identifying natural chemicals in petroleum hydrocarbons ... · identifying natural chemicals in...

© 2018 Chemistry Matters Inc.

Making chemistry data meaningful

Identifying natural chemicals in petroleum hydrocarbons analysis

Remtech 2018

October 10, 2018

Phil Richards and Court D Sandau

Chemistry Matters Inc., Calgary, AB

© 2018 Chemistry Matters Inc. 2Identifying natural chemicals in petroleum hydrocarbons analysis Remtech 2018

Nature contains pesky chemicals that get in the way

There is no such thing as zero in chemistry

Environmental chemistry is interesting !?


Nature + chemistryNatural VOCs in air samples

Analyzing for VOCs from oil tanks, but find lots of natural chemicals.

Natural PAHs in rivers

Confounding analysis for PAHs from oil.

Snowpack toluene

Looking for AOSR contaminants.

Natural SalinityConfounding produced water salinity impacts.


Peat

4Identifying natural chemicals in petroleum hydrocarbons analysis Remtech 2018

Soil? Waterbody? Chemical Soup?


Peat Analytical Data

5

Sample Benzene Toluene Ethylbenzene XylenesF1 C6-C10 -

BTEXF2 C>10-C16 F3 C>16-C34 F4 C>34

15-HA118 <0.035 7.5 <0.094 <0.38 <53 <94 1300 <470

15-HA119 <0.044 4.4 <0.053 <0.47 <65 <120 1300 <580

15-HA120 <0.045 34 <0.091 <0.36 <51 <91 980 <460

15-HA121 <0.040 <0.053 <0.11 <0.42 <59 <110 780 <530

15-HA122 <0.038 <0.038 <0.076 <0.30 <42 <76 980 <380

15-HA123 <0.031 0.38 <0.063 <0.25 <35 82 1100 <310

15-HA125 <0.042 <0.043 <0.085 <0.34 <47 <85 1300 <420

15-HA126 <0.037 2.3 <0.074 <0.29 <41 290 2300 800

15-HA127 <0.040 1.5 <0.079 <0.32 <44 <79 760 <400

15-HA128 <0.040 <0.053 <0.11 <0.42 <59 <110 640 <530

15-HA129 <0.035 <0.047 <0.093 <0.37 <52 <93 750 <460

15-HA130 <0.040 4.1 <0.079 <0.32 <44 <79 1400 <400

15-HA131 <0.036 0.31 <0.095 <0.38 <53 <95 1200 <480

15-HA132 <0.044 8.7 <0.053 <0.47 <65 <120 1000 <580

15-HA133 <0.040 1.9 <0.081 <0.32 <45 81 870 <400

15-HA134 <0.041 <0.055 <0.11 <0.43 <61 150 1600 <540

15-HA135 <0.054 <0.072 <0.065 <0.57 <80 <140 1000 <710

Bitumen at 15-HA124 0.8 2.1 0.71 2.6 49 31000 210000 430000

Peat at 15-HA124 <0.021 0.14 <0.042 <0.17 <23 <42 700 210

Bitumen at 15-HA136 0.1 0.23 0.067 0.26 <12 26000 190000 94000

Peat at 15-HA136 <0.042 <0.056 <0.051 <0.44 <62 2300 16000 31000

Bitumen at 15-HA137 0.5 1.3 0.42 1.6 30 23000 170000 81000

Peat at 15-HA137 <0.0050 <0.020 <0.010 <0.040 <12 140 1200 2100

AB T1 - Coarse, Surface,

Natural Areas0.078 0.12 0.21 28 210 150 300 2800

Identifying natural chemicals in petroleum hydrocarbons analysis Remtech 2018

Unimpacted peat contains chemicals in petroleum hydrocarbon analysis• PHC F3 (F2 and F4)• Toluene


Peat Sample

6

F2 F3 F4

Prominent peaksTypical pattern for peat


But what are they?


Peat Sample

7

SterolsFatty acids and alcohols


But what are they?


Plant Cell Structure

8

Sterols

phospholipidphospholipid


Environmental conditionsSterols

Fatty acids and alcohols

© 2018 Chemistry Matters Inc. 9

m/z 191Gamma-sitasterol

Cholestadienol

Cyclolanostanol


1 23 4

5

67 8

m/z 85

Fatty acids Fatty alcohols

Biomarker Analysis


Chemistry!!Sterols make steranes

10

Cholestadienol Cholestane

Diagenesis

Plant structural membrane chemical

Oil biomarker


reteneabeitic acidtoluenea-pinene


Burden of Proof



BTEXF2 C>10-C16 F3 C>16-C34 F4 C>34

15-HA118 <0.035 7.5 <0.094 <0.38 <53 <94 1300 <470

15-HA119 <0.044 4.4 <0.053 <0.47 <65 <120 1300 <580

15-HA120 <0.045 34 <0.091 <0.36 <51 <91 980 <460

15-HA121 <0.040 <0.053 <0.11 <0.42 <59 <110 780 <530

15-HA122 <0.038 <0.038 <0.076 <0.30 <42 <76 980 <380

15-HA123 <0.031 0.38 <0.063 <0.25 <35 82 1100 <310

15-HA125 <0.042 <0.043 <0.085 <0.34 <47 <85 1300 <420

15-HA126 <0.037 2.3 <0.074 <0.29 <41 290 2300 800

15-HA127 <0.040 1.5 <0.079 <0.32 <44 <79 760 <400

15-HA128 <0.040 <0.053 <0.11 <0.42 <59 <110 640 <530

15-HA129 <0.035 <0.047 <0.093 <0.37 <52 <93 750 <460

15-HA130 <0.040 4.1 <0.079 <0.32 <44 <79 1400 <400

15-HA131 <0.036 0.31 <0.095 <0.38 <53 <95 1200 <480

15-HA132 <0.044 8.7 <0.053 <0.47 <65 <120 1000 <580

15-HA133 <0.040 1.9 <0.081 <0.32 <45 81 870 <400

15-HA134 <0.041 <0.055 <0.11 <0.43 <61 150 1600 <540

15-HA135 <0.054 <0.072 <0.065 <0.57 <80 <140 1000 <710

Bitumen at 15-HA124 0.8 2.1 0.71 2.6 49 31000 210000 430000

Peat at 15-HA124 <0.021 0.14 <0.042 <0.17 <23 <42 700 210

Bitumen at 15-HA136 0.1 0.23 0.067 0.26 <12 26000 190000 94000

Peat at 15-HA136 <0.042 <0.056 <0.051 <0.44 <62 2300 16000 31000

Bitumen at 15-HA137 0.5 1.3 0.42 1.6 30 23000 170000 81000

Peat at 15-HA137 <0.0050 <0.020 <0.010 <0.040 <12 140 1200 2100


Natural Areas0.078 0.12 0.21 28 210 150 300 2800

How do we demonstrate this is natural?


Options


• Silica Treatment

• 2DGC

• F3 splitting

• Chromatogram analysis SterolsFatty acids and alcohols


Options


• Silica Treatment

• 2DGC

• F3 splitting

• Chromatogram analysis

Lab stage

Post-lab output


2DGC


2DGC has 2 columns• First is normal phase. • Second is polar (just like silica this separates out the polar natural chemicals).

But it does not affect the normal PHCs.


F3a - F3b


F3a = C16 – C22

F3b = C22 – C34

Kelly-Hooper. F., et al., 2013,

Is it clean or contaminated soil?...

Env. Toxicol. Chem., 32, 10, pp2197-2206.

Environment Canada white paper uses standard

analytical chemistry analysis of PHC Fractions.


F3a - F3b


• Applicable for light to medium crude.

• Not applicable for heavy oils and bitumen.


Weathered Diesel

Chromatograms


Medium Crude

DieselBitumen

Coal TarWeathered Medium Crude

Creosote


Chromatograms


Peat

Bitumen

Diesel


Background Statistics


Section 2.4.2 of Alberta Tier 1 Soil and Groundwater Remediation Guidelines allows for the background soil quality to be assessed statistically to derive a rational target for remediation.

427095-

Percen le

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

PHCF3(C>16-C34)Concentra

on(mg/kg)

BoxplotforPHCF3(C>16-C34),with95thpercen le

The application of site-specific targets allows for the site to be returned to its native state.

Caution: PHC F3 analysis does not necessarily represent a comparable measure for peat-F3 and petroleum-F3.



BTEXF2 C>10-C16 F3 C>16-C34 F4 C>34

15-HA118 <0.035 7.5 <0.094 <0.38 <53 <94 1300 <470

15-HA119 <0.044 4.4 <0.053 <0.47 <65 <120 1300 <580

15-HA120 <0.045 34 <0.091 <0.36 <51 <91 980 <460

15-HA121 <0.040 <0.053 <0.11 <0.42 <59 <110 780 <530

15-HA122 <0.038 <0.038 <0.076 <0.30 <42 <76 980 <380

15-HA123 <0.031 0.38 <0.063 <0.25 <35 82 1100 <310

15-HA125 <0.042 <0.043 <0.085 <0.34 <47 <85 1300 <420

15-HA126 <0.037 2.3 <0.074 <0.29 <41 290 2300 800

15-HA127 <0.040 1.5 <0.079 <0.32 <44 <79 760 <400

15-HA128 <0.040 <0.053 <0.11 <0.42 <59 <110 640 <530

15-HA129 <0.035 <0.047 <0.093 <0.37 <52 <93 750 <460

15-HA130 <0.040 4.1 <0.079 <0.32 <44 <79 1400 <400

15-HA131 <0.036 0.31 <0.095 <0.38 <53 <95 1200 <480

15-HA132 <0.044 8.7 <0.053 <0.47 <65 <120 1000 <580

15-HA133 <0.040 1.9 <0.081 <0.32 <45 81 870 <400

15-HA134 <0.041 <0.055 <0.11 <0.43 <61 150 1600 <540

15-HA135 <0.054 <0.072 <0.065 <0.57 <80 <140 1000 <710

Bitumen at 15-HA124 0.8 2.1 0.71 2.6 49 31000 210000 430000

Peat at 15-HA124 <0.021 0.14 <0.042 <0.17 <23 <42 700 210

Bitumen at 15-HA136 0.1 0.23 0.067 0.26 <12 26000 190000 94000

Peat at 15-HA136 <0.042 <0.056 <0.051 <0.44 <62 2300 16000 31000

Bitumen at 15-HA137 0.5 1.3 0.42 1.6 30 23000 170000 81000

Peat at 15-HA137 <0.0050 <0.020 <0.010 <0.040 <12 140 1200 2100


Natural Areas0.078 0.12 0.21 28 210 150 300 2800

How do we demonstrate this is natural?

Toluene


Toluene

https://doi.org/10.1002/etc.4008

https://doi.org/10.1002/etc.4008


pinene

limonene

p-cymene

sec-butyl benzene

Arson and biogenic toluene


Fingerprint of peat

23

Toluene p-cymene


Typical oil Peat

a.

b.

c.

d.

Toluene


Ecosite and Seasonality

24

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

0.45

1 2

TolueneConcentration(mg/kg)

0

0.005

0.01

0.015

0.02

0.025

0.03

0.035

0.04

0.045

0.05

May July August September October

TolueneConcentra

on(mg/L)


Poor bog Poor fen


Conclusions


• Natural chemicals interfere with PHC analysis.• Choose carefully the method you want to apply to

distinguish from impacts. • Lab based – silica clean-up, 2DGC.• Post-lab – F3 splitting, chromatograms, statistics.

• Toluene – be aware of natural toluene, what evidence do you need?


Conclusions


Environmental chemistry is interesting !?

identifying natural chemicals in petroleum hydrocarbons ... · identifying natural chemicals in...

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