ´ 11 cko et al., 2010a, b, 2011). Sig- 10 –C 4 0.3–0.7, = -chlordane, and no relationship apparent -HCH observed in surface seawater dur- 2 α r trans 16952 16951 erent snow types encountered during the CFL ff 0.5) of ´ cko et al., 2011). These relationships with density - and < -HCH in sea ice (Pu γ cis 40 %) from fresh snowfall via re-volatilization was observed - and ∼ α -HCH and γ -HCH (by γ - and ), with little evidence of contaminant enrichment in the various sea-ice α 1 ectively retain particulate matter, particularly following partial melt and wa- − ff - and α 24 h) following fresh snowfall (Pu Figure 5 presents a time-series of contaminant concentrations (HCB, More recently, winter-based studies, as part of the Canadian Circumpolar Flaw Lead < content exceeds 5 % (volume fraction) during the onset of melting. prior to May. Concentrations ofmid-May HCB onwards and accompanied HCHs in bycreasing the concentrations increasing in snow overlying concentrations appeared air to as indriven the decline by melt air. from season increased For progresses volatilization arefor from shown this to surfaces, comes be particularly from open theincreasingly signal seawater. of reflect Evidence the the enantiomeric EF fractionsing signal (EF) this ( of period (Wong etmelting al., snowpack 2011). are The therefore fractionice-floe likely of breakup, to contaminants although be retained percolation released in into to the surface the aged, marine ice waters matrix during may occur first as the brine measured in the ice snowpack offrom the Amundsen late Gulf April of to the Canadian earlyfrom Arctic June. during mid-May The CFL onwards, average daily resultingcover, air with in temperature the fluctuated a occurrence around notable ofJune, 0 melt-ponds reduction ice-cover on in in the the the sea-ice Amundsen snowpack surface Gulf by depth had late decreased and May. to By early increase in snow density( and reduction in theand SSA hence over SSA a indicate relatively thethe degree short snow to crystals, time which hence period a reductions in chemicalmore SSA is volatile are likely chemicals, likely to to whereas be resultthe lower vapor-sorbed in latter volatile to evaporative present loss chemicals in of the (e.g. the snowespecially PBDEs in if and their the anionic PFCAs compound form) – will has be a retained significant within particle-bound the fraction. snowpack, (although this fraction was notmay analyzed also separately) and e the older, higherter loss, density which snow may account forloss the of increase in concentrations. Conversely, awhen significant windy conditions were encountered on the sea-ice, again attributed to the rapid SSA). However, the particle-bound fraction of these chemicals is likely to be significant lationship was apparent with snowtheir density ( accumulation or enrichment within higher density snow (with presumably lower samples (i.e. melt waterdensity derived for HCB from and well theapparent mixed lower for snowpack chlorinated samples) PCB congeners, andfor with snowpack PBDEs a weaker (congeners relationship CAs). 47, In 99 this and case,snow snow 100) with density higher and was density used C are assumed asbased to a on have surrogate lower the SSA for (see SSA, observationscampaign. Legagneux Interestingly, where et of for samples al., the the 2002) of longer chain di PFCAs (C (CFL) system study, examinedsystem the of entrapment the and eastern dynamicsnation of Beaufort of POPs Sea the in and behavior the of Amundsennificant Gulf, sea inverse including ice relationships a were detailed evident exami- between chemical concentrations in snow well as the micro-environments of(Gustafsson ice-interstitial et water al., and 2005; ice-rafted Sobek particulate etto al., matter 2006). be PCB relatively concentrations, low however, were0.1–0.3 (e.g. found pg PCB-52 l in snowsub-compartments, and seawater like was the observed ice-meltconducted in water the during range ponds. the of However,activity warmer this and months field melting campaign of hadatmosphere-surface was July–August occurred, water gas when and exchange. when substantial considerable freeze-thaw time had elapsed to allow for ice-associated biota atentrainment a of waterborne biologically-important contaminants time withinpossible of seasonal sea-ice enrichment the and in year. their Furthermore, ice-brine subsequent re-release provides the of a contaminants mechanism to resultingthe marine MIZ in waters. of the the A concentrated Barents notable Sea summer examined field PCBs in investigation ice, in snow and beneath-ice seawater as melt ponds and accumulate as a buoyant layer under melting ice resulting in exposure 5 5 25 15 20 10 25 20 10 15 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | - 1 u- − α for OW ff K 1 − -HCH in 5 % (see γ > 0.3 ng l ± - and ´ α cko et al., 2010a, ´ cko et al., 2010b). PCBs, 9–48 pg l 15 ect HCH levels in sea ect chemical behavior P ff ciently for its brine vol- ff ffi 50). The concentrations of >> -HCH in the sea-ice system of the γ - and α 16954 16953 ect levels of salt and HCHs in the snow by di 3 in the spring (April–May) (Pu ff ∼ ect as new ice forms, reaching 4.0 -HCH. At this time, these concentrations represent ff γ for 1 − ´ cko et al. (2010a, b) examined the behavior of 0.01 ng l ± , for PCBs showed strong linear correlations with corresponding OC K -HCH levels decreased exponentially with increasing sea ice thickness fol- γ cients, ffi ´ cko et al., 2011). In contrast, and as stated above, ventilation under windy conditions In a warming Arctic, summer sea ice has experienced significant retreat in the past Figure 7 summarizes the behavior of of More recently, Pu Multi-year or “old” sea ice was sampled in the Arctic Ocean and the MIZ of the Bar- -HCH, and 0.42 Arctic Ocean and a shift from a multi-year ice cover to ice less than a year old (Stroeve ties) is significantlywarms smaller, enough and for restricted its brineto to volume determine fraction a whether to short this exceed behavior 5the period applies %. newer to Further POPs in other like research spring the contaminants, is perfluoroalkyl particularlywill needed when acids, be some which the of entrained are in ice present in newlysnowfall. seawater forming and sea hence ice and deposited to the surfacethree of decades the with ice decreasing with areafall freeze-up coverage, with reduced a growth lengthened after melt summer, season, delayed decrease in ice thickness over the central sion out of the shallowPu ‘slush’ layer, which maintains a brinewill volume lead fraction to a decreaseto in the HCH loss concentrations of in snow surface theice area. pore (and The spaces presumably extent of other to the which contaminants snowpack snow that can due possess a similar physicochemical proper- rejection) until the combinationinsulation of by declining a atmospheric thickeningume ice temperature fraction cover and to permit drop increasing below thewithin 5 ice % the (the to ice). fraction cool In belowbelow su which the 5 there %; winter, throughout is most this little timethe brine of the ice movement the will accumulating become ice HCH locked concentrations column astration at the exhibits of the ice the bottom a grows, water of thereby brine beneath initially thebrine reflecting volume ice. from the fraction After HCH the the concen- surface first of snow the deposition, ice upward will migration a of Canadian Arctic and illustrates theincluding physical the processes growth which of a likely sea-ice source during of fall/winter organic andtrations contaminants the in to desalination newly-forming of the seation, sea-ice beneath ice the as depend ice rate a primarily environment. of on HCH ice the concen- formation initial (HCH sea accumulation) water and concentra- desalination (concurrent HCH melting of the ice crystal matrix) and the brine salinity decreased (Pu by HCH rejection which, in turn,within will the yield ice elevated and concentrations in inice. the the beneath-ice HCH brine-channels seawater levels during in periodsbulk when the brine ice brine exits due in the sea- the toα winter the were freezing approximately out 13the e highest times HCH higher concentrations than in thewater in Arctic concentrations marine by environment, a exceeding under-ice factorb). of In spring, (i.e.found to from decrease mid-April gradually to with mid-May) time HCH as concentrations the brine in volume ice fraction brine increased were (due to both HCH isomers andthe their initial vertical entrapment distributions of brine in inHCH the young and ice ice and were the highly subsequentlowing desalination dependent the process. on sea ice desalination curveconcentrations, salinity (Fig. and 6). ice The thickness correlations imply observed that between brine HCH rejection is also accompanied coe values). In this older icewater, including there ice-brine. was However, at little one evidence sitethe of where least PCB seasonal elevated melting enrichment PCB had concentrations in progressed were ice-associated (by observed factors relative of to 5–10) the (Gustafsson other sample et sites al., 2005). seasonal and first year icehigher in in younger the ice CFL that campaign contained and brine found (brine HCH salinity concentrations to be ents Sea during July–August,of and showed ice low melt levels water) ofson PCBs et that al., ( had 2005). significant Thenotable role particulate particle-bound in organic dictating fractions particle-bound carbon (0.20–0.83) PCBlibrium content concentrations, partitioning (Gustafs- in with conditions evidence ice (i.e. of (and empirically near equi- snowpack) derived organic had carbon/water a partitioning 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | ect- ff N), their ◦ ective bar- ff ect the distri- ff 2 yr old) in the Arctic Ocean > 16956 16955 ect organic chemical solubility and partitioning ff 4 % decrease from 2005 to 2008) with a correspond- > 1 yr old) (Kwok et al., 2009). Diminishing perennial sea ect the dynamics of organic contaminants in the sea-ice ff < ect such properties to a great extent as compared to other -HCH, 2,4-dibromoanisole (DBA) and 2,4,6-tribromoanisole ff γ - and α ¨ ummel et al., 2003). Species with forage behaviors will accumulate As part of a critical review on the implication of global climate change for human In the last decade the proportion of older, multiyear ice ( way can dominatethemselves all (Kr others and be of far greater significance to the populations more influential to exposure than changes to the physical3.7 environment. Transport of contaminants by biotaBiota (biovectors) that undergoprovide seasonal a migrations transportnia, into route 1998; the for Blais contaminants cryosphere etson that al., to have 2007). mass bioaccumulate the Although transportand or capacity where this by biomagnify population to route air densities (Wa- is or become quantitatively water, large small it due in to is small compari- focused breeding within areas biological this compartments, path- and temperature increases in theuncertain. water Although column. However, salinity theproperties, magnitude would of the a change magnitude is of changesice/snow) in are unlikely salinity to linked a tochanges. climate Their change study (e.g. melting concluded that human behavioral change could be potentially sensitivity of the accumulation ofice organic cover contaminants reduction/elimination. in An the increaserelated Arctic in primary as to a productivity changes result in aquatic ofbution in systems, sea- of sea-ice organic cover contaminantsbound and between fraction. nutrient the While the freely availability, formervolatilization would dissolved drives to phase a pelagic the food and atmosphere, web the theand exposure deep latter particle- and ocean. would is Their enhance available calculations for deposition showedincrease that to for the very the freely hydrophobic dissolved sediments contaminants fraction with would unrealistic only temperature-dependencies tion from the snowpack into theagain, ice, providing once a brine direct levels increaseat contaminant with the pathway the base to onset of of ice-associated the spring; marine organisms, food which web. sit exposure to organic contaminants in the Arctic, Armitage et al. (2011) examined the between the snowpack and the ice, with potential for downward migration or percola- presence of ice-brine in younger ice also allows greater interaction of contaminants Ocean (Su et al.,rections 2006; varied for Lohmann et(TBA) al., by 2009; season and Wong locations et (Wong al., et al., 2011) 2011). andhas exchange diminished di- markedly (e.g. ing increase in younger iceice in ( favor of annual icesystem, will with a a widespreading predominance of the the exposure ice-brine of enrichment ice-associated pathway a organisms such as ice algae in the spring. The calculations show higher nettrations. deposition It of is uncertain PCBs whether becausePCBs this of to was the because higher melting atmosphere PCB ice orwere air margins occurring whether concen- (e.g. were more coupled a to complex source phytoplankton ice-water-atmosphere of activity).net interactions Note volatilization; that not recent all chemicals studies show have predicted net deposition of HCB into the Arctic the other hand, opention. water may The receive net more amount inputgacity and gradient of between direction POPs air of via and fluxwhich water atmospheric are and between deposi- temperature the air dependent. partitioning and Studies propertiesrier have water of for shown the air-ocean depends that compound, exchange sea on of ice contaminants theexpedition is (Jantunen fu- in an and e Bidleman, June–August 1996). 2004, During Gioiaconcentration an measurements et from al. which (2008) theyvolatilization performed inferred for coupled that air PCBs deposition and dominates in water over the Arctic region. However, near the MIZ (78–79 ter enhances solarmelt heat (Perovich, 2011). input Changes in resulting iceocean in coverage have and significant a temperature implications increase warming for inPOPs the the upper that exchange upper have ocean of accumulated POPs withstored between in in greater air the sea and water ice sea ocean. may ice volatilize to may the be atmosphere released when the during Arctic melt, Ocean and opens. On those et al., 2007; Steele et al., 2008; Lindsay et al., 2009; Perovich, 2011). More open wa- 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | er et al., 2008). Permafrost ff 16958 16957 Although far more remote from highly-industrialized temperate countries than Arctic For many Arctic settlements in regions of permafrost, historical containment of regions, the Antarctic also receivesinternational POPs research (Tanabe et stations al., along 1983;nificant Bargagli, the local 2008). Antarctic POP Large contamination coast sourcesbut have (Risebrough been strict et identified handling al., as 1990;case protocols sig- Choi of for et the waste al., Arctic, 2008), potentialcontained in in challenges Antarctica or may by minimize be ice expectedinants and this from due snow source. (secondary to contaminant sources) permafrost reservoirs As and and2009; the in ice Aronson release cover the et of reduction al., these (Curtosi contam- 2011). et al., 2007; Mayewski et al., thawing would result in enhancedaway transport from of these leachates sites, and promotingArctic associated input contaminants communities. to In aquatic Canada, systemsvelopment/approval of climate in waste-containment change close infrastructures for proximity has the to2011). been past major ten considered years (AMAP, during the de- lations (i.e. oil-drilling sumps) continuesdisposal to the in present (Macdonald landfills etceived and al., significant 2005). dumpsites attention Waste in is theing a case sites of potential (“DEW-line”) PCBs across local associated Arctic with Canadahave source the (e.g. been Brown of distant measured et early POPs al., in warn- 2009).tic soils and Recently, PBDEs Canada. around has Concentrations dumpsites re- in inthan landfill Cambridge concentrations soils Bay were, and measured in Iqaluitlocal in some in source background cases, Arc- of over soils, these 100-fold thereby higher persistent presenting chemicals a (Danon-Scha significant continent. wastes has depended in onemafrost way (ACIA, or another 2005). on Wastemilitary the handling installations advantage and of in solid containment the waste by dumps form per- in of small sewage communities and lagoons, industrial dumpsites instal- at under the Antarctic Treaty prevent industrial and some tourist-related activities on the dustrial/agricultural sources are in theconsidered Northern minimally impacted Hemisphere, by Antarctic primary biosystems sources are of contaminants. regulations Today, 3.8 Contaminants in thawing permafrost Human activities in remotelease of cold anthropogenic regions contaminants lead intoare surrounding to more ecosystems. the vulnerable The than Arctic production regions ulations those of in and waste Antarctica the and to locationand the such of in re- sources industry, terms given especially of therecovery). in extraction resident Given of the pop- resources the Eurasian from north lack the of (AMAP, continental 1998), these shelves sorts (e.g. oil of and sources gas in Antarctica, and that most in- but it seems likely thatlocations animals that that are time controlled theirpacted seasonally migrations by by and loss ice choose of ice specific coverthus in foraging stand have a to a warming subsequent be climate. impact These amongbiologically on changes the important) the in most breeding delivery migratory areas. im- behavior of could contaminants to these localized (but associated with these bird coloniesmaking are them on Arctic one oases, while hand onnifying provided the with industrial other enhanced organochlorine hand nutrients they compounds. are Insimilar contaminated Antarctica, set with penguins biomag- of clearly circumstances provide totions, a transport but in contaminants some and cases enrichby non-migratory harvesting them populations over in may a select wide produce ocean similar loca- areas area results and and simply concentrating contaminants associated into ecosystems localClimate rearing (e.g. change Roosens presents et many opportunities al., to 2007; alter Corsolini migratory et behavior in al., all 2007). regions, mulation points. Leading speciesmammals, engaging and in birds migratory with behavior(Evenset include the et fish, latter al., marine providing 2004, thethese 2007a, studies, best-known the b; examples birds Michelutti for feedand et from the rear surrounding al., Arctic their productive 2008, young ocean in 2009; areas colonies (e.g. Foster that polynyas), may et include al., over 20 2011). 000 birds. In The ponds or lakes contaminants from distributed sources and bring these contaminants to localized accu- 5 5 25 20 10 15 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | ´ an ´ an et mann, ´ a et al., ´ ff a et al., usion of ff ´ anov ´ anov cient di ffi erent products are ff and OH radicals) are irradiated C gave predominately reductive x ◦ 7 ´ a et al., 2003b; Heger et al., 2005; − ´ an et al., 2000a, 2001; Kl ´ anov mann, 2000), were found to give the same ff 16960 16959 ect (Heger et al., 2005) and e ff or less (Grannas et al., 2007). Photolysis of frozen 1 − ´ a et al., 2003b; Literak et al., 2003; Dolinova et al., 2006; ´ anov ); contaminant concentrations in natural snow are considerably 1 − 10 µg kg > ´ a et al., 2003a; Matykiewiczova et al., 2007b). In contrast, some compounds, ciently low activation energies can occur. The course of a photochemical reaction ´ anov ffi ´ Laboratory studies have raised the question of whether potential chromophoric or- Freezing of aqueous solutions of organic compounds results in substantial increased an, 2007) or altered acid/base concentrations caused by the freezing process (Heger produced due to chemistry in snow/ice, it will be important to assess their toxicity and related to a substantial concentration e reactive intermediates (Ruzicka et al., 2005).related The to specific the course fact of that the water2003b). reaction molecules is When of then ice chlorophenols do and notupon hydrogen act photolysis) as peroxide or nucleophiles (as (Kl inorganic a nitratesin (a source frozen source of of aqueous the NO solutions, OH(Kl oxidation/nitration radicals reactions compete withsuch the as photolysis 4-nitrophenol (Dubowskiphotoproducts and in Ho both liquid and frozen samples. In cases where di lower – on thesolutions order of, of for 10 ng example, kg haloarenesdehalogenation at and or coupling products, below insteadformed of in photosolvolysis irradiated products, liquid which aqueous2003b) are (Fig. solutions 8). (Kl Predominant formation of the coupling products has been shown to be ardous photoproducts, which caning later or evaporation be processes. introducedgenated Studies into aromatic have the compounds been environment (e.g. reportedal., via chlorobenzenes, for 2001, melt- chlorophenols, species 2000a, PCBs) b; suchMatykiewiczova Kl ( as et halo- Kl al.,2000), 2007b), or nitroaromatic organophosphorus compounds compoundsiments (Weber (Dubowski et employed and frozen al., aqueous 2009). Ho solutions However,trations these with ( exper- relatively high initial reactant concen- reaching the Earth’s surface,environmentally relevant making matrices the greater. likelihood of photochemical degradationganic in contaminants, depositedthe in atmosphere polar and exposed snowpacks to or solar adsorbed irradiation, on can ice produce environmentally crystals haz- in exhibit bathochromic shifts to wavelengths that overlap with those of solar radiation derivatives (Matykiewiczova et al., 2007b) or benzene (Kahan and Donaldson, 2010), local concentrations at theRuzicka ice/air et interface al., (Kl 2005;the McNeill gas et phase al., leads 2012) gradually2011; and to Kurkova their the et formation deposition al., of 2011; on ain Ray an monomolecular et liquid ice layer al., water (Heger surface do 2011). et from not Thebecause al., necessarily absorption of coincide spectra the with of specific chromophores those substance-ice ofKl or the substance-substance same interactions (Heger substances and in/onet ice al., 2006). For example, the spectra of simple aromatic compounds, such as phenol ties of the chromophoresproperties (light-absorbing of the species). host However,temperature matrix the also (snow/ice), optical play the and importantKahan presence phase and roles of Donaldson, (Grannas 2007; other Ram et reactiveKahan and al., et Anastasio, species, 2009; al., 2007 and Kahan 2010). and and Donaldson, references 2010; therein; of the products maying significantly atmosphere impact or the the aquatic compositioneither environment. and The be chemistry primary photochemically chemical of or transformations the thermallyradiation can they overly- initiated. may If still the react compoundschemically with do other reactive species not substances, present absorb for in solar example,can snow organic and undergo radicals, ice. carbanions, dark However, only orsu reactions oxygen, at low temperatures,depends on that many is, factors, only including reactions the which optical, have photophysical, and chemical proper- While the physical processingtheir cyrospheric of fate, contaminants field and instrated laboratory that ice/snow investigations organic is have compounds unambiguously criticaland can demon- Holoubek, in undergo 2002; chemical determining Grannas changes et in al., ice 2007; or McNeill snow et al., (Kl 2012). Subsequent release 3.9 Photodegradation of contaminants in ice and snow 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | ´ e et al., 2008). ects, and compared C. ff ◦ 15 − ´ an et al. (2003) demonstrated erent than the products formed ects. The authors concluded that ff ff cient amounts of hydrogen perox- ffi ´ e and Shepson, 2002; Domin 16962 16961 ´ e et al., 2008). Low concentrations of snow con- ects of chlorobiphenyldiols formed upon the photolysis of ff 5 days at sub-monolayer coverages and ∼ C, connected exclusively to this process, is 1–2 orders of magnitude longer than ◦ at low surface coverages (Domin cient sunlight-induced chemical reaction in experiments conducted using ice sam- The kinetics of ozonation reaction of 1,1-diphenylethylene in artificial snow has been While the majority of studies have been conducted in laboratory settings, several A laboratory study of the photochemical behavior of POPs, such as PCBs, in artificial The porous nature of ice surfaces, especially of snow crystals, allows for adsorp- Specific photoproduct formation in frozen solution is of considerable environmental 25 IA ffi way. The observed photoproducts could pose a high toxicological risk to biota if they eas (Ray et al.,(20 2011). ppbv), For it has typical been atmospheric estimatedof ozone that snow concentrations the grains half-life in is of polar an regions alkene deposited on thestudies surface conducted in the field pointdation to of the potential contaminants importance in/on ofthat snow photochemical several degra- and aromatic ice carbonyl, surfaces. chloro,e Kl nitro and hydroxyl compoundsples prepared underwent from very clean water, but irradiated in natural sunlight in Svalbard, Arctic Nor- ide (a photochemical OHprocesses radical could source) surpass are both present photoreductive inPCBs dechlorination as snow, and photoinduced the evaporative losses major oxidation of sink in a sunlit snowpack (Matykiewiczovameasured et in al., 2007a). order to evaluate the impact of the presence of ozone in the polar ar- snow at environmentally relevanttheir concentrations photochemical enabled changes and simultaneous volatilization monitoring fluxeszova from et of the al., solid 2007a). matrix Reductive (Matykiewic- way, dehalogenation competed (Fig. with 8), as a thesnow. desorption It major has degradation process path- been responsible estimated− for that the the contaminant lifetime of lossthat PCBs in from in surface snow water. under However, in solar radiation cases at where su to sub-monolayer coverages, someice/snow organic surface compounds (Kahan tend and toal., Donaldson, self-associate 2011). 2007, on 2010; Therefore, the Heger intramolecularor et as substance-gaseous al., reactant) well 2011; chemical as processes Kurkovafaces. intermolecular et are (substance-substance likely to occur on the ice sur- reaction (Ray et al., 2011). Even in the case of ice surface loadings which correspond a photofragmentation process (Heger et al., 2011; Kurkova et al., 2011) or ozonation investigations of ice surface/air exchangebic and organic photochemical compounds processes have ofet hydropho- been al., carried 2007a; outduced Heger using by et artificial a al., shock-freezing snowexposed 2011; preparation (Matykiewiczova to Kurkova technique vapors et either of asrectly al., an pure from 2011; organic snow the Ray compound), (whichand et corresponding or is Hilker, as al., aqueous then 2007; contaminated 2011). solutions Matykiewiczova snow et2011; It (Jacobi Kurkova al., prepared et is et 2007a; di- al., pro- al., Bock 2011;snow Ray and 2004, et grains Jacobi, al., 2006; by 2010; 2011). hydrophobic Jacobi Heger The organic specific et compounds surface al., coverage has of been artificial estimated with the help of Their concentrations aresnow then specific directly surface proportional area,K and to inversely their proportional partial totaminants pressure the and snow and the sorption complexity the to of constant study the the system physical are and great challenges chemical to processes those occurring who in want natural snow. Therefore, to those manifested bysolutions product (Blaha (dihydroxybenzenes) et formation insamples al., elicited the 2004). significant liquid inductions Contrary of aqueous the dioxin-like to e photochemistry the can aqueousorganic have solutions, contaminants an are the unexpected present irradiated in impact ice/snow ice to as trace pristine constituents. polartion of regions, volatile when and semi-volatiletants organic (Wania compounds, et such al., as 1998b, persistent 1999a; organic Domin pollu- from gas phase or aqueous (liquid) chemistry. interest. Indeed, the toxic e 2- and 4-chlorophenol inluminescence frozen test aqueous and solutions in were vitro evaluated biomarker using assay for a dioxin-like bacterial e bioaccumulation potentials, as these may be quite di 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | . Additionally, ff erent ff erent in, for example, ff ect snow-atmosphere transfer, ff 16964 16963 ort to elucidate the various chemical mechanisms at play at the molecular ff environments erent depending on the environment. For example, as discussed in Halsall (2004), ects contaminant distributions and the subsequent entry of these contaminants into Another comparison can be made at the large scale between sea ice produced in An additional factor influenced by the local environment is the snowmelt process. As ff ff There are currently several knowledgestanding of gaps contaminant and fate and research the needs potential impact that of limit climate change our on under- contaminant a marine ecosystems. It is,of however, un-flooded clear sea thatArctic ice general Ocean cannot itself, conclusions sea-ice be flooding based issurges extended on known (Carmack to to and studies occur Macdonald, ice in 2008). coastal that regions prone has to storm been flooded. Within4 the Knowledge gaps and research needs from the relatively fewSouthern detailed Ocean, studies sea of ice initially contaminantsbottom. forms in However, in a ice much substantially the larger reviewed same snow above.seawater, way, loading which In accreting then favors new flooding the freezes ice together of at with theice the the sea snowpack (Lange ice to et with form al., layers at 1990). the We top know of nothing the about how the flooding of snow-covered ice crucial that lab orthe field-based physicochemical studies properties investigating contaminant ofevolution fate the of consider contaminants, a not but snowpack only over also the the timescale physical of nature the and processthe being Arctic studied. Ocean and inby the Southern freezing Ocean. at For the theof former, bottom the the while ice ice a generally due accretes relatively tomuch small the snow of desert-like load the conditions is of Arctic’s accumulated the ice at Arctic the these (e.g. top large-scale Serreze et circumstances al., allow 2006). us For to infer generality discussed in Sect. 3.4, the springtimedepends contaminant “pulse” in observed in part receiving waters the on the early extent elution ofdeep of and ground water aged infiltration soluble snowpack and thatwith compounds is surface hydraulic was melting run-o barriers rapidly, found while and to it in is be attenuated snowpacks most in that layered pronounced are snow in subject to bottom melt. Thus, it is as discussed in Sect. 3.3. of SSA. The physical processesthe controlling high SSA Arctic will as betion compared quite amounts di to and warmer frequentshaped windstorms sub-arctic by during areas. winter repeated In result theresults wind in Arctic, in events, the a low rather surface hard precipita- snow thanatively wind-packed being shallow numerous snow, with depth. fresh the In snowfallSSA, surface contrast, events. dominated higher sub-arctic This by depths, snow sastrugi,higher tends higher with to temperatures. permeability rel- exhibit These and lower variables is density will exposed and certainly to a lower wind speeds and Various interactions between contaminantsin and Sect. the 3.1–3.9. cryosphere Each cryospheric havetaminant compartment been plays transport described a unique and roledi in fate. influencing It con- should besnow-atmosphere chemical noted exchange that will these in interactions large part may be be controlled very by the evolution tant photosensitizer for environmental photochemicalchemical reactions complexity in of snow/ice. Given snow/icespecies the may in be the incorporated environment,portant, into and the e snow/ice the matrix, variouslevel. it ways will in be which a challenging, but im- 3.10 Comparison of contaminant/cryosphere interactions in di tion of several organochlorine compoundsphoto-oxidant via induced both reaction direct during photodegradation fieldInterestingly, as experiments samples well conducted made as in using Barrow,greatest Alaska. snow reactivity collected (when from comparedhypothesized the to that Barrow natural several area organic control showed matter experiments), the present and in the the authors snowpack could be an impor- entered the environment. Rowland et al. (2011) studied the photochemical degrada- 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | 16966 16965 cult. Snow and ice samples must be melted prior ecting the behavior of organic compounds in cold ff orts is hampered by the large sample sizes typically ffi ff ecting contaminants in a snowpack or in sea ice simultaneously, i.e. exper- ff Contaminant fate during sea iceof formation, contaminants growth from and snowpacks melting, accumulating including and the melting fate onAir-snow top exchange of ice, of contaminantsand wind and conditions, its dependence on snow permeability Photochemical, microbial and other transformationsnow. processes of contaminants in Mobility, reactivity, andglacier potential ice, in for particular redistribution during time of periods of contaminants seasonal in melting, firn and – – – – Assessment of spatial and temporal trends of contaminants in snow and ice is and particle-phase contaminants inThe snow best and way ice to should assessthrough long the be term various interpreted and sources high with resolutionduct of caution. sample such both analysis. large Unfortunately, spatial scale the monitoring and ability e torequired temporal con- for variability snow/ice is analysis andand the analysis careful process. and Thus, time-consuming the sample developmentsensitivity of preparation analytical and techniques decrease that can interferences increase wouldthe door allow to for higher smaller spatial sample and sizes temporal and resolution open studies. partitioning is an additional factorenvironments. Assessment a of snow/ice concentrations ofciation contaminants with and the their asso- particleto phase analysis, is and di this willcontaminants likely (Wania result et in al., a redistribution 1999b). of As dissolved such, and particle-phase quantitative assessments of dissolved complicated by post-depositional changescess, in and the analytical snowported challenges. concentrations, concentrations of It sampling organic contaminants has ac- depositional in been snow processes. can suggested be Revolatilization partly of thatplace attributed to organochlorines in the post- response has wide to been(Blais range increases et shown of in al., to snow re- 1998; take Seasonal density Herbert snowmelt and (Gustafsson et decreases et al., in al.,1996) 2005b; snow 2005) are Finizio and surface et also chemical area degradation al., important (Hoyau 2006, factors et Burniston al., contributing et to al., within-region 2007). variability. Gas-particle cal conditions. Another possibility issamples a are hybrid approach, transferred where to environmentalreproducible a snow/ice conditions, cold-room thereby avoiding to the conduct questionsamples to experiments are what representative under extent of controlled artificial the snow/ice and real environment. are governed by snowpack/ice characteristics, chemical properties, and meteorologi- Examples include: iments that investigate theand loss interaction by between melt contaminant water reactions, or redistribution brine, and in the vapor phase, and how these interactions One of the great challengeslarge of heterogeneity studying of contaminant snow fate andmay in ice impact the on contaminant cryosphere fate. both Laboratory is a experiments the spatial oning contaminant snow very and behavior have temporal proven in scale useful melt- in anda gaining how important quantitative this description mechanistic insights of and contaminant inprocesses fate facilitating related during to snowmelt. the Other cryosphere contaminant maya fate be set amenable of to similar highly approaches controlled relying and on reproducible experimental conditions within a cold room. Ultimately, comprehensive experiments may becesses feasible that a look at all of the fate pro- modeling studies. Adequate consideration ofstudies these at issues a will variety require ofies. interdisciplinary scales, from molecular level processes to global4.1 transport stud- Experimental challenges transport and processing. These include challenges related to field, laboratory and 5 5 25 15 20 10 15 25 10 20 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | ectively ff erentiate cient use ff ffi erent environmen- ff in the Beaufort Sea providing facilities cients need to be measured for a larger et al., 1995; Roth et al., 2004). Although ffi cients exist (Roth et al., 2004), they may ff ffi orts is the European Space Agency Cryosat- ff 16968 16967 ected. These types of studies will require increas- Amundsen ff ` ere et al., 2006; Bizzotto et al., 2009a, Meyer et al., 2011a, ect snowmelt-induced contaminant pulses, especially by comparing ff ´ cko et al., 2010a, b; Codling et al., 2012). However, these opportunities While modeling should continue and increasingly be used to understand the role of One advance that will aid in modeling e of the available opportunitiesnant and research community field does research work platforms. at a Additionally, variety the of contami- scales, from experiments aimed at been opportunities to collectcontaminant processes appropriate, can year-round be data inferred. ForCanadian at example, Coast the field CFL Guard camps project icebreaker overwintered fromand the which time to conductbiota a (e.g. variety Pu of contaminantare measurements rare on and snow, require ice,munity expensive water commitments currently and in faces logistics. increasinglycommunicate Because limited the key scientific resources, research com- it priorities is and crucial work that collaboratively we to e make e cial to obtain an accurate assessmentocean of and contaminant distribution, the storage state byare the of few upper equilibrium ice-breakers between capableplus of ocean doing clean and such atmosphere. laboratory work Presently, andprofiling). there (requirements Some sampling include Arctic facilities ice countries plus capability that (USA, ancillary will Canada) require geochemical/instrumental face years to the bring issue replacements of on aging line ice-breakers (NRC, 2011). Recently there have estimation methods for thesenot partition be coe appropriate for moresome complicated of chemicals such the as semi-volatile current-use emerging pesticides contaminants. and 4.3 Logistics and community coordination For many of the POPs, we haveor few along or no transects reliable from ocean shelf data to collected basin as depth interior profiles locations. These sorts of profiles are cru- els that attempt to quantify the role of meltingthe sea ice/glaciers cryosphere on in contaminant contaminant fate. fateparticular, snow-air processes, and input snow-ice values partition still coe set need of improvement. chemicals In than currently available (Ho 10–20 cm (Parrinello et al., 2012). This information will be a critical component in mod- contaminant releases due toclimate the change induced melting glacier of melt.taminants Likewise, seasonal it in will snowpack polar be marine versus important systems thosesea to predominantly snowpack understand due come or if to from directly con- melting from glaciers, the sea atmosphere. ice, 2 mission. Cryosat-2 was launchedthickness in and 2010 extent with of the polarunprecedented goal ice. view of Recent monitoring of reports changes the indicateas in that seasonal the well Cryosat growth as is and information delivering retreat on an the of thickness sea of ice the across Greenland the ice Arctic, sheet, accurate to within ing collaboration between chemistsimportance of and contaminant ecologists/ecotoxicologists. exposure Additionally, viafrom snowmelt the other should sources of be contaminant compared exposure.need to Similarly, more to that field arising be and modeling conducted studies from to melting determine glaciers the may cause degree biological to impacts. which It the will release be of important contaminants to di phenomenon is. For example, we needtal to conditions better understand a how di field and modelinglar results. systems We and also locations needcontaminant in the pulses. to world Moreover, identify more that thelikelihood might studies and types be need degree most to of to prone which be mountainlogical snowmelt-induced to impacts conducted contaminant and snowmelt-induced (i.e. pulses extension to po- of are determine the causingaquatic work bio- the by organisms Bizzotto might et be al., most 2009b) and a to identify which Although contaminant pulses resulting from springmodeling snowmelt and have been lab predicted studies from field (reviewed in in a few Meyer cases and (LaFreni b), Wania, more 2008) field and studies observed are in needed the to determine how common and how important this 4.2 Validation and improvement of models 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | ective communication across mul- ff 16970 16969 This manuscript arose from discussions during and following the 3rd c. Contaminants interact with the cryosphere in varied and complex ffi ects of climate change are becoming more pronounced in the cryosphere, ff The greening of the Arctic will likely impact air/surface exchanges, may increase for- The e Finally, opportunities should be sought to extend collaboration between the science Acknowledgements. Workshop on Air-Ice Chemicalshop Interactions was (AICI) sponsored in inApplied June part 2011, Sciences. by in IGAC We and New wishA.M.G. the York, to NY. wishes Columbia This acknowledge University to work- School IGAC acknowledgewishes of for to support Engineering acknowledge financial from support and support from theand the for the NSF Grant publication project Agency CAREER CETOCOEN of costs. award (CZ.1.05/2.1.00/01.0001) thevelopment (ATM-0547435). Czech Fund. granted Republic P.K. by (P503/10/0947), the European Regional De- these are often studied as isolatedpicture processes, it of is contaminant crucial cycling, to develop whichtiple an will disciplines. interdisciplinary require e types of events are currently unknown. est/tundra fire frequency, and couldwith lead plant to and remobilization soil of carbon.opment In contaminants of addition associated the to Arctic climate may changetrends have impacts, a within the large the future expanding region, devel- impact asto on energy organic shipping resource contaminant exploration tra levels expands and andways, waterways involving open the interplay of biological, chemical, and physical processes. Although dra vegetation (e.g. Olsen et al.,the 2011; subsequent Callaghan formation et of sheet-ice al., once 2011).implications temperatures This decline of is again. these often The followed events ecological by onresearch terrestrial (e.g. flora Bokhurst and fauna etthe are seasonal al., the snowpack subject 2011) and of their but ecological potential the impact release as additional and stressors fate during these of contaminants from resulting in partial melt of the winter snowpack and the exposure of the underlying tun- pact of climate changeter on warming cryospheric anomalies contaminant in cycles. the For example, Arctic recent are win- resulting in rapid temporary thawing events The scientific community hascontaminant made transport much and progress redistribution in withinimpacted the elucidating by cryosphere, a the and changing mechanisms how climate. of these may be evidenced for example by unprecedentedchanges declines to in the sea cryospheremospheric ice will and extent. certainly oceanic Climate-induced transport impactmelting and the ice releasing fate and previously of trapped glaciers. contaminants, contaminants There from remain altering many at- unanswered questions regarding the im- cycling of contaminants. Field, laboratory, andand modeling ice studies are have crucial shown components thattaminants, of snow through the both Earth uptake system andring that release can in mechanisms. influence Chemical snow the processesproducts fate and occur- potentially of ice more con- toxic may or more also bioaccumulative impact than the contaminant original contaminant. fate, in some cases generating tential to engage localprohibitively communities expensive. in Collaboration monitoring then activities, leadsporating which local to otherwise knowledge, better and could monitoring better be communication designmunities. between by scientists incor- and local com- 5 Conclusions The cryosphere has the capacity to significantly impact the local, regional and global transport at the globalical scale. Interdisciplinary to collaboration link and the communicationaccurate various manner. is individual crit- studies done at multiple scalescommunity in and a the meaningful people and who live in cold regions. One immediate benefit is the po- a molecular-level understanding of chemical degradation to modeling of atmospheric 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | en, K., Thomas, R., ff , J., Li, Y. F., Lockhart, ff erent Altitudes in the Tatra ff ˚ a, K., Christensen, J. H., Dowdall, M., Odland, 16972 16971 ects of Selected Pollutants and Climate Change in the ff huber K., Pawlak, J., and Reiersen, L.-O., Arctic Monitoring and ff , K., Fahnestock, M., Marshall, S., Rosing, M., Ste ff ´ andez, P., Tatosova, S., Stuchlik, E., and Grimalt, J. O.: Long-Range Trans- er, M., van den Broeke, M., and van der Veen C. 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4 to 5 ring PAHs, PCBs, alkanes semifluorinated long chain perfluoroalkyl acids, chlorpyrifos lindane, fluorene intermediate chain perfluoroalkyl acids Examples atrazine, chlorothalonil, short chain perfluoroalkyl acids Body

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opernicus.org 16992 16991 Contaminant characteristics water soluble strongly sorbing to particulate matter (PM) or snow grain surfaces somewhat water soluble and at the same time for snow high affinity grain surfaces partially dissolved in the aqueous melt water phase and partially sorbed to PM sorption to snow grain surface decreasing during the melt

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Types of snowpack elution behavior observed in the laboratory.

Copernicus Bahnhofsallee 1e 37081 Göttingen Germany Martin Rasmussen (Ma Nadine Deisel (Head of P 5 2 3 4 the laboratory. behavior observed in elution Table 1. Types of snowpack Type 1 13, 1827–1842, 1999. nia’s Central Valley to the Sierra Nevada Mountains, J. Environ. Qual., 22, 80–90, 1993. rinated acids in Arctic snow:41, new 3455–3461, evidence for 2007. atmospheric formation, Environ. Sci. Technol., Table 1. Zhao, L. T. and Gray, D. M.: Estimating snowmelt infiltration into frozen soils, Hydrol. Process., Zabik, J. and Seiber, J. N.: Atmospheric transport of organophosphate pesticides from Califor- Young, C. J., Furdui, V. I., Franklin, J., Koerner, R. M., Muir, D. C. G., and Mabury, S. A.: Perfluo- 5 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | the (c) the pro-glacial Lake Stein, and (b) 16994 16993 the pro-glacial Lake Oberaar, (a) Schematic diagram illustrating the various elements of and interactions occurring in the Annual input fluxes of PCBs and DDTs (left y-axes) into sediment in three Swiss Alpine lakes including Fig. 2. non-glacial Lake Engstlen. Foris pro-glacial provided lakes, (right the y-axes) annual withvalue movement a to positive of value a the corresponding glacier adjacent to retreat.by a glacier Note glacier three growth that and to the a valuesal. fit negative for (2011). to PCBs in the Lake y-axis Oberaar scale. have been Figure multiplied adapted from Bogdal et al. (2009) and Schmid et Fig. 1. cryosphere that impact contaminant cycling and fate. Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | 16996 16995 Temporal trend for hexachlorobenzene (HCB) in air at Zeppelin, Norway during the Average air levels (top) and enantiomer fractions (bottom) at Resolute Bay before and af- monitoring period 1993–2010. Fig. 4. ter the seasonal ice meltReported (Jantunen errors et represent al., 1 2008). standard Picture deviation modified based according on to method AMAP uncertainties. (2011b). Fig. 3. Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | C. HCB and HCH ◦ -HCH (bottom) concentrations in snow and air γ ´ cko et al., 2010a). 16998 16997 -HCH (middle) concentrations and ice salinity (bot- γ - and α -HCH (top) and α Time-series of HCB (top) and Dependence of concentrations in air are shown on the secondary y-axes. Data from Codling et al. (2012). Fig. 6. measured in the Amundsen Gulf,imately Canadian denote Arctic the (April–June period 2008). when The average vertical air lines temperatures approx- were at or above 0 tom) on sea ice thickness (adapted from Pu Fig. 5. Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | ecting HCH con- ff 17000 16999 erent mechanisms and products that occur in liquid water and ice. ff ´ cko et al., 2011). Comparison of photochemistry of haloarenes in water and frozen aqueous solutions, Schematic diagram of atmosphere-snow-sea ice-ocean processes a illustrating the di Fig. 8. centrations in various compartmentsfrom Pu of the Arctic environment in various seasons (adapted Fig. 7.