Mother Nature As Engineer and Witness! Dr. Joel G. Burken & Matt Limmer Missouri University of Science & Technology

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1 Mother Nature As Engineer and Witness! Dr. Joel G. Burken & Matt Limmer Missouri University of Science & Technology

2 What PLANTS can do And what WE can learn PhytoForensics PhytoRemediation Evapotranspiration = Ecohydrology Organic Carbon = Energy

3 Volatilization Degradation Plant Mediated Mechanisms Metabolism Sequestration Rhizodegradation Stabilization Hydraulic Control 3

4 Phytoforensic Conceptual Model Transport characterized by bio-physico-chemical properties Leaf-Air Exchange Wood-Air Partitioning Metabolism Growth Dilution Wood-Air Partitioning Root Membrane Wood-Water Partitioning Degradation Solubility 4 Advection Dispersion Sorption

5 Tree Coring Collect a core sample Place into vial Wait Test Via Gas Chromatography Map trees -> groundwater

6 Demonstration Sedalia Missouri PCE and TCE contaminated site in Old railroad yard. Site investigation over 10 years, 40 sampling points. Roughly $220,000 spent

7 Chlorinated Solvents Sampling Project, Sedalia Missouri 114 samples = 1 day, 4 person crew

8 Plants to Built world.. And us. Plants buildings breath the same air from the subsurface THE BUILT ENVIRONMENT Contaminant Fluxes Current Models Proposed Model Subsurface Building Environmental Volume RESIDENCE This Proposal PLANTS Subsurface Tree Environmental Volume Vapor Intrusion J&E Model Phytoscreening Phytoremediation GROUNDWATER CONTAMINATION

9 Comparison: Plants & Indoor Air Phytoforensics testing and Indoor Air studies in Cambridge Canada showed that inplanta sampling can indicate potential indoor air contamination, i.e. vapor intrusion

10 Old & New Approaches > 50 sites in 13 states, 8 countries Cl-VOCs, BTEX, CFCs, Explosives, Perchlorate, PAHs Sampling does not need to bring the tree into the lab. Rather let s bring the lab to the tree! In-planta sampling: SPME Solid Phase Samplers GC/MS

11 In Planta SPME and SPS analysis S&T Patent!

12 Phytoforensics Benefits

13 Green Infrastructure Integrating Greentechnologies (plants) into urban grey hardscapes Multiple benefits can be gained but are difficult to accurately value and compare to accepted Grey technologies. Challenge: Benefits not observed by those bearing costs. 13

14 Benefits Quantifiable? Ecosystem services - Habitat Regulatory - water/soil treatment, CO 2 Sequestration Provisioning - Biomass Fuel, Fiber, Food Cultural - Aesthetics Acceptance Comforting Health Mother Nature s Sum

15 Integrating Green Infrastructure Design 15

16 Integrating Green Infrastructure Design 16

17 Integrating Green Infrastructure Design Case study of Arsenic soils in Washington DC brownfields 17

18 Integrating Green Infrastructure Design 18

19 Urban redevelopment Petrol station Integrating Green Infrastructure Design Existing conditions 2006

20 Integrating Green frastructure Design

21 Integrating Green Infrastructure Design

22 What is Value? How assigned? How compared? We value remediation because we value water, air, soil, ecosystems Efficacy: treatment level and cost Confidence and reliability Speed NOW CAN WE compare and link the two? Establishing values for local decision makers Provisioning services Regulatory services Supporting services Cultural services How to translate values through economic tools?

23 If your plan is for one year plant rice. If your plan is for ten years plant trees. If your plan is for one hundred years educate people. - Confucius Thank you! Burken@mst.edu

24 Predictions of plant uptake 1 Predicted TSCF Log Kow Environ. Sci. Technol. Lett., 2014, 1 (2), pp

25 Phytoforensics Tech Transfer EPA-USGS User s Guide Burken@mst.edu vroblesk@usgs.gov EU supported Biotool

26 Sampling for Directional Data Most trees exhibit sectoriality, water flows vertically, with little mixing Limmer, Shetty et al. Directional analysis. Environ. Sci. Technol., 2013, 47 (16),

27 Directional Introduced pollutant in one quadrant of 240 l mesocosm Monitored with in-planta sampling and ended with destructive sampling Limmer, Shetty et al. Directional analysis. Environ. Sci. Technol., 2013, 47 (16),

28 Field confirmation Shanley Street, Waterloo Ontario Limmer, Shetty et al. Directional analysis. Environ. Sci. Technol., 2013, 47 (16),

29 Now Announcing: Explosives Phytoforensics Nitroaromatics Nitramines Nitroimino Nitrate esters TNT C 7 H 5 N 3 O 6 (227.13) DNAN C 7 H 6 N 2 O 5 (198.14) RDX C 3 H 6 N 6 O 6 (222.12) HMX C 4 H 8 N 8 O 8 (296.15) Nitroguanidine CH 4 N 4 O 2 (104.07) PETN C 5 H 8 N 4 O 12 (316.14) GTN C 3 H 5 N 3 O 9 (227.09) 2 9

30 Separation: Chromatogram Standard mixture Standard mixture in Sap Peak area Concentration (ppb) Mu, R. et al. (2012) A fast separation and quantification method for NG and 2, 4-DNA by liquid chromatography/tandem mass spectrometry, Analytical Chemistry 84(7),

31 Sap Sample in < 2 hours, NO Solvents! Freeze 2 hr. 23,000 G 20 min 30 kda sieve / 0.22 μm filter Fresh Plant Tissues Analytic

32 Correlation of Solvent Extraction and Centrifuge Sap Extraction 32

33 Sap RDX concentration, mg/l Correlation of Centrifuge Sap Extraction 0.01 and porewater exposure concentration R² = R² = R² = R² = Pore water RDX concentration, mg/l 100 Yuan, Y., (2013 Submission) Developing phytoforensic strategies for energetics I: Novel solvent free centrifuge extraction to determine plant concentration. To Environmental Science and Technology Willow Poplar Ryegrass Bigbluestem Power (Willow) Power (Poplar) Power (Ryegrass) Power (Bigbluestem)

34 PCE >10 ppb 1-10 ppb ppb ppt 1-10 ppt ppt ND NS

35 In-planta Concentrations Not just testing and delineation, but monitoring and remediation. Concentration (µg/l) 2 years PCE TCE

36 Tree 2 Northern Port SPME & core analysis 1000 PCE TCE cdce PCE MQL TCE MQL cdce MQL Core PCE Core TCE Core cdce 100 Concentration (µg/l) Port 3 48 cm DBH Baldcypress 36 (Taxodium distichum)

37 Mass removal rates Penman Monteith for determining ET potential Mass= Et o * C TCE

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39 What else can Mother Nature tell us about???? Climate change?

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41 @ S&T Modest Greenhouse 800 ft 2 Atop analytic facilities: SPME GCMS, ICPMS, LC/MS-MS, Single nanoparticle ICPMS. Climate control chambers Computational biology and statisticians 41

42 Interests Advancing field methods, on the fly sampling approach Remote sensing Plant stress Plant cover changes over time Dendrochemistry approaches 42

43 Green Roof Benefits Water and Heat Island 43

44 What can trees tell us? How? 44

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