PS 26 Playground - Soil Analysis

Analytical Chemistry of PollutantsDr. Joe Gardella

Todd M. Alonzo, Dominic O. Hull, Doris J. Glykys, Ed Tasber, and David G. Twoey

Why Did We Choose PS26?Why Did We Choose PS26? Soil AnalysisSoil Analysis GC/MSGC/MS Elemental Analysis - Why Lead?Elemental Analysis - Why Lead?

• Requested by CommunityRequested by Community• Buffalo ChinaBuffalo China• Very Toxic MetalVery Toxic Metal

Sampling TechniqueSampling Technique Donned Gloves Donned Gloves

and Safety Glassesand Safety Glasses Spade Rinsed with Spade Rinsed with

50/50 v/v Nitric 50/50 v/v Nitric Acid/DI WaterAcid/DI Water

Dig Hole and Dig Hole and Obtain sample at Obtain sample at 6” Depth6” Depth

Refill HoleRefill Hole

JarsJars• Amber to Avoid Amber to Avoid

PhotolysisPhotolysis• No Head Space No Head Space

Above SampleAbove Sample• Sealed with FoilSealed with Foil• Cooled on Dry IceCooled on Dry Ice

Sampling Sites

Synthetic Organic Compounds

Lead

Harrison St. (Dead End)

Sampling Sites

Synthetic Organic Compounds

Lead

Harrison St. (Dead End)

Sampling Sites

Synthetic Organic Compounds

Lead

Harrison St. (Dead End)

Sampling Sites

Synthetic Organic Compounds

Lead

Harrison St. (Dead End)

Sampling Sites

Synthetic Organic Compounds

Lead

Harrison St. (Dead End)

Sampling Sites

Synthetic Organic Compounds

Lead

Harrison St. (Dead End)

Sampling Sites

Synthetic Organic Compounds

Lead

Harrison St. (Dead End)

Sampling Sites

Synthetic Organic Compounds

Lead

Harrison St. (Dead End)

Elemental AnalysisElemental Analysis DigestionDigestion Flame Atomic Absorption Flame Atomic Absorption

SpectroscopySpectroscopy Inductively Coupled Plasma / Inductively Coupled Plasma /

Atomic Emission Atomic Emission Spectroscopy Spectroscopy

Standard AdditionStandard Addition ResultsResults

DigestionDigestion EPA Method 3050 EPA Method 3050

• Successive Nitric Acid Additions and RefluxSuccessive Nitric Acid Additions and Reflux• Reduce VolumeReduce Volume• Peroxide NeutralizationPeroxide Neutralization• Reduce VolumeReduce Volume

– GFAA and ICP/MSGFAA and ICP/MS• Addition of HCl AcidAddition of HCl Acid

– FLAA and ICP/AESFLAA and ICP/AES

Direct Aspiration Atomic Direct Aspiration Atomic Absorption Spectroscopy Absorption Spectroscopy (FLAA)(FLAA)

A sample is aspirated and atomized in a flame.A sample is aspirated and atomized in a flame.

A characteristic light beam is directed through A characteristic light beam is directed through the flame into a monochromator, and onto a the flame into a monochromator, and onto a detector that measures the amount of detector that measures the amount of absorbed light.absorbed light.

Absorption depends upon the presence of free Absorption depends upon the presence of free unexcited ground-state atoms in the flame.unexcited ground-state atoms in the flame.

»Beer-Lambert LawBeer-Lambert Law

Standard AdditionStandard Addition The preparation of standards that match the The preparation of standards that match the

samples is often impossible or extremely difficult.samples is often impossible or extremely difficult.

Accurate determinations are possible by making Accurate determinations are possible by making the concentration calibration in the presence of the concentration calibration in the presence of the matrix.the matrix.

By adding aliquots of a standard to portions of the By adding aliquots of a standard to portions of the sample, any interferent present in the sample will sample, any interferent present in the sample will affect the standard and sample absorbance affect the standard and sample absorbance similarly.similarly.

If Interferences are If Interferences are present: present:

The number of ground state atoms producing The number of ground state atoms producing atomic absorption will be affected. atomic absorption will be affected.

The absorbance increase from the added standard The absorbance increase from the added standard will also change by the same proportional amount will also change by the same proportional amount since the concentration of interferent is the same since the concentration of interferent is the same in each solution.in each solution.

T

xxadd

T

xx

T

ss V

VbCbCVVbC

VVbCA

Determination of Determination of ConcentrationConcentration

T

xxadd VVbCbbmbmCA ;

x

Tx

T

xx

VV

mbC

VVbC

bbm

Comparison of Lead Comparison of Lead ResultsResults

0

400

E & E, Inc. Joe's Class

Synthetic Organic AnalysisSynthetic Organic Analysis DigestionDigestion Volume ReductionVolume Reduction GC-MS AnalysisGC-MS Analysis Qualitative AnalysisQualitative Analysis Quantitative AnalysisQuantitative Analysis

DigestionDigestion EPA Method 3550EPA Method 3550

– Addition of NaSOAddition of NaSO44

– Successive Addition of 50/50 v/v Successive Addition of 50/50 v/v Methylene Chloride/Acetone with Methylene Chloride/Acetone with Ultrasonic ExtractionUltrasonic Extraction

– Vacuum FiltrationVacuum Filtration– Reduce Volume Reduce Volume

GC-MS AnalysisGC-MS Analysis Separation of ComponentsSeparation of Components

– Using Capillary ColumnUsing Capillary Column– by Molecular Weightby Molecular Weight

Mass AnalysisMass Analysis– Fragmentation of CompoundsFragmentation of Compounds– Mass Separation by Mass-Charge RatioMass Separation by Mass-Charge Ratio

Qualitative ResultsQualitative Results AcenaphtheneAcenaphthene AnthraceneAnthracene Bis(2-ethylhexyl)Bis(2-ethylhexyl)

PhthalatePhthalate DibenzofuranDibenzofuran FlurantheneFluranthene FluoreneFluorene

2-Methyl-2-Methyl-NaphthaleneNaphthalene

NaphthaleneNaphthalene PyrenePyrene 4-Fluoro-1,1’-4-Fluoro-1,1’-

BiphenylBiphenyl 1,2-Dihydro-1,2-Dihydro-

AcenaphthyleneAcenaphthylene

Quantitative AnalysisQuantitative Analysis

Play Area

Basketball Court

Bleachers

Dead End

0.000.050.100.150.200.250.300.350.40

ppb

4-Fluoro-1,1'-Biphenyl Fluoranthene 1,2-Dihydro-Acenaphthylene

ConclusionsConclusions Lead and PAHs were detected in the Lead and PAHs were detected in the

soilsoil Concentration of lead in the park was Concentration of lead in the park was

below action levelbelow action level Concentration of lead at the dead Concentration of lead at the dead

end was above 400 ppm levelend was above 400 ppm level Many of the PAHs detected could Many of the PAHs detected could

not be quantifiednot be quantified