Using Fingerprinting Techniques and Multivariate Statistics to Identify Natural Salinity versus Anthropogenic Salinity in Soil - CLRA 2017
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This document presents the findings of a study using fingerprinting techniques and multivariate statistics to distinguish between natural and anthropogenic salinity in soil samples. Radar plots and statistical analysis of parameters like chloride, calcium, sodium, and sulfate concentrations were used to group 54 site samples. Three distinct fingerprint patterns were identified, with two samples having natural salinity fingerprints similar to background samples, 48 samples having anthropogenic fingerprints different than background, and 3 samples having another separate fingerprint. Spatial analysis found the sample groupings correlated with wellsite features. The techniques were able to distinguish anthropogenic impacts despite low overall salinity levels.
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Using Fingerprinting Techniques and Multivariate Statistics to Identify Natural Salinity versus Anthropogenic Salinity in Soil - CLRA 2017
- 1. © 2017 Chemistry Matters Inc. Making environmental data meaningful Using Fingerprinting Techniques and Multivariate Statistics to Identify Natural Salinity versus Anthropogenic Salinity in Soil Presented at CLRA 2017, Red Deer, Alberta
- 2. © 2017 Chemistry Matters Inc. 2Natural versus Anthropogenic Salinity in Soil Copyright Statement All rights reserved. No part of this publication may be reproduced, distributed, or transmitted in any form or by any means, including photocopying, recording, or other electronic or mechanical methods, without the prior written permission of Chemistry Matters Inc.
- 3. © 2017 Chemistry Matters Inc. Salinity in the Oilfield • Produced water from oil well (Brine) – High concentration of salt (200 – 200,000 + ppm) • Different formations present different salinity patterns • Other spills may be a result of drilling processes (drilling fluids) 3Natural versus Anthropogenic Salinity in Soil
- 4. © 2017 Chemistry Matters Inc. Salinity • Two groups of salinity – Naturally occurring salinity – Anthropogenic salinity (resulting from human activities) • Both may or may not have salinity concentrations above applicable guidelines • Difficult to distinguish between the two 4Natural versus Anthropogenic Salinity in Soil
- 5. © 2017 Chemistry Matters Inc. Common Salinity Parameters • Calcium • Magnesium • Sodium • Potassium • Sulphate • Chloride • pH • Electrical Conductivity • Sodium Adsorption Ratio 5Natural versus Anthropogenic Salinity in Soil
- 6. © 2017 Chemistry Matters Inc. Soil Contamination Assessment Tool • A tool used for distinguishing between natural and anthropogenic salinity – User input • Separate background and site samples • Separate based on depth (surface vs subsoil) – Normalize data (mg/kg – meq/kg - % total) – Radar Plots 6Natural versus Anthropogenic Salinity in Soil SCAT
- 7. © 2017 Chemistry Matters Inc. Radar Plots 7 • Web Definition – Displays multivariate data in the form of a two-dimensional chart of more than 3 variables represented on axes starting from the same point (www.amcharts.com) • Easier Definition – A Fingerprint! Natural versus Anthropogenic Salinity in Soil
- 8. © 2017 Chemistry Matters Inc. Technique • Use the shape of an individual site sample plotted against the background 8Natural versus Anthropogenic Salinity in Soil Cl- Ca2+ Na+SO42- Mg2+ Cl- Ca2+ Na+SO42- Mg2+ Not Impacted Potentially Impacted Blue – background Pink – site sample (Based on % values)
- 9. © 2017 Chemistry Matters Inc. All Sites Not Created Equal • Generally background are all similar onsite • Fingerprints may be affected by: – Sample depth – Sample location (slough, up gradient) – Soil stratigraphy (soil types) • Site may also have: – Multiple source fingerprints 9Natural versus Anthropogenic Salinity in Soil
- 10. © 2017 Chemistry Matters Inc. Complex Sites Need Extra Analysis • Large number of samples or multiple fingerprints • Exploratory statistical techniques help identify groups of samples • We use Principle Component Analysis (PCA) and Hierarchical Cluster Analysis (HCA) – Sometimes used to validate radar plots – Sometimes used to give additional information about how the samples group (or don’t group) together 10Natural versus Anthropogenic Salinity in Soil
- 12. © 2017 Chemistry Matters Inc. HCA 12Natural versus Anthropogenic Salinity in Soil • Dendrogram • Read right to left • Cluster with the longest horizontal line are the most similar
- 13. © 2017 Chemistry Matters Inc. All Together • Relate the radar plots to the results of the PCA and HCA – Are the same samples in the radar plot groups the same as in the PCA/HCA groups? • Identify commonality between samples in groups • Identify distinguishing traits between samples from different groups 13Natural versus Anthropogenic Salinity in Soil
- 14. © 2017 Chemistry Matters Inc. Case Study • 7 background samples • 54 site samples • Entered data into SCAT for salinity fingerprints • Used statistical analysis to validate SCAT outputs Natural versus Anthropogenic Salinity in Soil 14
- 15. © 2017 Chemistry Matters Inc. 15Natural versus Anthropogenic Salinity in Soil Raw Chloride Concentrations • Max [Cl-] – 170 mg/kg • Background some of the highest values O – Background X – No Match Y – Match (Green – low environmental risk Orange – possible environmental risk Red - environmental risk)
- 17. © 2017 Chemistry Matters Inc. Background Locations Natural versus Anthropogenic Salinity in Soil 17
- 18. © 2017 Chemistry Matters Inc. • Background samples were plotted on radar plots to see each fingerprint compared to the average background fingerprint • Two samples showed a distinctly different fingerprint Background Locations Cl- Ca2+ Na+SO42- Mg2+ Cl- Ca2+ Na+SO42- Mg2+ Natural versus Anthropogenic Salinity in Soil 18
- 19. © 2017 Chemistry Matters Inc. Cl- Ca2+ Na+SO42- Mg2+ Cl- Ca2+ Na+SO42- Mg2+ Cl- Ca2+ Na+SO42- Mg2+ Cl- Ca2+ Na+SO42- Mg2+ Cl- Ca2+ Na+SO42- Mg2+ • Background fingerprints that match averaged background fingerprint Background Locations Natural versus Anthropogenic Salinity in Soil 19
- 20. © 2017 Chemistry Matters Inc. Background samples with site samples Background Locations O – Background X – No Match Y – Match (Green – low environmental risk Orange – possible environmental risk Red - environmental risk) • PCA showed similar results – Two background samples grouped with site samples Natural versus Anthropogenic Salinity in Soil 20
- 21. © 2017 Chemistry Matters Inc. 2112 2113 2114 2115 2116 2117 2118 2119 2120 2121 2122 2123 2124 2125 2126 2127 2128 2129 2130 2131 2132 2133 2134 2135 2136 2137 2138 2139 2140 2141 2142 2143 2144 2145 2146 2147 2148 2149 2150 2151 2152 2153 2154 2155 2156 2157 2158 2159 2160 2161 2162 2163 2164 2165 2166 2167 2168 • HCA showed similar results – Two background samples clustered with site samples Background Background Background Locations Natural versus Anthropogenic Salinity in Soil 21
- 22. © 2017 Chemistry Matters Inc. • Two samples are from the same borehole located close to well center • Samples removed from analysis SITE FLOWLI MONI REFERENCE LIST OF APPLICABLE APEC AREA OF POTENTIA m METRE ORIGINAL DRAWING OBTAINED NO.: E14-041; SCALE: 1:1,000; DA Background Locations Natural versus Anthropogenic Salinity in Soil 22
- 23. © 2017 Chemistry Matters Inc. • Radar plots for site samples were reviewed and manually grouped • 3 distinct groups of fingerprints were identified – Group 1 - 2 site samples similar to background – Group 2 - 48 samples different to background – Group 3 - 3 samples separate from all – One with mixed fingerprint Site Sample Radar Plots Natural versus Anthropogenic Salinity in Soil 23
- 24. © 2017 Chemistry Matters Inc. Cl- Ca2+ Na+SO42- Mg2+ Cl- Ca2+ Na+SO42- Mg2+ Cl- Ca2+ Na+SO42- Mg2+ Ex. TP13-02-10 Ex. BH14-02-03 TP13-02-10 Group 1 Site Sample Radar Plots Cl- Ca2+ Na+SO42- Mg2+ Group 2 Group 3 Mixed Fingerprint Ex. BH14-03 Natural versus Anthropogenic Salinity in Soil 24
- 25. © 2017 Chemistry Matters Inc. • Some samples in between Group 1 and 2 showing increasing salinity concentrations as they move Group 1 Principal Component Analysis Group 2 Group 3 Natural versus Anthropogenic Salinity in Soil 25
- 26. © 2017 Chemistry Matters Inc. • Group 1 – 2 samples from 2 different wells • Group 2 – samples from all over the wellsite • Group 3 all from 1 well • Did look at depth relations but none were found SITE PLAN FLOWLINE, TES MONITORIN REFERENCE LIST OF APPLICABLE ABBREVI APEC AREA OF POTENTIAL ENVIRONME m METRE ORIGINAL DRAWING OBTAINED FROM LN LAN NO.: E14-041; SCALE: 1:1,000; DATE: MAY 02, 2 IMPE FO 13 WIZARD Spatial Relations Natural versus Anthropogenic Salinity in Soil 26
- 27. © 2017 Chemistry Matters Inc. Conclusion • Even with low impacts for the site the statistics and radar plots were able to distinguish samples with anthropogenic salinity impacts from background • The PCA confirmed the differences noted in radar plots of background 27Natural versus Anthropogenic Salinity in Soil
- 29. © 2017 Chemistry Matters Inc. Case Study 2 (Spatial Relation) • 10 background samples • 62 site samples 29Natural versus Anthropogenic Salinity in Soil
- 30. © 2017 Chemistry Matters Inc. 30 Cl- Ca2+ Na+SO42- Mg2+ Cl- Ca2+ Na+SO42- Mg2+ MW13-01-01 BH13-01-01 Cl- Ca2+ Na+SO42- Mg2+ TP12-08-10 • General pattern of 8 of the background samples • Pattern of 2 of the background samples Natural versus Anthropogenic Salinity in Soil
- 31. © 2017 Chemistry Matters Inc. 31 • PCA verified that these 2 background samples are different from the other background samples 2 different background samples Natural versus Anthropogenic Salinity in Soil
- 32. © 2017 Chemistry Matters Inc. 32 2 different background samples • 2 background included in analysis because of where they plot on PCA Natural versus Anthropogenic Salinity in Soil
- 33. © 2017 Chemistry Matters Inc. 33 • 29 samples were included in Group 1 • 19 samples were included in Group 2 with the newly characterized background • Remaining samples from Group 3 all have similar fingerprints to each other, but are distinctly different from background. Blue line – averaged background sample fingerprint Pink line – various site sample patterns seen across the site Cl- Ca2+ Na+SO42- Mg2+ FL12-02-07 (1.4mbg) Ex of Group 3 fingerprint Natural versus Anthropogenic Salinity in Soil
- 34. © 2017 Chemistry Matters Inc. 34 Group 1 Group 2 Group 3 Natural versus Anthropogenic Salinity in Soil Cl- Ca2+ Na+SO42- Mg2+ FL12-02-07 (1.4mbg) Cl- Ca2+ Na+SO42- Mg2+ Cl- Ca2+ Na+SO42- Mg2+
- 35. © 2017 Chemistry Matters Inc. 35 100/02-29 20.12 m ACCESS ROAD CROPLAND CROPLAND CROPLAND WELL CENTRE WELL CENTRE 10.06m NEP PIPELINE RIGHT-OF-W AY 20.00 m NEP PIPELINE RIGHT-OF-WAY 102/02-29 ELINERIGHT-OF-WAY GHT-OF-WAY CENTRAL SUSPECTED SUMP NORTHWEST EM ANOMALY WEST SUSPECTED SUMP AND NEP PIPELINE RIGHT OF WAY APEC CENTRAL EM ANOMALY 102/02-29 WELL CENTRE APEC 100/02-29 WELL CENTRE APEC TP12-04 TP12-01 TP12-15 TP12-03 TP12-05 TP12-08 TP12-09 TP12-07 TP12-02 TP12-06 TP12-10 TP12-11 TP12-14TP12-13 TP12-12 FL12-01-01 FL12-01-02 FL12-01-03 FL12-01-04 FL12-01-05 FL12-02-02 FL12-02-01 FL12-02-03 FL12-02-04 FL12-02-05B FL12-02-06 FL12-02-07 FL12-02-05A MW13-01 BH13-02 BH13-01 MW13-02 MW13-04MW13-03 BH13-04 BH13-05 BH13-03 SITE PLAN WITH TEST PIT, FLOWLINE SAMPLE, BOREHOLE AND MONITORING WELL LOCATIONS FIGURE: 5 IMPERIAL OIL LIMITED FORMER WELLSITE 100/ AND 102/02-29-050-26 W4M LEDUC FIELD, ALBERTA ORIGINAL DRAWING OBTAINED FROM LN LAND DEVELOPMENT TECHNOLOGIES INC. : LNLD JOB No.: E13-231; SCALE: 1:1,000; DATE: OCTOBER 23, 2013. REFERENCE LIST OF APPLICABLE ABBREVIATIONS APEC AREA OF POTENTIAL ENVIRONMENTAL CONCERN EM ELECTROMAGNETIC m METRE NEP NEWTON ENERGY PARTNERS 4, 1964) FLOWLINE SAMPLE LOCATION TEST PIT LOCATION WELL CENTRE 100/02-29 20.12 m ACCESS ROAD CROPLAND CROPLAND CROPLAND CULVERT 5.0mHIGH-GRADEGRAVELROAD WELL CENTRE WELL CENTRE 20.12mACCESSROAD 10.06m NEP PIPELINE RIGHT-OF-W AY 20.00 m NEP PIPELINE RIGHT-OF-WAY 10.06mPIPELINERIGHT-OF-WAY 10.06mPIPELINERIGHT-OF-WAY 102/02-29 INERIGHT-OF-WAY HT-OF-WAY CENTRAL SUSPECTED SUMP NORTHWEST EM ANOMALY WEST SUSPECTED SUMP AND NEP PIPELINE RIGHT OF WAY APEC CENTRAL EM ANOMALY 102/02-29 WELL CENTRE APEC 100/02-29 WELL CENTRE APEC TP12-04 TP12-01 TP12-15 TP12-03 TP12-05 TP12-08 TP12-09 TP12-07 TP12-02 TP12-06 TP12-10 TP12-11 TP12-14TP12-13 TP12-12 FL12-01-01 FL12-01-02 FL12-01-03 FL12-01-04 FL12-01-05 FL12-02-02 FL12-02-01 FL12-02-03 FL12-02-04 FL12-02-05B FL12-02-06 FL12-02-07 FL12-02-05A MW13-01 BH13-02 BH13-01 MW13-02 MW13-04MW13-03 BH13-04 BH13-05 BH13-03 SITE PLAN TEST PIT, FLOWLINE S AND MONITORING W IMPERIAL OIL FORMER WE 100/ AND 102/02-29 LEDUC FIELD, ORIGINAL DRAWING OBTAINED FROM LN LAND DEVELOPMENT TECHNOLOGIES INC. : LNLD JOB No.: E13-231; SCALE: 1:1,000; DATE: OCTOBER 23, 2013. REFERENCE LEGEND LIST OF APPLICABLE ABBREVIATIONS APEC AREA OF POTENTIAL ENVIRONMENTAL CONCERN EM ELECTROMAGNETIC m METRE NEP NEWTON ENERGY PARTNERS LEASE BOUNDARY RECLAMATION BOUNDARY (CERTIFICATE No. 1202, ISSUED SEPTEMBER24, 1964) UNDERGROUND PIPELINE END UNDERGROUND PIPELINE (FORMER) WORK AREA BOREHOLE LOCATION BOREHOLE LOCATION COMPLETED AS A MONITORING WELL FLOWLINE SAMPLE LOCATION TEST PIT LOCATION WELL CENTRE 100/02-29 20.12 m ACCESS ROAD CROPLAND CROPLAND CROPLAND CULVERT 5.0mHIGH-GRADEGRAVELROAD WELL CENTRE WELL CENTRE 20.12mACCESSROAD 10.06m NEP PIPELINE RIGHT-OF-W AY 20.00 m NEP PIPELINE RIGHT-OF-WAY 10.06mPIPELINERIGHT-OF-WAY 10.06mPIPELINERIGHT-OF-WAY 102/02-29 10.06mNEPPIPELINERIGHT-OF-WAY FLOWLINERIGHT-OF-WAY CENTRAL SUSPECTED SUMP NORTHWEST EM ANOMALY WEST SUSPECTED SUMP AND NEP PIPELINE RIGHT OF WAY APEC CENTRAL EM ANOMALY 102/02-29 WELL CENTRE APEC 100/02-29 WELL CENTRE APEC TP12-04 TP12-01 TP12-15 TP12-03 TP12-05 TP12-08 TP12-09 TP12-07 TP12-02 TP12-06 TP12-10 TP12-11 TP12-14TP12-13 TP12-12 FL12-01-01 FL12-01-02 FL12-01-03 FL12-01-04 FL12-01-05 FL12-02-02 FL12-02-01 FL12-02-03 FL12-02-04 FL12-02-05B FL12-02-06 FL12-02-07 FL12-02-05A MW13-01 BH13-02 BH13-01 MW13-02 MW13-04MW13-03 BH13-04 BH13-05 BH13-03 a) b) c) Group 1 Group 2 Group 3 Green circles are locations where surface samples are from Group 2 and the deeper samples are from Group 1 All cluster together in the middle of the site Mostly all cluster together at the top portion of the site Natural versus Anthropogenic Salinity in Soil
- 36. © 2017 Chemistry Matters Inc. Conclusion • Radar plots and PCA/HCA showing similar groups • Groups are geospatially organized in areas that make sense • Multiple lines of evidence give higher degree of confidence in interpretation 36Natural versus Anthropogenic Salinity in Soil
- 37. © 2017 Chemistry Matters Inc. Case Study 3 (Depth Relation) • 7 background samples • 65 site samples 37Natural versus Anthropogenic Salinity in Soil
- 38. © 2017 Chemistry Matters Inc. • PCA shows background grouping together Natural versus Anthropogenic Salinity in Soil 38 Group 1 Cl- Ca2+ Na+SO42- Mg2+
- 39. © 2017 Chemistry Matters Inc. • Group 2 consists of site samples with fingerprints different than background Natural versus Anthropogenic Salinity in Soil 39 Group 2 Cl- Ca2+ Na+SO42- Mg2+ Group 1 Cl- Ca2+ Na+SO42- Mg2+ Cl- Ca2+ Na+SO42- Mg2+
- 40. © 2017 Chemistry Matters Inc. a) b) 5 out of 6 samples are > 0.5 mbg All but one samples are < 0.5 mbg • This indicates surface samples are similar and any samples below 0.5 mbg are similar Natural versus Anthropogenic Salinity in Soil 40
- 41. © 2017 Chemistry Matters Inc. Group 3 • Group 3 includes 3 distinct samples Natural versus Anthropogenic Salinity in Soil 41
- 42. © 2017 Chemistry Matters Inc. • These 3 samples had another distinct pattern not seen in any other samples Blue line – averaged background sample fingerprint Pink line – the general fingerprint of a site sample seen across the site Cl- Ca2+ Na+SO42- Mg2+ Cl- Ca2+ Na+SO42- Mg2+ Cl- Ca2+ Na+SO42- Mg2+ S12-18 Topsoil (0mbg) S12-18 Subsoil (0.3mbg) S12-18 Subsoil (1.3mbg) Natural versus Anthropogenic Salinity in Soil 42
- 43. © 2017 Chemistry Matters Inc. • These samples were all from one borehole Natural versus Anthropogenic Salinity in Soil 43
- 44. © 2017 Chemistry Matters Inc. Overall Conclusions • Radar plots create fingerprints to visually identify samples different from background • Multivariate statistics verify radar plots and may add information to investigation • Heterogenic site conditions may make the investigation more complex but does not make it impossible • Do not need high levels of contamination to find differences 44Natural versus Anthropogenic Salinity in Soil
- 45. © 2017 Chemistry Matters Inc. Thank you for your attention Contact Info: Chemistry Matters Inc. Court Sandau Cell: 403.669.8566 Email: csandau@chemistry-matters.com URL: chemistry-matters.com Visit our website and sign up for email for automatic receipt of the blog! Twitter: @Chem_Matters Slideshare: www.slideshare.net/csandau 45www.chemistry-matters.com