An IR-Based Rapid Field Analytical Method for TPH Measurement- Field Deployment and Performance Evaluation

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An IR-Based Rapid Field Analytical Method for TPH Measurement- Field Deployment and Performance Evaluation Deyuan Kong and Sara Mcmillen, Chevron Energy Technology Company USA Timothy Vidra, Yohanes Kurniawan, Sarah Chitra, Dicky Saputra and Dion Kumboro PT. Chevron Pacific Indonesia

Opportunity Project Background Soil samples from hydrocarbon impacted soil in Exploration and Production operations need to be tested for Total Petroleum Hydrocarbon (TPH) Delays in sample analyses and decision making due to large # of soil samples per week needing analysis Lab analysis can take 2-4 weeks Approach Development of rapid TPH analytical method to increase accuracy and efficiency 1) real-time remediation process monitoring 2) reducing the number of samples going to lab 2

Handheld IR Instrument for non-destructive TPH measurement Portable handheld IR instrument Diffuse reflectance of IR light reflected from the sample The world s first handheld instrument for the direct measurement of TPH in soil User simply pulls the trigger for a 15 second reading of TPH (C 10 -C 36 ) in mg/kg IR light is emitted Interacts with the surface of the sample Light is diffusely reflected back to detector IR spectrum (readout) is produced 3

Field Pilot Approach Collect field Soil Samples Load the Calibration Model on to Instrument Potential Field Deployment Process samples (split) Reference Lab GC-FID IR analysis Build Model Using Partial Least Square Method Predict TPH values and validation tests completed with blind samples 4

Handheld IR Instrument Predicted TPH Concentration (mg/kg) Pilot Studies Results Evaluation- A Field Calibration model completed with 111 soil samples from A field at TPH range 0-120,000 mg/kg 20,000 Handheld IR Instrument vs Laboratory TPH (C 10 - C 36 ) Concentrations Using calibration model A vs. GCFID Data for validation Test Validation Samples ( )& Calibration Samples ( ) 15,000 10,000 Outliner analysis- spectrum suggests the high clay contents of those samples 5,000 Detection limit of this model- 170 mg/kg 0 0 5,000 10,000 15,000 20,000 Laboratory TPH Concentration (mg/kg) 5

Handheld IR Instrument Predicted TPH Concentration (mg/kg) Pilots Studies Results Evaluation- B Field 60,000 Handheld IR instrument vs Laboratory TPH (C 10 - C 36 ) Concentrations 50,000 40,000 Calibration model completed with 200 soil samples from B field at TPH range 0-50,000 mg/kg 30,000 20,000 Using calibration model B vs. GCFID Data for validation Test Validation Samples ( )& Calibration Samples ( ) 10,000 Detection limit of this model- 380 mg/kg 0 0 10,000 20,000 30,000 40,000 50,000 60,000 Laboratory TPH Concentration (mg/kg) 6

Accuracy for various assay ranges for calibration samples for soils in two different oil fields (A & B) A field (wide range of calibration up to 12%) Assay Ranges (mg/kg TPH) RMSECV mg/kg TPH Correlation Coefficient s (r 2 ) 0-3,000 170 0.92 3,000-5,000 184 0.96 5,000-15,000 410 0.98 15,000-30,000 803 0.99 30,000-120,000 2,375 0.99 B field (limited calibration up to 5%) Assay Range (mg/kg TPH) RMSEC V (mg/kg TPH) Relative Standard Deviation * (%) 0-5,000 376 n/a 5,000 15,000 930 19 15,000 20,000 1,390 9 20,000 30,000 2,107 11 30,000 50,000 2,815 9 RMSECV: Root-mean-square Error of Cross-Validation 7

Field Application- For existing Soil Stockpiles RemScan works best when the soil is dry & sample is measured directly on site 8

Field Application- What we can do to meet the 5% free moisture in the soil sample? if the soil is wet, measurement can be done after drying the sample. Or Press the soil sample into the drying tray and use the drying box to dry the sample in 30 minutes/36 samples Samples put in drying in the morning can be measured for TPH in the afternoon 9

Field Application How RemScan used in different operational settings Other scenario: when the sample is wet, measurement can be done after drying the sample. Measurement at office Collection of samples from multiple sites For samples that need longer drying time RemScan is not readily available on site Result comes out the next day 10

Handheld IR Predicted TPH Concentration (mg/kg) Handheld IR Predicted TPH Concentration (mg/kg) Field Deployment Model Performance Check 3-5 RemScan Units had been deployed for field TPH measurements Monthly split sampling program has been established to monitor the accuracy. 70% of the handheld IR measured data are within +/- 30% of Lab GCFID results Handheld IR vs Laboratory TPH Concentration - A 50,000 Handheld IR vs Laboratory TPH Concentrations B 50,000 40,000 40,000 30,000 30,000 20,000 20,000 10,000 10,000 0 0 10,000 20,000 30,000 40,000 50,000 0 0 10,000 20,000 30,000 40,000 50,000 Laboratory TPH Concentration (mg/kg) Laboratory TPH Concentration (mg/kg) 11

Data Check- Precision Evaluation Precision evaluation Sample was homogenized and divided into 5 sub-samples. Each sub-samples then measured 3 times. Test with RemScan using the same sample to check it s precision and repeatability. Sample ID Coordinate REMSCAN Soil Type Color North East % mg/kg DR-01 753771 142256 Clayey Silt Dark Brown 2.36 23,600 6.02 DR-02 753771 142256 Clayey Silt Dark Brown 2.54 25,400 9.05 RSD (%) DR-03 753776 142270 Clayey Silt Dark Brown 1.99 19,920 10.86 DR-04 753764 142276 Clayey Silt Dark Brown 1.92 19,220 2.45 DR-05 753763 142276 Clayey Silt Dark Brown 2.29 22,860 5.20 DR-06 753778 142275 Clayey Silt Light Brown 0.25 2,473 9.60 DR-07 753762 142281 Clayey Silt Brown 1.23 12,340 5.52 DR-08 753804 142186 Clayey Silt Dark Brown 2.67 26,747 11.80 12

Summary Portable handheld IR Instrument will enable rapid and accurate delineation of sites & allows real time process monitoring for different remediation technologies Significant time reductions Real-time process monitoring Rapid, field-based testing Improve data density for site assessment Less waiting time for soil excavation and transport Improved Safety Prevents worker exposure and generation of waste by eliminating the use of solvents (used in the lab and in other field test methods) Potential Cost Savings 13

Slide 14 Acknowledgements The authors gratefully acknowledge the support and discussion from Ziltek Pty. Ltd and ALS lab in Bogor, Indonesia for deployment of Handheld IR Instrument 14