Chemical Elements (the Periodic “The highest form of human intelligence is the ability to Table) and those essential for life observe without judging” Krishnamurti Of the 103 elements in the Periodic Table, only “The intuitive mind is a sacred gift and the rational mind is 24 are required by organisms a faithful servant. We have created a society that honors the servant and has forgotten the gift” Albert Einstein Macronutrients: Required in large “The mind is everything, amount (“Big Six”: C, N, P, S, O, H) what you think you become” Buddha Micronutrients: small or moderate amount Required elt Required for some life forms Toxic elt

Chemical Elements - Essential for life Chemical Elements - Essential for life Carbon Nitrogen

Carbon forms three-dimensional molecules of large size and Nitrogen (along with carbon) is the essential complexity in organic (carbon-containing) compounds that element that allows formation of amino acids ( form large molecules (amino acids, sugars, enzymes, DNA), proteins) and DNA. and other chemicals vital to life on Earth. Proteins contain up to 16% N Chemical Elements - Essential for life Chemical Elements - Essential for life Phosphorus Carbon:Nitrogen:Phosphorus Ratios

Phosphorus is the “energy element” occurring in Organisms actively concentrate certain elements compounds called ATP and ADP important for energy essential for life: Algae concentrate Iron (Fe) 100,000 transfer processes and DNA. times vs. its concentration in the Ocean • Most organisms keep a rather constant chemical composition Algae and plankton C:N:P ratio of 106:16:1 (Redfield Ratio) Soil microbes maintain a relatively constant proportion of nutrients in their biomass (and at higher levels than the OM they decompose)

Chemical Elements - Essential for life Molecular (bio)markers • Availability of some elements (particularly N & P) is often limited and the supply of these elements may control the rate Source/Process Molecular Markers Example Complementary (or type) of primary production in terrestrial ecosystems. Isotope Proxies • External sources of nutrients are varied and depend of Vascular Plants Lignins/Tannins !13C - (!15N - !14C) nutrient Annual circulation dominates most inputs of limiting Waxes-Cellulose elements (N, P, K) Phytoplankton Lipids-Aliphat. !13C - !15N Pigments Lipids-Aliphat. Microbes Aminosugars !13C - !15N

Diagenesis Amino acids !15N - !34S (Soils-Sedts) Aromatic Carbox. Ac. Thermal Lipids-Aliphat. !13C - (!15N - !34S) Maturation Hopanes-PAHs Combustion PAH, anhydro-sugars !13C - !14C Carbox. Acids (!15N - !34S) Characterization of TOM using Lignin as a biomarker Lignin as a Biomarker Why? Its presence in the aquatic systems ! TOM Macromolecule: Part of Lignocellulosic complexes How? Oxidative cleavage of 3-D polymer exclusive to vascular plants (“nature's cement”) into 4 types of monomers which retain structural information Multifunctionality: Support, Defense, Impermeability

Cinnamyls (C) Syringyls (S) p-hydroxyls (P) Vanillyls (V)

Lignin as a Biomarker Using the right endmembers!

30% Anthr.

70% Anthr.

Up to 15% of industrial effluents buried in estuarine sediments – 100 103 T (1980-92) What is Black Carbon (BC)? From aquatic geochemistry to soil/atmospheric chemistry BC Ring Trial: Comparative analysis of reference materials

BC and matrices containing pyrogenic material: NIST SRMs ! Aerosols (UD), Water way sediment (WWS), Diesel particulate matter (DPM) and bituminous coal (CB); Soils (CSRIO); Chars (U. of Zurich); Soot (U of Denver); Interferences: NOM (IHSS); Shale (USGS); H/C Ratio 1.3 1.0 0.8 0.6 0.3 0.0 Coals (Argonne) Masiello (2004) Marine Chemistry. Vol. 92; Hammes et al. (2007) Global Biogechemistry. Vol. 21 Chemically heterogeneous, biologically refractory class of carbon compounds produced during biomass burning and fossil fuel combustion ! Charcoal: Remains of solid fuel phase (retain structural character) ! Soot: Condensation of hydrocarbon radicals from gas phase into submicron particles (usually nucleated - onion structure)

How extensive is an airshed? a) Since we are dealing with ultra-fine particles ! we are bound to see some wide geographical distribution

Why Study Black Carbon?

! Radiatively important aerosols (direct and indirect impacts) ! “Short-circuit” in the carbon cycle?

!Atmospheric chemistry and health impact (PM , PAHs, BC, VOCs) (PM2.5-10, PAHs, BC, VOCs) Hadley et al. (2007) J. Geophys. Res. Vol. 112. ! Prescribed fires and wildfires contribute 20% of the PM emissions in the U.S. 2.5 North American emissions of BC: 41.5 G/Month Cooney, C. (2008) ES&T. Vol. 42( 5). Input transport: 32 G/Month (75% originates from Asia!) How extensive is an airshed? BC inputs to urban systems: b) Since we are dealing with particles ! we are bound to have some geographical heterogeneity The legacy of geography

Are some urban systems are “underserved” by their geography?

Los Angeles

Mexico City

Malm et al. (2004) J. Geophys. Res. Vol. 109.

Molecular markers of biomass combustion What about more “open” urban airsheds? Levoglucosan: Pyrogenic derivative of cellulose combustion

Houston

New York Central American Smoke Event (May 1998) Fraser, M.P. and Laksmanan K. Fraser, M.P. and Laksmanan K. Elias et al. (2001) Geochim. Cosmochim. Acta. Vol. 65(2) (2000). Env. Sci. & Technol. Vol. 34. Fraser, M.P. and Laksmanan K. (2000). Using Levoglucosan as a Molecular Marker Intercomparison for the Long-Range Transport of Biomass Combustion Aerosols. ES&T. Vol. 34. Washington D.C. Urban Dust

(n = 11) (n = 2)

Wetlands as “memory” of environmental change Piermont Tidal Wetland

The influence of biomass combustion on paleoproxies (charcoal fluxes)

! Important component in the carbon cycle? Carbon stocks (up to 10% of terrestrial SOC storage!) in <0.5% of the surface ! Memory of coastal systems

Pederson, Peteet, Guiderson, and Kurdyla (2004). Environment during the Last Millenium in the Lower Hudson Valley, NY - Medieval Warming, Little Ice Age, and European Impact. Quat. Res. Pederson, et al. (2004). Quaternary Research. Piermont Tidal Wetland Levoglucosan “Yields”: Thermal dependence

2500.0

2000.0 Cordgrass char Loblolly Pine char Honey Mesquite char

1500.0 (ug/goc)

1000.0 Levoglucosan

500.0

0.0 0 100 200 300 400 500 600 700 800 900 Combustion temperature (degree C)

Kuo, Herbert, Louchouarn. (2008b-in review) Org. Geochem.

Molecular markers of biomass combustion Internal Standards in GLC Levoglucosan: Pyrogenic derivative of cellulose combustion • An internal standard (IS) is a substance which is similar in the chemical behavior (chemical structure - polarity) and analytical response to a certain target analyte. • A defined volume of the IS solution is added to both the sample and calibration solutions such that they both contain an identical concentration. • When the sample and the calibration solutions are analyzed, the peaks for both the IS and the target analyte are integrated. • The area of the analyte peak is divided by the area of the internal standard peak to produce a peak area ratio Kuo et al. (2008b-submitted) Org. Geochem. (PAR) value. Internal Standards in GLC Internal Standard Quantification • This method corrects for run-to-run-variation in extraction efficiency and chromatographic response. IS • The use of an IS eliminates all injection volume related IS sources of error and leads to an improvement of method precision and is a powerful tool to monitor the sample preparation. • The IS must not overlap with the sample peak and may elute near before or after the peak of interest. • To convert the peak areas to mass of analyte, the peak areas must be calibrated. • The two main strategies are based on repeated one- The relative response factor (RRF) is: points standard calibration and multiple-points

calibration curves. Amtx AreaIS RRFStd = x Areax Std AmtIS Std

! Internal Standard Quantification Internal Standard Quantification The relative response factor (RRF) is:

IS IS RRFSpl = RRFStd

Amt Area Amt Area x x IS = x x IS Areax Spl AmtIS Spl Areax Std AmtIS Std ! Amt Amt = Area x IS xRRF The relative response factor (RRF) is: x Spl x Spl Area Std ! IS Spl Amtx AreaIS RRFStd = x Areax Std AmtIS Std

! ! Methods Internal Standard Quantification Molecular markers of biomass combustion Levoglucosan: Pyrogenic derivative of cellulose combustion

Solvent extraction ! sonication (DCM:MeOH - 3x10 min) Analysis: GC/MS (phenols - organic acids - sugars)

Amtx AreaIS The relative response factor (RRF) is: RRFStd = x Areax Std AmtIS Std

!

Internal Standard Quantification Multiple-points IS Quantification Amt Area RRF = x ÷ x Keeping the [IS]std constant: Std AmtIS Std AreaIS Std

! Multiple-points IS Quantification Multiple-points IS Quantification Amt Area Amt Area x x x x Keeping the [IS] constant: RRFStd = ÷ RRFStd = ÷ std Amt Area Keeping the [IS]std constant: IS Std IS Std std AmtIS Std AreaIS Std

! !

Multiple-points IS Quantification Amt Area RRF = x ÷ x Keeping the [IS]std constant: Std AmtIS Std AreaIS Std

!