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Impacts of Climate Change on Cycling, Accumulation and Feedbacks of Chemicals in Aquatic Ecosystems Jordi Dachs Department of Environmental Chemistry, IDAEA-CSIC, Barcelona, Catalunya, Spain. . Introduction : Definition of POPs Some chemicals represent an environmental risk • 1- Persistence • 2- Bioaccumulation • 3- Long-range transport • 4- Toxicity and exposure routes • 5- Quantity produced / discharged to the environment • 6- Other adverse effects: on atmospheric chemistry,… Persistent Organic Pollutants Environmental fate of organic pollutants Gas-Particle Partitioning Atmospheric Transport CA CG Dry Deposition Air-Water Exchange Water-Particle Continental Partitioning Inputs CP CW Advection Vertical Fluxes Degradation Bioaccumulation Major permanent sinks: - Ocean interior (sediments, deep waters) - Atmospheric OH degradation Wet Deposition Concentration (ng m-3) Influence of T on atmospheric concentrations 40 Sandy Hook E- NPs PCBs If temperature increases from 1 to 4°C degrees then: 30 Gas Phase 20 Aerosol Phase 10 0 Log CG ( ng m-3) Jun Jul Aug Sep Oct Nov Dec Jan Nonylphenols 2 Enhanced mobility and long range transport of chemicals 1 0 -1 Gas-phase concentrations of chemicals will increase between 20% (PCBs) to 100% (Nonylphenols). Log Cg = -9135/T + 31.7 R2 = 0.88 0.0033 0.0034 0.0035 1/Temp (K-1) 0.0036 (IPCC Synthesis Report 2007) Influence of Temperature on environmental partitioning H= K AW CiA, eq Ciw, eq air KOA C iO, eq CiA, eq octanol water Kow CiO, eq Ciw, eq Predicted percent change in airwater (H), octanol-air (Koa) and octanol-water partition coefficients associated to a 5°C increase for selected chemicals (from Macdonald et al. 2005). (IPCC Synthesis Report 2007) How pollutants reach the Arctic and Antarctica? Air-water gradient of PCB fugacity (Gioia et al. J. Geophys. Res. 2008) Case Study: POPs in the Arctic (MacDonald et al. Sci. Total Environ. 2005) Case Study: POPs in the Arctic - MacDonald and coworkers have published the first comprehensive study on the implications of climate change on POP cycling and impact. This will modify: - Atmospheric inputs of POPs/pesticides - Atmosphere-ocean gas exchange and delivery of ice-cover content of POPs - Riverine inputs - Chemical partitioning and degradation of POPs. - These changes are also linked to: - Altered food web structure - Food deprivation or shifts in diet - Altered migration pathways and invading species -The literature suggests that there is a dynamic link between organochlorine compounds and disease and epidemics in wildlife arctic populations. Environmental fate of organic pollutants Gas-Particle Partitioning Atmospheric Transport CA CG Dry Deposition Air-Water Exchange Water-Particle Continental Partitioning Inputs CP CW Advection Vertical Fluxes Degradation Bioaccumulation Wet Deposition Influence of trophic status on POP accumulation by biota (- Berglund. O. Limnol. Oceanogr. 2003 - Dachs, J. Hoff,R. S.J. Eisenreich, Environ. Sci. Technol. 2000. - Berglund, O., P. Larsson, G. Ewald, L. Okla. Ecology 2001) Climate Change and Soil Respiration (Nature 440, 165-171, 2006) (Nature 439, 711-714, 2006) (PNAS 101, 423-428, 2004) (soot responsible for a quarter of global warming) Atmospheric Deposition of PCBs to European Marine Waters (PCB 153) Dry deposition flux [pg m-2 d-1] Wet deposition flux [pg m-2 d-1] Net air-water exchange flux [pg m-2 d-1] (IPCC Synthesis Report 2007) Predicted precipitation changes in Europe Wet deposition flux [pg m-2 d-1] Importance of precipitation as a driver of water column chemical concentration variability (Example: Adriatic Sea) FSINK PCB 180 precipitation B epth [m] depth [m] PCB 28 depth [m] A CWT [ng m-3] PCB 28 (Jurado et al. 2006, In press) Extreme Events and POP Remobilization Elbe River Flood 2002 Re-distribution of Contaminants - Dioxins Behind broken dams Riverbanks Elbe River Flood 2002 Re-distribution of Contaminants – Dioxins and other POPs -In the Elbe River Flood, no significant increase was measured in levels of PCDDs/Fs and PCBs in river and floodplain sediments, with few exceptions. - The 2002 flooding event did not result in a large-scale contamination of the areas affected by the floodwaters. However, the relatively high contamination levels in the floodplains represent the historic dimension of repeated floods events in upstream industrial regions. - Repeated incidence of floods have the capacity to re-mobilize and re-distribute large amounts of contaminants and cause widespread contamination. Soils Are an Important Environmental Reservoir of POPs PCB usage (tn) 0 -30 30ºS -60 60ºS -90 0 20000 40000 60000 80000 100000 0º 90ºS 180ºW 135ºW 90ºW 45ºW 0º 45ºE 90ºE 135ºE 180ºE S oi l c on c (p g/ g dr y wt) 120000 La titude 60 30ºN 0 60ºN 30 90 20000 40000 60000 80000 100000 120000 T ot al PC B u sag e ( to nn es ) 90ºN Soil Conc (pg g-1) 0 20 40 60 80 100 120 140 160 180 200 Inventory in soil or ocean mixed layer / Inventory in atm boundary layer PCB 101 (Dalla valle, M., Dachs, J., Sweetman, A.J., Jones, K.C. Global Biogeochem. Cycles 2004. Dalla valle, M., Jurado, E., Dachs, J., Sweetman, A.J., Jones, K.C. Environ. Pollut. 2005.) Soils Are an Important Environmental Reservoir of POPs Influences of climate change -The capacity of soils to accumulate and sequestrate atmospheric chemicals is a strong function of organic carbon quantity and quality, temperature, humidity…. - Changes in soil organic matter quality or quantity may affect chemical concentrations in soils. - Underlying climate change processes that result in a change of soil use and management, can be expected to influence the storage capacity of “old” and “new” chemicals. Climate fluctuations and atmospheric occurrence of POPs - Changes in atmospheric circulation patterns and air-masses can induce changes in POP fate and impact. -“Inter-annual variations of POPs air concentrations from the Great Lakes region and the arctic have been strongly associated with atmospheric lowfrequency fluctuations, notably the North Atlantic Oscillation (NAO), the El Niño-Southern oscillation and the Pacific North American (PNA) pattern. This suggests interactions between climate variations and global transport and distribution of POPs” (Ma et al. Environ. Sci. Technol. 2004). CONCLUSIONS - The influence of Temperature on environmental partitioning and rates of organic chemicals can be predicted with moderate uncertainty. These predictions suggest higher concentrations in the atmosphere. - The impact of higher remobilization is complex due to multiple of interactions of trophic and physical processes. - Extreme events may remobilize POPs and affect their impact. - Pristine environments far from sources may be more exposed to anthropogenic chemicals. - Little is known on how climate change will affect impact of chemicals to ecosystems. - Legislation on POPs are based on scientific criteria for persistence, long range transport potential and bioaccumulation, which may need to be revised under climate change scenarios. Anthropogenic perturbations of Coastal regions (Dachs & Méjanelle. Estuaries and Coasts 2010) Efecte dels contaminants orgànics en el cicle del C - Hi ha multitud d’articles sobre efectes de contaminants individuals en organismes - Hi ha molt poca feina feta sobre els efectes de les mescles reals de contaminants en els organismes - L’ECO-toxicologia ha oblidat l’”ECO”? - Poden els contaminants afectar el cicle del carboni mitjançant els seus efectes en fitoplancton i bacteris? Pollutant effects on Phytoplankton Pollutants effects on phytoplankton: Single chemical Cultures Effects of phenanthrene on cultured phytoplankton Pollutant effects on Phytoplankton: single chemical NE Atlantic Ocean Effects of phenanthrene on natural Atlantic Ocean phytoplankton Pollutant effects on phytoplankton: mixtures NE Atlantic Ocean Prochlorococcus sp Synechococcus sp Chlorophyll a 21 ± 6 27 ± 3 40 ± 22 23 ± 13 31 ± 12 36 ± 8 Mixtures of PAHs 661 ± 588 812 ± 262 2448 ± 8092 Phenanthrene 5020 ± 1230 5880 ± 1450 21340 ± 7090 Pyrene 3130 ± 1420 8590 ± 2110 35010 ± 16390 Non-polar organic compounds Polar organic compounds LC10 given as C/Ccontrol (Echeveste et al. Chemosphere 2010) LC10 (Relative concentration at which abundance or chlorophyll a is reduced by 10%) Pollutant effects on Phytoplankton: Mixtures Mixture of PAH Non-polar Organic Pollutants 45 30 15 1 24 16 8 Dead cells (%) 18 12 6 37 10 1 16 8 1 Prochlorococcus sp 34 31 28 1350 C/CControl (Echeveste et al. Chemosphere 2010) 37 10 100 C/CControl 40 Prochlorococcus sp 34 31 28 25 25 0 Synechococcus sp 24 100 C/CControl 40 Prochlorococcus sp 32 0 1 1350 C/CControl 30 Dead cells (%) Synechococcus sp 0 0 24 32 Dead cells (%) Synechococcus sp Dead cells (%) 60 40 40 Dead cells (%) Dead cells (%) 75 Polar Organic Pollutants 1 10 C/CControl 100 1 10 C/CControl 100