Q1 Research Update

1. Q1 Research Update Tanvir Khan Environmental Engineering Doctoral Program Department of Civil & Environmental Engineering Michigan Technological University 11/14/2013

2. Presentation Outline • Atmospheric-surface exchangeable pollutants (ASEPs) • Terrestrial-atmosphere exchange processes of ASEPs • Air-water • Air/soil-plant • Research questions (Q1 – Q3) • Components of Q1 Tasks • Environmental compartments of ASEPs • Parameters for database development for PAHs and PCBs • Parameterization for various environmental compartments • Air-surface exchange parameterization • Comparison of global models of terrestrial net primary productivity

3. Atmosphere-Surface Exchangeable Pollutants (ASEPs) Resist rapid degradation Atmosphere ASEP characteristics Semivolatile Surface Accumulate in organic rich media Proposed compounds to study: Mercury (Hg) Polycyclic aromatic hydrocarbons (PAHs) Polychlorinated biphenyls (PCBs)

4. Dynamically Coupled Human-Natural ASEP System Human ASEP System Ecosystem Services Safe food Well-being Safe water Socioeconomic activity Perceptions, beliefs, goals Safe air Sequestration Governance, adaptation Stressors Population growth Biogeochemical Cycle of ASEPs in Nature Land use/cover Atmospheric transport Energy sources Natural & secondary emission Anthropogenic emission Ecosystem impact, process change Deposition Climate change

5. Air-Water Exchange Process of ASEPs Atmosphere Particle-bound POPs, Hg (II) Gas-phase POPs, Hg (II) Gas-phase Hg (0) Gas/particle partitioning Dry deposition (particle) Air-water exchange Wet deposition (particle + gas) Loss through outlet Dissolved-phase POPs, Hg (II) Dissolved-phase Hg(0) Inputs Water column Particle-bound Hg (II), POPs DOM-bound POPs Diffusive exchange Resuspension Settling Dissolved-phase POPs, Hg (II) Degradation Surface layer Sediment Sediment-bound POPs and Hg (II) Burial into deep sediment POPs=Persistent Organic Pollutants Rowe et al. (2008)

6. Air-Soil/Plant Exchange Process of ASEPs Atmosphere Gaseous dry deposition Wet deposition (particle + gas) Particle dry deposition Reemission/ Volatilization from soil Uptake by plant cover Reemission/Volatilization from plant cover Top soil Uptake by plant root Leaching Diffusion Intermediate soil Degradation Burial Reservoir Layer Palm et al. (2004)

7. Global ASEP Cycling High latitudes (Deposition > Re-emission) Mid-latitudes (Re-emission and deposition dominated by seasonal cycles) Global Distillation Long-range atmospheric transport Low latitudes (Re-emission > deposition) ‘Grasshopping’ effect Vallack et al. (1998)

8. Research Questions “What features of secondary emissions lead to added impact, in terms of elevated deposition, to ecosystems, now and in future, and in what environments does ASEP sequestration mitigate ecosystem service losses?” Q1 “How will alteration in global secondary emissions of Hg due to global change alter U.S. regional household income due to health effects caused by fish consumption, and what assumptions are needed to extend this work to other ASEPs?” Q2 “How can governance be improved to reduce the negative impacts of ASEPs and enhance adaptive management across multiple jurisdictional scales?” Q3

9. Tasks Involved in Answering Q1 Model Applications Model Development Model Improvement A) Development of PCB and PAH GEOS-Chemmodels (Selin Group) [Sensitivity analysis] E) Scenario development F) Historical and current simulations G) Future simulation H) Atmospheric deposition to fish [Sensitivity analysis] B) Improved method to incorporate land use/cover effects on ASEP cycling C) Incorporate new ASEP air-surface exchange parameterizations D) Improvement in NPP-ASEP coupling [Sensitivity analysis]

10. Model ASEP Environmental Compartments Soils Ocean Lakes, rivers Lake, river, and ocean sediments Leaves and grass Snow/ice

11. Parameters Needed to Describe PAH and PCB Measurements in soils • Sampling location details: • Latitude, longitude, altitude, land utilization type, population in the sampling area, distance from major road networks, etc. • Types of soil: • Natural, forest soil, urban, rural, upland soil, industrial soil, grassland, waste water irrigated soil, arable/paddy soil, etc. • Types of contamination: • Non-contaminated • weakly/heavily contaminated • Depth of sediment core sampled: • Minimum/Maximum/average depth • Sampling/identification technique • Other soil parameters: • Black carbon content • Organic matter content • Organic carbon content • Sediment grain size distribution • Soil pH

12. Parameters Needed to Describe PAH and PCB Measurements in Oceans, Rivers, and Lakes • Surface microlayermeasurement: • Temperature • Relative humidity • Atmospheric pressure • Wind direction/speed • Sun irradiation • Concentrations of PCBs/PAHs: • Dissolved, particulate • concentration in air • concentration in water • Other parameters: • Henry’s law constant • Fugacities • Deep-ocean measurement: • Sampling location, date (time period) meteorological parameters • Water quality parameters: • oxygen content • Salinity • temperature

13. Parameters needed for leaves/grass Parameters needed for snow/ice • Sampling location details: • Sampling period, geographic location • (latitude, longitude, altitude) • Meteorological parameters: • Annual precipitation, Snow precipitation, temperature, etc. • Snow sample characteristics: • Sample types: (core or layer?) • Snow depth • Snow density • Water equivalents • Suspended particulate matter concentration in snow • PAH/PCB fluxes in snow • PAH/PCB concentration: • Total PAH/PCB concentration • Individual PAH/PCB concentration • Sampling location details: • Types of forest (examples: deciduous, boreal coniferous forest, etc.) • Leaf characteristics: • Leaf area • Lipid content • Exposure time • Sampling/identification techniques: • Sampling tools • Storage devices • Extraction methods

14. Air-surface Exchange Parameterization Air-soil exchange parameters Air-water exchange parameters • Mass concentration based model: • Dissolved concentration (Cw) • Gas-phase concentration (Ca) • Mass-transfer coefficient (ka/w) • Flux (F) • Fugacity based model: • Dissolved concentration expressed in fugacity (fw) • Gas-phase concentration expressed as fugacity (fa) • Mass transfer coefficient (Daw) • Flux (F) • Additional parameters: • Molecular weight • Henry's law constant • Temperature • Octanol-air partition coefficient (Koa) • ……more…. • Concentrations of ASEPs: • in soil (Cs) • in air (Ca) • Fugacities of: • in soil (fs) • in air (fa) • Other soil parameters: • Fraction of organic matter (fom) • Octanol-air partition coefficient (Koa) • Soil water partition coefficient (Kd) • Soil air partition coefficient (Ksa) • Henry's law constant • Soil bulk density • Aqueous solubility • …..more…

15. Comparing Global Models of Terrestrial Net Primary Productivity CASA, GLO-PEM, SDBM, SIB2, and TURC #5 Satellite-based models BIOME-BGC, CARAIB 2.1, CENTURY 4.0, FBM 2.2, HRBM 3.0, KGBM, PLAI 0.2, SILVAN 2.2, and TEM 4 #9 Terrestrial models of biogeochemistry Models for seasonal fluxes Models for seasonal fluxes and vegetation structure BIOME3, DOLY and HYBRID 3.0 #3 Major processes are: Photosynthesis Growth and maintenance respiration Evapotranspiration (d) Uptake and release of N Allocation of photosynthate to various parts of plant Litter production and decomposition Cramer et al. (1999)

16. Comparison of Three Model Types Use satellite data Determine temporal behavior of photosynthetically active tissue Asses climate variability of NPP Satellite based models Use soil and climate characteristics to simulate fluxes Describe functional changes within particular vegetation type Possible re-distribution of vegetation is ignored Models for seasonal fluxes Equilibrium between climate and vegetation is assumed Simulate changes in both ecosystem structure (vegetation distribution) and function (biogeochemistry) Models for seasonal fluxes and vegetation structure

17. Thank you.

18. References Cramer et al. (1999) Comparing global models of terrestrial net primary productivity (NPP): overview and key results, Global Change Biology (5), 1-15 Palm et al. (2004),Evaluation of sequentially-coupled pop fluxes estimated from simultaneous measurements in multiple compartments of an air–water–sediment system, Environmental Pollution (128) 85–97. Rowe, M.D. (2008), State Of Lake Superior, Ecovision World Monograph Series, Burlington, Canada. Vallack et al. (1998), Controlling persistent organic pollutants–what next?, Environmental Toxicology And Pharmacology (6) 143–175.