A TPH Criteria Working

Group method for New

Zealand
Consultant’s perspective

9/11/2017
 Introduction
 What are hydrocarbons
 Hydrocarbon F&T
 NZ approach to analysis
 CWG approach to analysis
 Attenuation mechanisms
 Benefits of CWG method
 Case Study: Tory Street soils

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 What are we talking about?

 “The definition of TPH depends on the analytical method used because the TPH
measurement is the total concentration of the hydrocarbons extracted and
measured by a particular method.” - TPH Criteria Working Group 1998.

R R
| |
R‒C‒C‒R
| |
R R
alkanes
3
 Basics of Hydrocarbon F&T
 Most organic chemicals are fuels in Straight chain alkanes
an environment containing oxygen
(chemical half life)
 The less saturation (absence of
multiple bonds/ branching/ aromatic
rings) the less polar (water soluble)
and less reactive they tend to be
 The larger the molecule the less
reactive and less polar they tend to
be

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 Assessing Hydrocarbons in New Zealand
 1999 Guidelines for Assessing and Managing Petroleum Hydrocarbon
Contaminated Sites in New Zealand
− 3 generic bands
− Chromatographs
− C7 – C36 (approx.)
− ‘The guidelines focus on sites that have stored, handled, or distributed petroleum
products. ‘ page 2.

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 Assessing Hydrocarbons elsewhere…
 CWG (Vol. 1 - 5) banding
− Aliphatic and aromatic
− Chromatographs
− 15 (or so) bands
− C5 – C44 (approx.)
− ‘The goal of the Working Group is to provide the technical information needed by
regulators, risk assessors, and site managers to implement health risk-based
decisions at petroleum contaminated sites.’ Page 1, Volume 1.

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 NZ CWG

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 Basics of hydrocarbon attenuation
 Physical ‘weathering’ mechanisms
− Solubility
− Volatilisation
− Dilution
 Biological/ Chemical weathering
mechanisms
− Methanogensis
− Oxidation
− ‘tarificiation’/ branching/ reconfiguration

 Front. Microbiol., 18 November 2014

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 Benefits
 Mixed source identification
 Semi quantitative
assessment of aging
 Source profiling
 QA

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 Discussion of Tory Street Gas works

 NZ OIWG  CWG method

Sample ID BH6 Depth_4.5 BH6 Depth_5.8
Reference 17-16530 17-16530 Project ID RDG CPK RDG CPK
Date received 21/07/2017 21/07/2017
Description 249874 249874
Laboratory ID 17-16530-03 17-16530-04
Sample Description BH6 BH6 Contaminant Category Coal Tar Coal Tar
Depth_4.5 Depth_5.8
C7-C9 123 1161 VPH Analyte
>EC5-EC6 Aliphatic <1 <1
C10-C14 1655 7841 >EC6-EC8 Aliphatic <1 <1
C15-C36 8228 9172 >EC8-EC10 Aliphatic 2 46
>EC5-EC7 Aromatic (Benzene)
C7-C36 (Total) 10006 18175 <1 91
EC7-EC8 Aromatic (toluene) <1 181
>EC8-EC10 Aromatic <1 156

EPH Analyte
>EC10-EC12 Aliphatic 15 1007
>EC12-EC16 Aliphatic 182 249
>EC16- EC21 Aliphatic 193 152
>EC21 - EC35 Aliphatic 276 239
>EC10-EC12 Aromatic 37 2913
>EC12-EC16 Aromatic 709 1075
>EC16- EC21 Aromatic 1523 1498
>EC21 - EC35 Aromatic 3221 3648
Total EPH and VPH 6158 11256

TPH Analyte
EC7-EC8 22 41
>EC8-EC10 <10 423
>EC10-EC12 39 5929
>EC12 -EC16 943 1844
>EC16 - EC21 1659 2047
>EC21 - EC35 3955 4732
Total TPH 6618 15015

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 Data assessment

Current method What were missing out on

NZOIWG CWG
20000 4000
3500
18000
3000
16000 2500
14000 2000
1500
12000
1000
10000 500

8000 0

6000

4000

2000

0
C7-C9 C10-C14 C15-C36 C7-C36 (Total)

BH6 Depth_4.5 BH6 Depth_5.8 BH6 Depth_4.5 BH6 Depth_5.8

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 Cheap tricks

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A Robust TPH Speciation
Analytical Method
Terry Cooney
Analytica Laboratories
 Overview Of This Presentation
• Methodology comparison of current NZ Oil Industry Working Group
(NZOIWG) methodology with TPH CWG Speciation Methodology,

• Data output comparison of NZOIWG TPH vs TPH Speciation.

• Comparison of various contaminant sources using the TPH Speciation

methodology

• Concluding comments
 Methodology Comparison of NZOIWG to TPH CWG
NZ TPH OI TPH CWG Speciation

Solvent
Extraction
Sample
Preparation
Silica
Clean-up

Analysis GC-FID
 Methodology Comparison of NZOIWG to TPH CWG
NZ TPH OI TPH CWG Speciation

EPH VPH
Solvent Solvent Methanol
Extraction Extraction Extraction
Sample
Preparation
Silica Silica
Clean-up Fractionisation

GC-FID GC-FID
Analysis GC-FID GC-MS
Aliphatic Aromatic
Data output comparison of NZOIWG to TPH CWG Methods
NZ OI TPH TPH CWG
VPH EPH
EC7 – EC9 Aliphatic >EC5 - EC6 Aliphatic >EC10 - EC12
EC10 - EC14 Aliphatic >EC6 - C8 Aliphatic >EC12 - EC16
EC15 - EC36 Aliphatic >EC8 - C10 Aliphatic >EC12 - EC16
Aliphatic >E16 - EC21
Aromatic >EC5 – EC7 Aliphatic >EC21 - EC35
Benzene Aliphatic >EC35 - EC44
Aromatic >EC7 – EC8
Toluene Aromatic >EC10 - EC12
Aromatic >EC8 - EC10 mg/kg Aromatic >EC12 - EC16
Ethylbenzene Aromatic >EC16 - EC21
m&p-Xylene Aromatic >EC21 - EC35
o-xylene Aromatic >EC35 – EC44

Naphthalene(EC 11.7)
 Key PAH content in the Aromatic bands
Aromatic Band PAHs
>EC5 – EC7 Benzene
>EC7 – EC8 Toluene
>EC8 – EC10 Ethyl Benzene, Xylenes
>EC10 – EC12 Trimethylbenzenes, Alkyltoluenes, other alkylbenzenes and Naphthalene
>EC12 – EC16 Methylnaphthalenes, Acenaphthalene, Acenaphthene, Fluorene
>EC16 – EC21 Phenanthrene, Anthracene, Pyrene
>EC21 – EC35 Fluoranthene, Benzo[a]anthracene, Chrysene, Benzo[b]fluoranthene,
Benzo[k]fluoanthene, Benzo[j]fluoranthene, Dibenzo[a,h]anthracene, Benzo[a]pyrene,
Indeno[1,2,3-cd]pyrene, Benzo[g,h,i]perylene
Diesel Contaminated Soil - TPH Speciation - EPH
EPH Aliphatic and Aromatic Chromatograms
Coal Tar Contaminated Soil - TPH Speciation - EPH
EPH Aliphatic and Aromatic Chromatograms

Coal Tar is an Aromatic dominated contamination source

Coal Tar Contaminated Soil - TPH Speciation - EPH

Aromatic Chromatogram overlaid with PAH Analytical Standard

Coal Tar Contaminated Soil - TPH Speciation - EPH
Coal Tar contaminated soil dominated by Naphthalene (EC11.7)
Petrol Standard - TPH Speciation - VPH
Petrol Standard – VPH Method – GCMS differentiates aliphatic vs aromatic
Petrol Contaminated Soil - TPH Speciation - VPH
Petrol contaminated Soil – identical to petrol standard as expected
 TPH Speciation – When To Use & Cost
• TPH speciation is split into two methods:
• VPH for >EC5 to EC10 and includes mono-aromatics (BTEX and naphthalene):
$35 - $40
• EPH for >EC10 to EC35 (or up to EC44) – PAHs and Aliphatics: $70 - $80

• A decision to run VPH, EPH, or both can be made following NZOIWG

TPH analysis, based on levels and chromatographic profile.
• VPH for a petrol or light fuels contamination
• EPH for a diesel or heavy fuels contamination
• VPH and EPH for a coal tar contamination
 Concluding Comments
• TPH speciation is a robust and affordable methodology.

• Use the TPH NZOIWG method to screen samples, followed up by EPH

and/or VPH speciation if appropriate.

• VPH gives a lot more detailed information – particularly

mono-aromatics (benzene, ethylbenzene, xylenes) and naphthalene.

• Data generated help with more accurate risk assessment and decision
making.
Acknowledgements

Hao Wang, Technologist at Analytica labs, for his rigorous and dedicated analytical
skills to help develop the method.

Tim Dee and Nick King, Aurecon NZ, for their advise, support and sourcing of
samples for the method development.