““The highest form of human intelligence is the ability toThe highest form of human intelligence is the ability to

observe without judgingobserve without judging””

KrishnamurtiKrishnamurti

““The intuitive mind is a sacred gift and the rational mind isThe intuitive mind is a sacred gift and the rational mind is

a faithful servant. We have created a society that honorsa faithful servant. We have created a society that honors

the servant and has forgotten the giftthe servant and has forgotten the gift””

Albert EinsteinAlbert Einstein

““The mind is everything,The mind is everything,

what you think you becomewhat you think you become””

BuddhaBuddha

Chemical Elements (the PeriodicTable) and those essential for life

Of the 103 elements inthe Periodic Table, only24 are required byorganisms

Required elt Required for some life formsToxic elt

Macronutrients:Macronutrients:Required in largeRequired in largeamountamount ((““Big SixBig Six””: C,: C,N, P, S, O, H)N, P, S, O, H)

Micronutrients: smallMicronutrients: smallor moderate amountor moderate amount

Chemical Elements - Essential for lifeCarbon

Carbon forms three-dimensional molecules of large size andcomplexity in organic (carbon-containing) compounds thatform large molecules (amino acids, sugars, enzymes, DNA),and other chemicals vital to life on Earth.

Chemical Elements - Essential for lifeNitrogen

Nitrogen (along with carbon) is the essentialelement that allows formation of amino acids ( proteins) and DNA.

Proteins contain up to16% N

Chemical Elements - Essential for lifePhosphorus

Phosphorus is the Phosphorus is the ““energy elementenergy element”” occurring in occurring incompounds called ATP and ADP important for energycompounds called ATP and ADP important for energytransfer processes and DNA.transfer processes and DNA.

Chemical Elements - Essential for life

Carbon:Nitrogen:Phosphorus Ratios

Organisms actively concentrate certain elementsessential for life: Algae concentrate Iron (Fe) 100,000times vs. its concentration in the Ocean

• Most organisms keep a ratherconstant chemical composition

Algae and plankton C:N:Pratio of 106:16:1 (RedfieldRatio)

Soil microbes maintain arelatively constant proportion ofnutrients in their biomass (andat higher levels than the OMthey decompose)

Chemical Elements - Essential for life

• Availability of some elements (particularly N & P) is oftenlimited and the supply of these elements may control the rate(or type) of primary production in terrestrial ecosystems.

• External sources of nutrients are varied and depend ofnutrient Annual circulation dominates most inputs of limitingelements (N, P, K)

Molecular (bio)markersMolecular (bio)markers

!13C - !14C

(!15N - !34S)

PAH, anhydro-sugars

Carbox. Acids

Combustion

!13C - (!15N - !34S)Lipids-Aliphat.

Hopanes-PAHs

Thermal

Maturation

!15N - !34SAmino acids

Aromatic Carbox. Ac.

Diagenesis

(Soils-Sedts)

!13C - !15N

Lipids-Aliphat.

AminosugarsMicrobes

!13C - !15NLipids-Aliphat.

Pigments

Phytoplankton

!13C - (!15N - !14C)Lignins/Tannins

Waxes-Cellulose

Vascular Plants

Complementary

Isotope Proxies

ExampleMolecular MarkersSource/Process

Characterization of TOMCharacterization of TOMusing Lignin as a biomarkerusing Lignin as a biomarker

Macromolecule: Part of Lignocellulosic complexesMacromolecule: Part of Lignocellulosic complexes

exclusiveexclusive to vascular plants ( to vascular plants (““nature's cementnature's cement””))

Multifunctionality: Support, Defense, ImpermeabilityMultifunctionality: Support, Defense, Impermeability

How?How? Oxidative cleavage of 3-D polymer Oxidative cleavage of 3-D polymer

into 4 types of monomers which retain structural informationinto 4 types of monomers which retain structural information

Cinnamyls (C)Cinnamyls (C)

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

Lignin as a BiomarkerLignin as a BiomarkerWhy?Why? Its presence in the aquatic systems Its presence in the aquatic systems !! TOMTOM

Lignin as a BiomarkerLignin as a Biomarker Using the right endmembers! Using the right endmembers!

70% Anthr.

30% Anthr.

Up to 15% of industrial effluents buried inUp to 15% of industrial effluents buried in

estuarine sediments estuarine sediments –– 100 10 100 1033 T (1980-92) T (1980-92)

BC and matrices containing BC and matrices containing pyrogenic pyrogenic materialmaterial: NIST : NIST SRMs SRMs !!

Aerosols (UD), Water way sediment (WWS), Diesel particulateAerosols (UD), Water way sediment (WWS), Diesel particulate

matter (DPM) and bituminous coal (CB); Soils (CSRIO); Charsmatter (DPM) and bituminous coal (CB); Soils (CSRIO); Chars

(U. of Zurich); Soot (U of Denver);(U. of Zurich); Soot (U of Denver);

InterferencesInterferences: NOM: NOM

(IHSS); Shale (USGS);(IHSS); Shale (USGS);

Coals (Argonne)Coals (Argonne)

From aquatic geochemistry to soil/atmospheric chemistry From aquatic geochemistry to soil/atmospheric chemistry

BC BC Ring Trial: Ring Trial: Comparative analysis of reference materialsComparative analysis of reference materials

What is Black Carbon (BC)?What is Black Carbon (BC)?

Masiello Masiello (2004) (2004) Marine ChemistryMarine Chemistry.. Vol Vol. 92; Hammes et al. (2007) . 92; Hammes et al. (2007) Global Global BiogechemistryBiogechemistry.. Vol Vol. 21. 21

H/C Ratio 1.3 1.0 0.8 0.6 0.3 0.0

Chemically heterogeneous, biologically refractory class of carbon compoundsChemically heterogeneous, biologically refractory class of carbon compounds

produced during biomass burning and fossil fuel combustionproduced during biomass burning and fossil fuel combustion

!! CharcoalCharcoal: Remains of solid fuel phase (retain structural character): Remains of solid fuel phase (retain structural character)

!! SootSoot: Condensation of hydrocarbon radicals from gas phase into: Condensation of hydrocarbon radicals from gas phase into

submicron particles (usually nucleated - onion structure)submicron particles (usually nucleated - onion structure)

!!Atmospheric chemistry and health impactAtmospheric chemistry and health impact

(PM(PM2.5-102.5-10, , PAHsPAHs, BC, , BC, VOCsVOCs))

!! Prescribed fires and wildfires contributePrescribed fires and wildfires contribute 20%20%

of the PMof the PM2.52.5 emissions in the U.S. emissions in the U.S.

!! Radiatively Radiatively important aerosols (direct and indirect impacts)important aerosols (direct and indirect impacts)

!! ““ShortShort-circuit-circuit”” in the carbon cycle? in the carbon cycle?

Why Study Black Carbon?

Cooney, C. (2008) ES&T.Cooney, C. (2008) ES&T. Vol Vol. 42( 5).. 42( 5).

How extensive is an How extensive is an airshedairshed??a)a) Since we are dealing with ultra-fine particles Since we are dealing with ultra-fine particles !! we are bound to we are bound to

see some wide geographical see some wide geographical distributiondistribution

Hadley et al. (2007) J. Hadley et al. (2007) J. GeophysGeophys. . ResRes. . VolVol. 112.. 112.

North American emissions of BC: 41.5 G/MonthNorth American emissions of BC: 41.5 G/Month

Input transport: Input transport: 32 G/Month (75% originates from Asia!)32 G/Month (75% originates from Asia!)

How extensive is an How extensive is an airshedairshed??

b)b) Since we are dealing with particles Since we are dealing with particles !! we are bound to have we are bound to have

some geographical heterogeneitysome geographical heterogeneity

Malm Malm et al. (2004) J. et al. (2004) J. GeophysGeophys. . ResRes. . VolVol. 109.. 109.

BC inputs to urban systems:The legacy of geography

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

Mexico CityMexico City

Los AngelesLos Angeles

HoustonHouston

New YorkNew York

What about more What about more ““openopen”” urban urban airshedsairsheds??

Molecular markers of biomass combustionLevoglucosanLevoglucosan: : Pyrogenic Pyrogenic derivative of cellulose combustionderivative of cellulose combustion

Central American Smoke Event (May 1998)

Fraser, M.P. and Fraser, M.P. and Laksmanan Laksmanan K.K.(2000). (2000). EnvEnv. . SciSci. & . & TechnolTechnol. . VolVol. 34.. 34.

Elias et al. (2001) Elias et al. (2001) GeochimGeochim. . CosmochimCosmochim. . ActaActa. . VolVol. 65(2). 65(2)

Fraser, M.P. and Fraser, M.P. and Laksmanan Laksmanan K. (2000).K. (2000).Using Levoglucosan as a Molecular Markerfor the Long-Range Transport of BiomassCombustion Aerosols. . ES&T.ES&T. Vol Vol. 34.. 34.

IntercomparisonWashington D.C. Urban DustWashington D.C. Urban Dust

(n = 11)(n = 11) (n = 2)(n = 2)

Pederson, Pederson, PeteetPeteet, , GuidersonGuiderson, and , and Kurdyla Kurdyla (2004). Environment during the Last (2004). Environment during the Last Millenium Millenium in thein the

Lower Hudson Valley, NY - Medieval Warming, Little Ice Age, and European Impact. Lower Hudson Valley, NY - Medieval Warming, Little Ice Age, and European Impact. Quat. ResQuat. Res..

Wetlands as “memory” of environmental change Piermont Tidal Wetland

The influence of biomassThe influence of biomass

combustion on combustion on paleoproxiespaleoproxies

(charcoal fluxes)(charcoal fluxes)

!! Important component in theImportant component in the

carbon cycle?carbon cycle?

Carbon stocks (up to 10% ofCarbon stocks (up to 10% ofterrestrial SOC storage!) interrestrial SOC storage!) in<0.5% of the surface<0.5% of the surface

!! Memory of Memory of coastal systemscoastal systems

Pederson, et al. (2004). Pederson, et al. (2004). Quaternary ResearchQuaternary Research..

Piermont Tidal Wetland Levoglucosan “Yields”: Thermal dependence

0.0

500.0

1000.0

1500.0

2000.0

2500.0

0 100 200 300 400 500 600 700 800 900

Combustion temperature (degree C)

Levo

gluc

osan

(ug

/goc

)

Cordgrass charLoblolly Pine charHoney Mesquite char

KuoKuo, Herbert, Louchouarn. (2008b-in review) , Herbert, Louchouarn. (2008b-in review) OrgOrg. . GeochemGeochem..

Molecular markers of biomass combustionLevoglucosanLevoglucosan: : Pyrogenic Pyrogenic derivative of cellulose combustionderivative of cellulose combustion

Kuo Kuo et al. (2008b-submitted) et al. (2008b-submitted) OrgOrg. . GeochemGeochem..

Internal Standards in GLCInternal Standards in GLC•• An internal standard (An internal standard (ISIS) is a substance which is similar) is a substance which is similar

in the chemical behavior (chemical structure - polarity)in the chemical behavior (chemical structure - polarity)and analytical response to a certain target analyte.and analytical response to a certain target analyte.

•• A defined volume of the A defined volume of the ISIS solution is added to both the solution is added to both thesample and calibration solutions such that they bothsample and calibration solutions such that they bothcontain an identical concentration.contain an identical concentration.

•• When the sample and the calibration solutions areWhen the sample and the calibration solutions areanalyzed, the peaks for both the analyzed, the peaks for both the ISIS and the target and the targetanalyte are integrated.analyte are integrated.

•• The area of the analyte peak is divided by the area ofThe area of the analyte peak is divided by the area ofthe internal standard peak to produce a peak area ratiothe internal standard peak to produce a peak area ratio(PAR) value.(PAR) value.

Internal Standards in GLCInternal Standards in GLC•• This method corrects for run-to-run-variation inThis method corrects for run-to-run-variation in

extraction efficiency and chromatographic response.extraction efficiency and chromatographic response.•• The use of an The use of an ISIS eliminates all injection volume related eliminates all injection volume related

sources of error and leads to an improvement of methodsources of error and leads to an improvement of methodprecision and is a powerful tool to monitor the sampleprecision and is a powerful tool to monitor the samplepreparation.preparation.

•• The The ISIS must not overlap with the sample peak and may must not overlap with the sample peak and mayelute near before or after the peak of interest.elute near before or after the peak of interest.

•• To convert the peak areas to mass of analyte, the peakTo convert the peak areas to mass of analyte, the peakareas must be calibrated.areas must be calibrated.

•• The two main strategies are based on repeated one-The two main strategies are based on repeated one-points standard calibration and multiple-pointspoints standard calibration and multiple-pointscalibration curves.calibration curves.

Internal Standard QuantificationInternal Standard Quantification

The The relative response factor (RRF)relative response factor (RRF) is: is:

ISIS

!

RRFStd =AmtxAreax Std

x AreaISAmtIS Std

Internal Standard QuantificationInternal Standard Quantification

The The relative response factor (RRF)relative response factor (RRF) is: is:

!

RRFStd =AmtxAreax Std

x AreaISAmtIS Std

IS

IS

Internal Standard QuantificationInternal Standard QuantificationThe The relative response factor (RRF)relative response factor (RRF) is: is:

!

RRFSpl = RRFStd

!

Amtx

Areax Spl

xAreaIS

AmtIS Spl

=Amtx

Areax Std

xAreaIS

AmtIS Std

!

Amtx Spl = Areax Spl xAmtIS

AreaIS Spl

xRRFStd

Solvent extraction Solvent extraction !! sonicationsonication (DCM:MeOH - 3x10 min)(DCM:MeOH - 3x10 min)

Analysis: GC/MS (phenols - organic acids - sugars)Analysis: GC/MS (phenols - organic acids - sugars)

MethodsMethodsMolecular markers of biomass combustionMolecular markers of biomass combustion

LevoglucosanLevoglucosan: Pyrogenic derivative of cellulose combustion: Pyrogenic derivative of cellulose combustion

Internal Standard QuantificationInternal Standard Quantification

The The relative response factor (RRF)relative response factor (RRF) is: is:

!

RRFStd =AmtxAreax Std

x AreaISAmtIS Std

Internal Standard QuantificationInternal Standard Quantification Multiple-points IS QuantificationMultiple-points IS Quantification

Keeping the [IS]Keeping the [IS]stdstd constant: constant:

!

RRFStd =AmtxAmtIS Std

÷AreaxAreaIS Std

Multiple-points IS QuantificationMultiple-points IS Quantification

Keeping the [IS]Keeping the [IS]stdstd constant: constant:

!

RRFStd =AmtxAmtIS Std

÷AreaxAreaIS Std

Multiple-points IS QuantificationMultiple-points IS Quantification

Keeping the [IS]Keeping the [IS]stdstd constant: constant:

!

RRFStd =AmtxAmtIS Std

÷AreaxAreaIS Std

Multiple-points IS QuantificationMultiple-points IS Quantification

Keeping the [IS]Keeping the [IS]stdstd constant: constant:

!

RRFStd =AmtxAmtIS Std

÷AreaxAreaIS Std