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Transcript of Andre Hauser - kisr
Near-Infrared (NIR) Spectroscopy as a Rapid Monitoring Tool for Total Petroleum Hydrocarbon (TPH) as Environmental Hazard in
Contaminated Soils and Sediments
byAndre’ Hauser*, Fatima Ali and Bashayer Al-Dosari
Central Analytical Laboratory, Kuwait Institute for Scientific Research,
P.O. Box 24885, 13109 Safat, KUWAIT
*Tel.: 00965-4989053E-Mail: [email protected]
3. Remediation of Contaminated Areas- A Challenge
OUTLINE
4. TPH Analysis- Conventional & NIR Technique
1. TPHs-A Short Description
5. Case Study- Testing of Real Field Samples
6. Conventional vs. NIR Analysis- Cost, Efficiency & Throughput Considerations
7. Summary
2. Oil Pollution-A Daily Hazard
TPHsA Short Description
TPHs
TPHs(Total Petroleum Hydrocarbons)
Grease,Lubricants
Refinery Products
Weathered Oil
Transposition Fuel
Crude Oil
TPHsA Short Description
TPHs consisting mainly of C and H and to a much lesser extend of S, N, O and heavy metals (V, Ni)
TPHs is a classes of compounds that does not naturally occur in the environment
TPHsA Short Description
Typical entities are: Saturates,
S
N
aromatics and heterocyclic compounds
TPHsA Short Description
Examples of TPHs
TPHs b.p. /C Aromatics /%
Heavy Metal/ppm
Crude Oil 35 - 700
21 <1,000
Weathered Oil 250 - 700
75 >5,000
Gasoline 35 - 150
20 0
TPHsA Short Description
TPHs differ in their toxicity
The higher the content of polyaromatic hydro- carbons (PAHs) and polar compounds (S,N,O) in TPHs the higher is their water solubility
Entity Unit Value
Benzene mg/L 10
Toluene mg/L 25
Benzo(a)pyrene mg/L 0.01
Nickle mg/L 20
WHO-Guidelines for Drinking Water
TPHsA Short Description
In arid, oil rich countries like Kuwait high risk of taking up air-borne particles covered with TPHs
Some PAHs are extremely carcinogenic
TPHsA Short Description
Source: CA EPA, 1999
PAHs FormulaHealth Risk Value in
µg/(80kg*day)
Benzo[a]pyrene 0.08
Chrysene 0.0008
Dibenzo[a,h]pyrene 0.8
Benz[a]anthracene 0.08
1-Nitropyrene 0.08
Oil (TPH) PollutionA Daily Hazard
Environmental disasters such as:
Oil (TPH) PollutionA Daily Hazard
Environmental pollution by oil industry:
Oil (TPH) PollutionA Daily Hazard
Environmental pollution by negligence:
Remediation of Contaminated Soil A Challenging Task
Waste disposal (excavation & transportation) Extraction with organic solvents (excavation & washing) Bio-remediation (excavation & mixing with bacteria) Agro-remediation (in situ treatment)
Remediation of Contaminated Soil Tasks for Analytical Chemistry
Screening of large areas for TPH-contamination Assessment of the extent of TPH-contamination Monitoring of clean up process
Determination of end point of clean up process
Remediation of Contaminated Soil A Challenge for Analytical Chemistry
High number of samples
High throughput required
No or low waste disposal per sample
Accuracy as good as needed Low cost per sample
TPH AnalysisConventional Method vs. NIR Spectroscopy
Feature Conventional Method
NIR Spectroscopy
Certification EPA, ASTM No
Sample Preparation Solvent Extraction No
Extract Treatment Silica Gel No
Calibration Yes Yes
Detection Device IR NIR
Detection Limit ppm %
Waste Perhalogenated Solvent
No
Drying Homogeniz Weighing Loading the Soxhlet-extractor
TPH AnalysisConventional Method
Adding of 100ml CCl4/Freon/S-316 (Chlorotrifluoroethylene) Extracting at a rate of about 20 cycles per hour for eight hours
TPH AnalysisConventional Method
Sample
Solvent
Shaker/Ultra Sonic Bath Extraction
Shaking or sonicating for four hours at RT/300 C.
TPH AnalysisConventional Method
Sample +Solvent +Silica Gel
Dilution
Filteration
Sample treatment with silica gel for 5 min
TPH AnalysisConventional Method
TPH AnalysisConventional Method
Calibration
IR-Measurement
0 1 2 3 4 50
1
2
3
4TPH/IR-Calibration
TPH Conc.
IR-R
esp
on
ds
NIR is a spectroscopic technique that uses infrared (IR) light diffuse scattered on the sample surface (DRIFT) to quantify the analyte (TPHs) in a matrix (soil).
Light Source Detector
TPH AnalysisNIR Spectroscopy
While the IR-light interacts with the sample it leaves its fingerprint on the detected light
Sample
Light Source Detector
TPH AnalysisNIR Spectroscopy
NIR measures the amount of light absorbed by a sample vs. the wavelength of the IR-light.
3700
4200
4700
5200
5700
6200
100000000
200000000
300000000
400000000
500000000
600000000
NIR-Fingerprints
Clean SoilContaminated Soil
Wave Length/cm-1
NIR
-Resp
onds
TPH-Signals
TPH AnalysisNIR Spectroscopy
NIR-Spectroscopy is
• Non-destructive
• Without sample preparation
• Uses DRIFT-technique
TPH AnalysisNIR Spectroscopy
• Needs calibration
Sample
NIR-spectrometer MPATM
from BRUKER
• No waste
Calibration• NIR predicts TPH-concentration using spectra from similar samples (Reference Value) with known TPH- concentration
TPH AnalysisNIR Spectroscopy
• Calibration equations are found by chemometric
methods such as principal component analysis (PCA) and principal component regression (PCR) • Result: Model (equation) were TPH-
concentration is correlated with NIR-spectral features (wavelength, intensity, spectral shape)• QC of the model by cross-validation: Correlation coefficient (R2)≈ 1 Root mean square error (RMSE) ≈ 0.1
• NIR uses calibration equations (Model)
Reference samples ( S =43)
TPH AnalysisNIR Spectroscopy
TPHs Matrix TPH-Con./%
No. of Samples
non Soil (particle size <2mm)
Blank 4
Gasoline Soil (particle size
<2mm)002 – 0.51 6
Jet Fuel Soil (particle size
<2mm)0.04 – 1.43 6
Kerosin Soil (particle size
<2mm)0.04 – 1.33 6
Diesel Soil (particle size
<2mm)0.05 -1.88 6
Crude Oil Soil (particle size
<2mm)0.02 – 1.36 7
Atmospheric Residue (I)
Soil (particle size
<2mm)0.5 -1.9 3
Atmospheric Residue (II)
Soil (particle size
<2mm)0.39 – 2.19 4
Weathered Oil
Soil (particle size <2mm)
2.08 1
Cross validation of the model (PCA-Equation)
TPH AnalysisNIR Spectroscopy
Cross validation result: R2 = 0.9415; RMSE = 0.158
Case StudyTesting of Real Field Samples
Matrix TPH-Contaminant
Kuwait Soil (north) Crude Oil
Kuwait Soil (north) Weathered Oil
Sediment Atmospheric Residue (II)
Ottawa Sand(certified) Atmospheric Residue (II)
US sand (certified) Atmospheric Residue (I)
Field samples ( S =24)
Case StudyTesting of Real Field Samples
Field samples were analyzed by conventional (certified) and NIR technique
Data from conventional technique were considered as true
Comparison between data from both technique
Case StudyTesting of Real Field Samples
Comparison of data from all field samples
Matrix TPH-Contamination
Kuwait Soil (north) Crude Oil
Kuwait Soil (north) Weathered Oil
Sediment Atmospheric Residue (II)
Ottawa Sand(certified)
Atmospheric Residue (II)
US sand (certified) Atmospheric Residue (I)
0 1 2 3 4 5 60
5
10
15
20
25
30
35
40
45
R² = 0.362316798189909
Conventional vs. NIR Technique
Conv. Technique (TPH in %)
NIR
Tech
niq
ue (
TP
H i
n %
)
Case StudyTesting of Real Field Samples
Comparison of data from Kuwait Soil (north) samples
Matrix TPH-Contamination
Kuwait Soil (north) Crude Oil
Kuwait Soil (north) Weathered Oil
Sediment Atmospheric Residue (II)
Ottawa Sand(certified)
Atmospheric Residue (II)
US sand (certified) Atmospheric Residue (I)
0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.50
2
4
6
8
10
12
R² = 0.850444628094841
Conventional vs. NIR Technique
Conv. Technique (TPH in %)
NIR
Tech
niq
ue (
TP
H i
n %
)
Case StudyTesting of Real Field Samples
0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.50
2
4
6
8
10
12
R² = 0.917870654566115
Conventional vs. NIR Technique
Conv. Technique (TPH in %)
NIR
Tech
niq
ue (
TP
H i
n %
)
Comparison of data from Kuwait Soil (north) samples contaminated by weathered oil
Matrix TPH-Contamination
Kuwait Soil (north) Crude Oil
Kuwait Soil (north) Weathered Oil
Sediment Atmospheric Residue (II)
Ottawa Sand(certified)
Atmospheric Residue (II)
US sand (certified) Atmospheric Residue (I)
Case StudyTesting of Real Field Samples
Comparison of data from sediment samples contaminated by atmospheric residue
Matrix TPH-Contamination
Kuwait Soil (north) Crude Oil
Kuwait Soil (north) Weathered Oil
Sediment Atmospheric Residue (II)
Ottawa Sand(certified)
Atmospheric Residue (II)
US sand (certified) Atmospheric Residue (I)
0.5 1 1.5 2 2.5 3 3.5 4 4.50
1
2
3
4
5
6
7
8
R² = 0.998695063772374
Conventional vs. NIR Technique
Conv. Technique (TPH in %)
NIR
Tech
niq
ue (
TP
H i
n %
)
Case StudyTesting of Real Field Samples
Comparison of data from certified soil samples contaminated by atmospheric residue
Matrix TPH-Contamination
Kuwait Soil (north) Crude Oil
Kuwait Soil (north) Weathered Oil
Sediment Atmospheric Residue (II)
Ottawa Sand(certified)
Atmospheric Residue (II)
US sand (certified) Atmospheric Residue (I) 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
0
5
10
15
20
25
30
35
40
45
R² = 0.955223590954123
Conventional vs. NIR Technique
Conv. Technique (TPH in %)
NIR
Tech
niq
ue (
TP
H i
n %
)
Conventional vs. NIR AnalysisCost, Efficiency & Throughput Considerations
Feature TechniqueConventional NIR
Capital Cost ~12,000 KD ~20,000 KD
Cost/Sample (Consumable)
~5-6 KD <0.250 KD
Time/Sample ~2 h 5 min
Calibration rather fast time consuming
Waste Disposal/Sample
>100 ml non
Accuracy high medium
Detection Limit 1 ppm 0.5%
Summary
TPHs in the environment pose a potential health risk to humans and destroy the nature
Total petroleum hydrocarbons (TPHs) are a mix of petroleum based chemicals that do not exist naturally in the environment
TPH-contaminated areas need to be identified, their health risk assessed and cleaned up
TPH-quantification is inevitable for hazard evaluation and clean-up activities
Conventional technique is time consuming, costly and harmful to the environment
Conventional technique for TPH-quantification are regulated by EPA & ASTM
Near infrared (NIR) spectroscopy can replace conventional technique
Summary Advantages of NIR: Environmentally friendly, fast and cost effective
NIR is the method of choice for monitoring soil clean-up:
Disadvantages of NIR: Large-scale calibration needed, high detection limit (%) and medium accuracy
• TPHs in %-range
• Large number of samples
• Trend monitoring
• End point determination
Thank You!
Q & A
Research Specialist: Dr. Andre’ Hauser Tel.: 24989053; [email protected] Specialist/Section Head: Dr. Fatima Ali Tel.: 24989050; e-Mail: [email protected] Ms. Bashayer Al-Dosery
Contacts