PS 26 Playground - Soil Analysis
Analytical Chemistry of Pollutants
Dr. 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 Successive Nitric Acid Additions and
RefluxReflux• 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 The absorbance increase from the added standard will also change by the same standard will also change by the same proportional amount since the concentration of proportional amount since the concentration of interferent is the same in each solution.interferent is the same in each solution.
T
xxadd
T
xx
T
ss V
VbCbC
V
VbC
V
VbCA
Determination of Determination of ConcentrationConcentration
T
xxadd V
VbCbbmbmCA ;
x
Tx
T
xx
V
V
m
bC
V
VbC
b
b
m
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
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
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 Concentration of lead in the park was below action levelwas below 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