Science of the Total Environment 907 (2024) 168039

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Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

On quantifying global carbon emission from oil contaminated lands

over centuries
Kaveh Sookhak Lari a, b, c, *, Greg B. Davis a, Trevor Bastow a, John L. Rayner a
a
CSIRO Environment, Private Bag No. 5, Wembley, WA 6913, Australia
b
School of Engineering, Edith Cowan University, 270 Joondalup Drive, Joondalup, WA 6027, Australia
c
Geothermal Energy and Geofluids Group, Department of Earth Sciences, ETH Zurich, CH-8092, Zurich, Switzerland

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Petroleum releases into the subsurface

contribute to global soil carbon
emissions.
• We modelled 150 years of emissions
from main major and minor releases
since 1950.
• Up to 2100 the carbon emitted is esti­
mated 4 to 6 Teragrams, with 60 %
currently released.
• Nomographs help predict the fate of
LNAPL plumes and carbon emissions
due to NSZD.
• The multi-physics method can include
additionally identified and future
releases.

A R T I C L E I N F O A B S T R A C T

Editor: Frederic Coulon Petroleum releases into the subsurface contribute to global soil carbon emissions. Quantifying releases and
changes in releases of carbon from soils over the lifetime of a spill is complex. Natural source zone depletion
Keywords: (NSZD) of light non-aqueous phase liquids (LNAPLs) embodies all key mechanisms for transformation to carbon
LNAPL gases and their release from soils including partitioning, transport and degradation of petroleum components.
NSZD
Quantification of the interconnected behaviours of the soil microbiome, fluid flow, multi-component transport,
Petroleum
partitioning, and biodegradation is crucial for understanding NSZD. Volatilization from LNAPL, aerobic
Carbon emission
Modelling biodegradation, methanogenesis, and heat production all lead to release of greenhouse gases to the atmosphere.
Multi-physics To estimate carbon emissions, using a validated computational platform, we modelled the long term NSZD of
Transient four petroleum hydrocarbon types; crude oil, diesel, jet fuel and gasoline, to span the major products used
globally. For two soil types, we estimated 150 years of carbon emissions from annual minor and 25 mostly major
petroleum hydrocarbon land release incidents since 1950 – with an estimated released mass of ~9 million tonnes
across the circumstances considered. Up to 2100 the mass of carbon emitted to the atmosphere is estimated to
range from 4 to 6 Teragrams, with nearly 60 % currently released. Nomographs generated help predict the fate of
LNAPL plumes and carbon emissions due to NSZD, which is crucially important to management of soil and

* Corresponding author at: CSIRO Environment, Private Bag No. 5, Wembley, WA 6913, Australia.
E-mail address: kaveh.sookhaklari@csiro.au (K. Sookhak Lari).

https://doi.org/10.1016/j.scitotenv.2023.168039
Received 30 August 2023; Received in revised form 9 October 2023; Accepted 20 October 2023
Available online 23 October 2023
0048-9697/© 2023 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC license (http://creativecommons.org/licenses/by-
nc/4.0/).
K. Sookhak Lari et al. Science of the Total Environment 907 (2024) 168039

groundwater contamination. The method provides a basis to include additionally identified and future petroleum
releases. It is noted that the petroleum mixture composition, degradation rates, volatilization, and subsurface
characteristics all can influence carbon emission estimations.

1. Introduction
More than one-third (>200 Teragrams (Tg) per year) of global
methane released is by anaerobic microbial degradation of organic
compounds including methanogenesis in soils, mostly within a few
meters of the surface (Bossio et al., 2020). Anthropogenic activities
including release of petroleum compounds as light non-aqueous phase
liquids (LNAPLs) into the subsurface affect natural biogenic greenhouse
gas (GHG) fluxes, especially resulting in increases in carbon dioxide and
methane emissions (Tian et al., 2016).
Predicting the long-term behaviour of the soil microbiome is key to
successful soil management (Sookhak Lari et al., 2019a). Despite ad­
vances in methods (Sihota and Mayer, 2012; Sihota et al., 2011), tech­
nical difficulties in measuring and prediction of field-scale GHG fluxes
highlights the necessity to characterise and quantify factors affecting
field-scale methane and carbon dioxide generation. Soil structures,
biogeochemical kinetics, and the soil depth where key processes occur,
all modify the timing and magnitude of net fluxes emitted at ground
surface. Modelling can assist to acceptable accuracy and with quantifi­
able uncertainty at relatively low cost, albeit with limitations due to our
current understanding of the governing processes and their accurate
representation of reality (Sookhak Lari et al., 2019a; Paustian et al.,
2016). Major gaps in soil carbon modelling exist (Bossio et al., 2020;
Paustian et al., 2016).
Subsurface petroleum pollution is not a well quantified source of
GHG, due to uncertainty in its global distribution (even in Antarctica)
(Rayner et al., 2007; MarineGroup, 2004; Etkin, 2009a; ITOFP, 2020;
IncidentNews, 2020) and due to the level of process complexity in
generating carbon emission flux estimates from petroleum release in­
stances. Process complexity is from the need to link multiple physical
and biochemical processes whereby multiphase transport of fluids,
partitioning between phases and multi-component transport of com­
pounds are coupled to component-based biodegradation processes. Such
processes are now embodied by the term natural source zone depletion
(NSZD) of petroleum hydrocarbons (Garg et al., 2017; Johnson et al.,
2006).
We note that petroleum released within soils open to the atmosphere
at ground surface, despite releasing volatile chemicals such as benzene
and producing methane within the soil profile, will largely biodegrade
these components aerobically releasing only carbon dioxide at the
ground surface (Davis et al., 2009; Davis et al., 2021).
Major inland oil releases globally (excluding marine tankers and
platforms) (MarineGroup, 2004; ITOFP, 2020; IncidentNews, 2020)
have occurred due to transportation incidents, pipelines, storage
leakage, sabotage, and blowouts during drilling wells (Essaid et al.,
2011; Tawfiq and Olsen, 1993; Patten, 1992). Focusing on the United
States of America (USA) (as a major consumer and producer), about 70
% of oil production is from inland crude oil wells. Land spills and re­
leases have reduced by half over 50 years, but 5000 spills still occur each
year. Annual minor spills to land and groundwater have decreased from
>40 million litres of petroleum hydrocarbons (75 % crude, 20 % gaso­
line) in 1960s to 20 million litres in 2000s (Etkin, 2009a; Etkin, 2009b).
Worldwide, releases are more pronounced in North America (47 %) with
a smaller number in Asia (29 %), Europe (16 %), Africa (4 %) and South
America (4 %) (Etkin, 2009a; Khan and Abbasi, 1999). Recently at
COP26 held in Glasgow Scotland some major petroleum user/producer

Fig. 1. Twenty five major global release incidents since 1950 – scaled to the size of the release. Borders and location of the releases are approximate.

2
K. Sookhak Lari et al.
Fig. 2. Cumulative released LNAPL mass. This includes the sum of reported minor release incidents in the USA (Etkin, 2009c) extrapolated and decreasing over time
to vanish by 2080. The global minor release was determined by scaling based on the USA to global GDP fraction (The World Bank, 2023), and major releases since
1950 (see Table 1).
countries disagreed with ending the subsidization of fossil fuels
(UNFCCC, 2021) prolonging the broader risks associated with leakage
and release of petroleum fuels from storage and handling of large vol­
umes into the foreseeable future.
Oil-contaminated soils are challenging with respect to site and GHG
emissions management. Remediation approaches are not always suc­
cessful in minimising hydrocarbon footprints, nor the emission of GHGs
(Sookhak Lari et al., 2019a; McAlexander, 2014; McAlexander and
Tuggle, 2015; Statham Tom et al., 2023). Successful bioremediation can
produce either methane or carbon dioxide (Davis, 2023; Smith et al.,
2023). Assessing management options has required a digital represen­
tation of linked physical and biochemical processes within multi-phase
non-isothermal subsurface environments. (McAlexander, 2014; McA­
lexander and Tuggle, 2015; Ganna et al., n.d.).
Recent advances in computational capacity and modelling capabil­
ities have made it possible to consider representative simulation of in­
tegrated GHG formation and emissions. This also enables prediction of
the fate of the hydrocarbon plumes themselves, which is significantly
important in risk management of soil and groundwater contamination
(Sookhak Lari et al., 2019a; Sookhak Lari et al., 2021a). It is now feasible
to conduct field scale modelling of emissions for complex problems such
as variably saturated oil-contaminated soils and subsurface systems,
undergoing biodegradation, i.e., NSZD of petroleum hydrocarbons
(Pishgar et al., 2022; Kulkarni et al., 2022; Mineo, 2023). However, until
recently such capabilities have never been used to representatively
simulate integrated GHCs formation and emission over the entire depth
of the affected subsurface (Sookhak Lari et al., 2019a; Sookhak Lari
et al., 2021a) or its transient behaviour to complete depletion of oil and
fuel releases. While longer term field studies have measured changes in
petroleum biodegradation and NSZD rates, these are so far only decadal
studies (Kulkarni et al., 2022; Davis et al., 2022) not extending to the
multiple decades and perhaps the century time-frames required.
2. The scale of the global release incidents
Not all inland release incidents are always well quantified and
documented. To provide an example of the methodology for GHG
emission estimation presented here, we identified 25 major petroleum
land release incidents since 1950s (>1000 t-see Figs. 1, 2 and Table 1),
across a range of fuel types. As the global data for minor petroleum
releases is incomplete, we estimated it based on data for the USA, by
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Science of the Total Environment 907 (2024) 168039
weighting it according to the gross domestic product (GDP), comprising
an average 30 % of the global economy (The World Bank, 2023; Etkin,
2009c; Etkin, 2001). We also applied a descending trend to minor re­
leases in USA and assumed these to vanish by 2080. With the approach
described in the next section, representative modelling of NSZD for
major and minor releases was conducted for a period of 150 years
(1950–2100).
3. Methods
3.1. The general approach
Greater than 30 codes were compared with respect to their capa­
bilities in addressing and mimicking the major NSZD processes (Sookhak
Lari et al., 2019a). Among them, TMVOCBio, based on TMVOC, showed
the greatest potential, and was evaluated against biodegradation data
collected at the crude oil release site at Bemidji (Sookhak Lari et al.,
2019a; Sookhak Lari et al., 2021a). Here we use the TMVOCBio
modelling framework for a wide range of LNAPL partitioning and
biodegradation attributes. The code encapsulates multi-physics at a
Darcy scale and simulates the compositional changes in different phases
due to solubility and volatilization, biodegradation reactions and tem­
perature whilst coupling multi-phase and multi-component aspects
allowing LNAPL (and air and water) saturations to vary over time.
We follow the approach in (Sookhak Lari et al., 2016a) to bundle
thousands of chemicals in each fuel into representative groups. Multi-
component gasoline, jet fuel, diesel and crude oil were simulated to
include a wide range of volatility, solubility and biotic degradation
(Sookhak Lari et al., 2016a). Compositional details as well as the pet­
rophysical properties of the component groups in each fuel are presented
in Table 4. Two types of soils (coarse and fine sand) are simulated to find
the upper and lower bounds of emissions for sandy systems. Soil mois­
ture parameters for these soils are reported in Table 2.
We assume 50 L/m2 of specific volume for the LNAPL plume at rest,
which results in the fluid profiles depicted in Fig. 3. This is supported by
field studies (Davis et al., 2022). The scenarios are simulated in one-
dimension vertically, with the vertical profile assumed to be located
within a laterally extensive LNAPL plume. Description of the key
equations and processes for an LNAPL profile undergoing partitioning
and biodegradation are given below. Fig. 4 provides a depiction of these
key processes with direct volatilization of vapours from the LNAPL, but
K. Sookhak Lari et al. Science of the Total Environment 907 (2024) 168039

Table 1
Compilation of well-known major release incidents since 1950 (C = crude, G = gasoline, J = Jet Fuel, D = diesel).
Country Year Mass Type Ref.
(kt)

Greenpoint NY USA 1950 55 C http://www.newtowncreekalliance.org/greenpoint-oil-spill/

Guadalupe Dunes CA USA 1960 25 C https://academic.oup.com/socpro/article/49/2/150/2277569
Trans Alaska USA 1978 2 C https://www.reuters.com/article/oil-pipeline-alaska-idUKN0920953120110109
W-D103 Libya 1980 120 C https://www.kbzk.com/cnn-world/2019/02/21/oil-spills-fast-facts/
Oganiland Nigeria 1982 250 C https://www.aljazeera.com/features/2022/12/21/timeline-oil-spills-in-nigerias-ogoniland
Perth, Western Australia 1985 100 C, G, J, Davis et al. 2022 (Davis et al., 2022)
Australia D
Arthur Kill NJ USA 1990 1.5 J https://inis.iaea.org/search/search.aspx?orig_q=RN:23063111
Kuwait Kuwait 1991 1500 C https://digitallibrary.un.org/record/186417?ln=en
Fergana Uzbekistan 1992 285 C https://www.britannica.com/list/9-of-the-biggest-oil-spills-in-history
Komi Russia 1994 120 C https://reliefweb.int/report/russian-federation/russian-federation-oil-spill-oct-1994-un-dha-infor
mation-reports-1-6
Bass Ent. Louisiana USA 2005 10 C https://www.nbcnews.com/id/wbna9365607#.Ut7Y2mQo6u4
Shell/Chevron USA 2005 15 C https://www.nbcnews.com/id/wbna9365607#.Ut7Y2mQo6u4
Louisiana
Citgo Ref. USA 2006 5 C https://www.newsweek.com/citgo-fined-19m-2006-spill-54000-barrels-slop-oil-louisiana-river-1601749
Oganiland Nigeria 2008 1 C https://www.aljazeera.com/features/2022/12/21/timeline-oil-spills-in-nigerias-ogoniland
Kalamazo Michigan USA 2010 3 C https://www.epa.gov/enbridge-spill-michigan
Oganiland Nigeria 2011 180 C https://www.aljazeera.com/features/2022/12/21/timeline-oil-spills-in-nigerias-ogoniland
Little Buffalo Alberta Canada 2011 4 C https://www.greenpeace.org/static/planet4-canada-stateless/2018/06/RainbowPipelineSpill.pdf
Arthur Kill NJ USA 2012 1 D https://www.nbcnewyork.com/news/local/arthur-kill-oil-spill-diesel-fuel-motiva-staten-island-woodbri
dge-nj/1966724/
North Dakota USA 2013 3 C https://www.nytimes.com/2013/10/24/us/oil-spill-in-north-dakota-raises-detection-concerns.html
EAPC Israel 2014 4 C https://www.reuters.com/article/us-israel-environment-pipeline-idUSKCN1N520T
Colonial Alabama USA 2016 1 G https://www.reuters.com/article/us-colonial-co-leak-alabama-idUSKCN1GR3F1
Keystone S. Dakota USA 2017 1 C https://edition.cnn.com/2017/11/16/us/keystone-pipeline-leak/index.html
Norilsk Russia 2020 17.5 D https://petroleumaustralia.com.au/bnf/nornickel-pays-full-damages-in-connection-with-2020-fuel-spill/
Colonial Alabama USA 2020 5 G https://www.fractracker.org/2021/05/august-2020-colonial-pipeline-spill-in-north-carolina/
Keystone Kansas USA 2022 2 C https://www.reuters.com/markets/commodities/tc-energy-receives-findings-root-cause-keystone-pipeli
ne-oil-spill-2023-04-21/

Table 2
Petrochemical properties of the formation and the fluids: Interfacial tension between fluid pairs (mN/m) (w: water, g: gas and n: LNAPL), multi-phase van Genuchten
parameter αa,b (=αd σgw/σa,b; αd (m-1) is the drainage α) and n (− ), the intrinsic permeability k (m− 2) and porosity Θ (− ) (Sookhak Lari et al., 2016b; Taban et al., 2018).
Variable Unit Value (Fine/Coarse) Variable Unit Value (C:D-Fine-G:J-Fine/C:D-Coarse: G:J-Coarse)
2 − 1
k m 1E-12/1E-11 αgn m 3–4.5/10–15
Θ – 0.38 αnw m− 1 2–1.63/6.67–5.454
1 1
αd m− 1.2 σgw mN.m− 75
1
n – 3.31/3.57 σgn mN.m− 20
1
Sr – 0.00 σnw mN.m− 55

also generation of methane within the LNAPL moving up into the vadose The substrate utilisation rate (Rs) and biomass growth/decay in the
zone and being aerobically degraded to CO2 within the shallower region code are governed by (Battistelli, 2004; Barry et al., 2002):
of the vadose zone (Davis et al., 2009). Additionally, CO2 also moves ( )( )
X S E
directly into the vadose zone from the LNAPL and groundwater having Rs = − μ m (1)
Ib Ks + S KE + E
been generated by biodegradation processes within those zones. The
parameters for the Monod kinetics of aerobic biodegradation and
dX
methanogenesis of different groups in each fuel are presented in the = − Y rs − bX (2)
dt
Table 3.
where X, E and S are the biomass, electron acceptor and substrate con­
centrations respectively [M/L3], KS and KE are the half-saturations of the
3.2. The modelling approach and key equations
substrate and electron acceptor [M/L3], μm is the maximum specific
growth rate [T− 1], Y is the biomass yield coefficient and b [T− 1] is the
The code TMVOC has been extensively verified with respect to multi-
first-order decay coefficient (Blanc et al., 1996).
phase fluid flow of non-aqueous phase liquids (Lekmine et al., 2017;
The general format of the substrate utilisation and end-products and
Lenhard et al., 2018; Sookhak Lari et al., 2016b; Sookhak Lari et al.,
biomass production may be represented as:
2015; Sookhak Lari et al., 2018; Sookhak Lari and Moeini, 2015; Soo­
khak Lari et al., 2017; Sookhak Lari et al., 2019b; Engelmann et al., Organic Matter + O2 →CO2 + H2 O + Heat
2021). TMVOCBio is a finite volume numerical simulator (based on
TMVOC/TOUGH3) for multi-phase multi-component multi-microbe Organic Matter + H2 O→α CO2 + 2α CH4 + Heat
transport phenomena at Darcy scale. This code has also been exten­
sively verified (Battistelli, 2004; Jung and Battistelli, 2017). A recent for aerobic and methanogenesis respectively. Multi-phase flow models
comprehensive verification was conducted by comparing the computed can simulate the simultaneous transport of aqueous, gaseous and LNAPL
NSZD rates, liquids and gases saturations and compounds concentra­ phases. Major gases include nitrogen, oxygen, methane, carbon dioxide
tions versus 27 years of field measurement at the oil-contaminated and volatile compounds. Except for nitrogen (inert) depletion/formation
Bemidji site in the USA (Essaid et al., 2011).

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K. Sookhak Lari et al. Science of the Total Environment 907 (2024) 168039

Fig. 3. Depth distributions of fluid phase saturations at commencement of multi-component partitioning and biodegradation simulation for fine and coarse sandy
soils (Sg = gas, Sw = water, Sn = NAPL, S_L = total liquids or Sw + Sn). Saturations changed from these as LNAPL mass became depleted.

Fig. 4. Pathways of greenhouse gas formation due to NSZD considered in the model.

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K. Sookhak Lari et al. Science of the Total Environment 907 (2024) 168039

Table 3
Parameters of the biochemical reactions. μm is the maximum specific substrate degradation rate (s− 1), KS (kg/kg) and KO (kg/kg) represent the half saturation of the
primary and secondary substrates (oxygen) and KE represent the non-competitive inhabitation coefficients (oxygen for methanogenesis kg/kg) and I is the biomass
inhabitation factor [− ]. (A) represents aerobic degradation and (M) stands for methanogenic degradation (Essaid et al., 2011; Sookhak Lari et al., 2021a; Essaid et al.,
2003). Methane is considered highly biodegradable under aerobic conditions - producing carbon dioxide. The maximum specific growth rates in parenthesis represent
values used for the sensitivity analysis (see Section 4.3).
Highly biodegradable Moderately biodegradable Lowly biodegradable

μm A 50E− 5 (25E− 5) 10E− 5 (5E− 5) 10E− 6 (5E− 6)

μm M 5E− 6 (2.5E− 6) 1E− 6 (5E− 7) 1E− 7 (5E− 8)
KSA 1E− 6 1E− 6 1E− 6
KSM 0.12E− 6 0.12E− 6 0.12E− 6
KO 1E− 6 1E− 6 1E− 6
IbA 0.15E− 5 0.15E− 5 0.15E− 5
Ibm 0.3E− 6 0.3E− 6 0.3E− 6
KE 1E− 6 1E− 6 1E− 6
YA 0.27/ 0.27 0.27
YM 0.08 /0.08 0.08
bA 1E− 7 1E− 7/ 1E− 7
bM 1E− 27 1e− 27 1E− 27

of other gases is considered (Sookhak Lari et al., 2021a). The mass The constituents are bundled into 7 representative groups with their
transport equation is (Sookhak Lari et al., 2016b; Pruess et al., 2002; physical properties represented in Table 4 (Sookhak Lari et al., 2016a;
Miller et al., 2013). Sookhak Lari et al., 2016b). The selection of representative groups for
[ N ] each petroleum product were limited to 7 groups (due to modelling
∑ p ( )
∂C i
+ ∇. i i
Cβ vβ − D∇Cβ = ri (3) constraints) and based on properties of the major individual components
∂t β=1 and carbon ranges present in each petroleum product (fresh and
weathered), such as volatility (C5 to C10 carbon range components),
where i and β refer to the component number k and phase β respectively water solubility (BTEX and C3-alkylbenzenes) and resistance to
(with Np is the total number of phases), D is the (effective) diffusion biodegradation (n-alkanes and lower molecular weight components
coefficient [MT− 1] (Millington and Quirk equation (Pruess et al., 2002)) generally more readily biodegraded, and higher molecular weight
and r is the sink/source term. The velocity v is calculated through the components comprising of branched/cyclic alkanes and aromatics
Darcy law equation: resistant to biodegradation).
krβ ( )
vβ = − k ∇Pβ − ρβ g , (4) 4. Primary results and limitations
μβ

with constitutive relationships to relate relative permeability of each 4.1. Time history of the mass loss of LNAPL components and the LNAPL
phase, pressure (P, including capillary) and the phase saturation (Len­ types
hard and Parker, 1990). Here, k and krβ are the absolute and relative
permeability to phase β ([L2] and [− ] respectively), ρ and μ are the Fig. 5 shows the overall volumetric loss percentage across all LNAPL
density [ML− 3] and viscosity of phase β [ML− 1 T− 1] and g is the gravity components for the different petroleum types over time and for the two
acceleration vector [LT− 2]. The constitutive relationship (van Gen­ sand formations. In general, the fine sand formation conserves the
uchten equation) between saturation and head (h = P/ρg) is LNAPL mass for a more prolonged period. Gasoline mass is removed
relatively rapidly, and loss of diesel mass is slowest. This is expected
Sijj − Sm [ ( )n ]− m given the overall volatility and degradability of the mass fractions of
= 1 + αij h , i, j = G, Aq, N, i ∕
=j (5)
1 − Sm gasoline and diesel.
Figs. 6 and 7 depict individual outcomes for the percentage loss of
where Sijj represents the effective wetting phase fluid saturation, n is a the assumed component groups in each of the crude oil, diesel, jet fuel
constant, m = 1/n − 1 and Sm is the irreducible saturation (of the and gasoline LNAPLs for coarse and fine sand scenarios. Notable, are the
wetting phase). The three-phase fluid flow requires the relative perme­ comparable time frames, with gasoline being largely depleted within 20
ability to be a function of phase saturation. We apply the van Genuchten- years in the coarse sand (Figs. 5 and 6), jet taking 100 years to fully
Muallem equation in the model for the relative permeabilities to gas (G), deplete, but crude and diesel extending well beyond 100 years.
aqueous (Aq) and LNAPL (N) phases (Jung and Battistelli, 2017; Parker For fine sands (Figs. 5 and 7) the timeframes are further extended, for
and Lenhard, 1987): example, with gasoline not fully depleted within 60 years. Note that the
√̅̅̅̅̅̅( component groups differ across each of the product types (Table 4).
)
1/m 2m
krG = SG 1 − SL (6)
4.2. Estimates of global emissions
√̅̅̅̅̅̅̅( ( ) )
1/m m 2
krAq = SAq 1 − 1 − SAq (7)
Fig. 8 depicts the cumulative carbon released to the atmosphere
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅(( across all relevant fuel types. The current major releases will emit up to 2
) ( )m )2
krN = SL − SN 1 − SAq
1/m m
− 1 − SL 1/m (8) Tg of carbon by the end of the 21st century. Including annual minor
releases in the USA, the maximum emission rises to 2.5 Tg. Including
global minor releases, the maximum emission is bounded between 4 and
where the saturations are in their effective form, with L representing the
6 Tg (based on the soil type). The modelling suggests that nearly 60 %
total liquid (Parker and Lenhard, 1987). Table 2 has the properties of the
may have already been released, assuming no major future releases.
fluids, the formation and the LNAPL (C: crude, D: diesel, J: jet fuel/
This rate of GHG emissions is modest compared to broader anthro­
kerosene and G: gasoline).
pogenic emissions from soil. However, it was not our intention to
Parameters of the biochemical reactions are presented in Table 3.
exhaustively include all sources, but to show that the complexity of the

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K. Sookhak Lari et al. Science of the Total Environment 907 (2024) 168039

Table 4
Physical properties of the LNAPL groups (Sookhak Lari et al., 2021a; Kulkarni et al., 2022; Sookhak Lari et al., 2016a; Miles et al., 2008; Rayner et al., 2020; Sookhak
Lari, 2020; Tomlinson et al., 2017). Columns include the groups names, representative molecules, pure solubility (assuming that gas phase fugacity coefficients and
liquid phase activity coefficients are equal to one, Henry’s and Raoult’s Law are applied in the model (Lekmine et al., 2017; Jung et al., 2018; Pruess et al., 2005)), pure
vapor pressure, tendency for methanogenesis and aerobic degradation (high, moderate and low), average molecular weight, density, viscosity, average number of
carbons and mass and mole percentage. Rep. MF: representative molecular formula, V.P.: vapor pressure, Aer.: susceptibility to aerobic biodegradation, Met.: sus­
ceptibility to methanogenesis, L: low, M: medium, H: High, Av: average, MW: molecular weight, #C: number of carbons, TPH: total petroleum hydrocarbons.
Fuel type # Compound groups Rep. MF. Solubility V.P. Met. Aer. Av. Density Viscosity Av. Mass Mole
mg/l kPa MW g/L mPa.s #C % %

Gasoline 1 Benzene C6H6 1.8 12.7 H H 78 876 0.7 6 1 1.4

Carbon 2 Toluene C7H8 0.5 2.8 H H 92 862 0.56 7 13 15.3
Range 3 Xylene C8H10 0.15 1 H H 106 864 0.8 8 14 14.3
C5-C14 4 Ethylbenzene C8H10 0.15 1.3 H H 106 866 0.67 8 3 3.0
5 Trimethylbenzenes (TMBs) C9H12 0.07 1.77 M M 240 850 0.8 9 10 4.6
6 C5 to C9 Carbon range alkanes (C5C9- C7H16 0.01 16.5 H H 100 500 0.4 7 54 58.3
Alkanes)
7 C10 to C14 Carbon range TPH C12H26 <1E− 3 0.05 H H 170 700 0.7 12 5 3.1
(C10C14-TPH)
Jet Fuel 1 C8 to C12 Carbon range n-alkanes C10H22 <1E− 3 0.46 H H 142 500 0.5 10 35 42.0
Carbon (C8C12-n-Alkanes)
Range 2 C13 to C18 Carbon range n-alkanes C15H32 <1E− 3 <1E− 3 H H 220 700 0.7 15.5 20 15.5
C8-C18 (C13C18-n-Alkanes)
3 C8 to C12 Carbon range branched/ C10H20 <1E− 3 0.46 H H 142 500 0.5 10 15 18.0
cyclic alkanes and aromatics minus
alkylbenzenes where the alkyl group
contains 3 carbons (C8C12-BCAs
minus C3-Benzenes/TMBs)
4 C13 to C15 Carbon range branched/ C15H24 <1E− 3 <1E− 3 M M 198 700 0.6 14 19 16.3
cyclic alkanes and aromatics minus
farnesane (C13C15-BCAs minus IP15)
5 C16 to C18 Carbon range branched/ C17H28 <1E− 3 <1E− 3 L L 240 800 0.7 17 3 2.1
cyclic alkanes and aromatics
(C16C18-BCAs)
6 Farnesane (IP15) C15H24 <1E− 3 0.01 L L 204 600 0.6 15 3 2.5
7 Alkylbenzenes where the alkyl group C9H12 0.07 1.77 M M 240 850 0.8 9 5 3.6
contains 3 carbons (C3-Benzenes/
TMBs)
Diesel 1 C9 to C16 Carbon range n-alkanes C12H26 <1E− 3 0.01 H H 177 500 0.5 12.5 15 21.6
Carbon (C9C16-n-Alkanes)
Range 2 C17 to C35 Carbon range n-alkanes C20H42 <1E− 3 <1E− 3 M M 350 800 0.7 20 30 21.9
C9-C35 (C17C35-n-Alkanes)
3 C9 to C10 Carbon range branched/ C10H20 <1E− 3 1 M M 135 500 0.5 9.5 5 9.5
cyclic alkanes and aromatics (C9C10-
BCAs)
4 C11 to C16 Carbon range branched/ C15H24 <1E− 3 0.01 L L 191 600 0.6 13.5 10 13.3
cyclic alkanes and aromatics
(C11C16-BCAs)
5 C17 to C35 Carbon range branched/ C19H40 <1E− 3 <1E− 3 L L 350 800 0.7 20 30 21.9
cyclic alkanes and aromatics minus
pristane (C17C35-BCAs minus
pristane)
6 Pristane C19H40 <1E− 3 <1E− 3 L L 268 700 0.6 19 5 4.7
7 Non-volatile dissolved organic C12H18O 0.21 <1E− 3 L L 180 600 0.5 12 5 7.1
compounds or polar compounds
(NVDOC)
Crude 1 C6 to C10 Carbon range TPH (C6C10- C7H16 0.002 4.8 H H 114 500 0.5 8 10 21.4
Carbon TPH)
Range 2 C11 to C12 Carbon range branched/ C11H16 <1E− 3 0.025 M M 163 600 0.6 11.5 5 7.5
C6-C40 cyclic alkanes and aromatics
(C11C12-BCAs)
3 C13 to C16 Carbon range branched/ C14H22 <1E− 3 <1E− 3 L L 198 700 0.6 14.5 10 12.4
cyclic alkanes and aromatics
(C13C16-BCAs)
4 C17 to C40 Carbon range branched/ C20H34 <1E− 3 <1E− 3 L L 350 800 0.8 27 35 24.5
cyclic alkanes and aromatics
(C17C40-BCAs)
5 C11 to C16 Carbon range n-alkanes C12H26 <1E− 3 <1E− 3 H H 191 600 0.6 13.5 5 6.4
(C11C16-n-Alkanes)
6 C17 to C40 Carbon range n-alkanes C20H42 <1E− 3 <1E− 3 L L 350 800 0.8 27 30 21.0
(C17C40-n-Alkanes)
7 Non-volatile dissolved organic C12H18O 0.21 <1E− 3 L L 180 600 0.5 12 5 6.8
compounds or polar compounds
(NVDOC)

7
K. Sookhak Lari et al. Science of the Total Environment 907 (2024) 168039

Fine Sand Coarse Sand

100 100
90 90

% Loss in LNAPL volume

% Loss in LNAPL volume
80 80
70 70
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100
Year Year

Crude Diesel Gasoline Jet Crude Diesel Gasoline Jet

Fig. 5. Simulated volumetric loss of LNAPL over time for the fine and coarse sand soils.

key processes could be accommodated, and embedded with a method to 4.3. Characteristics of the outcomes and limitations
generate a global rate from petroleum releases. It is likely that most
refineries that have operated globally would have had releases beyond 1 Here we emphasise limitations of the study and underlying as­
kt and hence would be termed major here. This would extend Table 1 sumptions. The scope of the work and interpretation of the results have
beyond 25 sites to many hundred sites. Such releases may not have been the following characteristics:
all at one time and as such create variable GSG emissions over time. We
believe the approach described here has yielded representative model­ • The study aimed to advance the development and application of a
ling and digital twin options that encompass the complex subsurface multi-phase multi-component multi-microbe verified computational
phenomenon relevant to petroleum hydrocarbons and broader appli­ methodology to allow estimation of GHG emissions from petroleum
cation (Sookhak Lari et al., 2019a; Sookhak Lari et al., 2021a). As major contaminated lands. Comprehensive investigation of the sensitivity
sources of GHG emission (from soil) are largely steady-state, the of the results across the parameter space was beyond the scope.
approach is potentially applicable to other sources such as nitrification/ • In an approximate way accommodate significant global petroleum
denitrification in agriculture and deforested lands (Tian et al., 2016; release occurrences into the assessment.
Paustian et al., 2016; Blagodatsky and Smith, 2012). The simulation
platform also allows inverse modelling and statistical studies to assess The primary assumptions are in two categories:
sensitivities to parameter variations. As more data on petroleum releases
become available re-analysis of the trends is possible. • The modelling code assumptions

Fig. 6. Percent loss of different LNAPL component groups (see Table 4) for the four petroleum types in coarse sand.

8
K. Sookhak Lari et al. Science of the Total Environment 907 (2024) 168039

Fig. 7. Percent loss of different LNAPL component groups (see Table 4) for the four petroleum types in fine sand.

• Parameters, and initial and boundary conditions
Regarding the first, capabilities of >30 models was reviewed and the
one used here was shown to be the most representative of the NSZD
processes (Sookhak Lari et al., 2019a). The reliability of the modelling
assumptions (e.g., the equilibrium condition and upscaling constitutive
relationship to Darcy scale) has been verified (Sookhak Lari et al., 2015;
Sookhak Lari and Moeini, 2015). However, a limitation is that there is no
such model with a systematic capability for multiphase hysteresis (Jung
et al., 2018).

Fig. 8. Accumulating global carbon release from 25 major petroleum hydrocarbon contaminated lands since 1950. The labels (e.g., W–D103, Fergana) relate to
selected major release incidents and the year is the date of the release (see Table 1 for details). The ‘upper limit’ curves (right) are calculated based on simulations of a
soil comprised of coarse and the ‘lower limit’ values (left) relate to fine materials. The figure is prepared based on the temporal summation of the degradation from
each release in Table 1.

9
K. Sookhak Lari et al.
Results presented here are sensitive to the parameters used, and the
initial and boundary conditions assumed. Some, such as different soil
types (with different geophysical parameters), were evaluated. How­
ever, finer soils (silts and clays) and evaluating the breadth of the
parameter space for all parameters is beyond the scope of this study.
Regarding the boundary conditions, we assumed a constant climate
condition (no rainfall, no water table fluctuations, constant background
temperature and atmospheric pressure). However, when considering the
response of gas transport to atmospheric pressure changes and baro­
metric pumping, it is reasonably accepted that such a surface effect
would compress or expand the gas column in the vadose zone propor­
tionally to the depth of the soil profile above the water table (Gliński and
Stępniewski, 1985). On average over decades to centuries it would be
unlikely to have an undue influence on net carbon gas emissions. In
contrast some moisture changes (due to rainfall/evapotranspiration)
could liberate or limit gas fluxes from and into the subsurface (e.g.,
(Davis et al., 2005)). Soil texture would play a role in the retention or
reduction of soil moisture. Long-term climate variations then may
change average soil moisture concentrations, and associated carbon
fluxes. Variations of this are additionally avenues for further studies
(Lenhard et al., 2018; Ramezanzadeh et al., 2023; Sun et al., 2023;
Koohbor et al., 2023; Ramezanzadeh, 2023), but can be accommodated
in the modelling platform and methodology used and proposed here.
For the LNAPL phase, the effect of specific mass was not evaluated as
it was in studies without the additional biodegradation processes
essential to NSZD (Sookhak Lari et al., 2016a; Sookhak Lari, 2020). Also
we did not consider mass reduction due to active remediation, which has
shown to be considerably effective at early stages of the release (Soo­
khak Lari et al., 2021b). A justification for this assumption is (1) the
recovered mass remains subjected to biodegradation and hence a source
of emission and residual levels always remain and biodegrade (2) many
of the major releases occur in areas where it is difficult to recover (e.g.
due to conflicts or where it is beneath infrastructure, or where it is in
remote regions) and (3) many of the releases remain unidentified.
Where remedial efforts are significant this would lead to overestimation
of GHG emissions as estimated here. However, where this is known such
mass reductions can be applied in the methodology. As already
mentioned, the scale of unknown sources and releases of petroleum
hydrocarbons into the subsurface is likely to be substantial – and would
to some degree offset mass removal by remedial efforts.
An additional preliminary sensitivity analysis was undertaken on the
maximum specific growth rate, μm, by halving the original values (see
Table 3). The least effect on depletion was observed for gasoline and the
greatest for diesel. This was expected as high rates of partitioning play a
critical role in mass depletion (see Table 4 to compare the values). By
halving μm and for the fine and coarse sand, gasoline mass depleted in 67
and 25 years respectively (versus 60 and 20 years for the initial μm; see
Fig. 5). Diesel lost 12 % and 33 % of its volume over 100 years (for fine
and coarse sand respectively) versus 20 % and 55 % for the initial μm
(see Fig. 5).
5. Conclusions
A framework and methodology have been presented that allows
estimation of GHG emissions from petroleum releases globally. Using
advances in measurement and modelling of NSZD the underlying pro­
cesses that lead to transformation of petroleum to carbon dioxide and
then net carbon fluxes at the ground surface from soils, are reliably
accounted for. By assessing global occurrences of well-known major
petroleum releases and approximating minor petroleum releases a
verified NSZD modelling platform was used to estimate the long term
GHG emissions over 150 years for four petroleum fuel types (gasoline,
diesel, crude oil, jet fuel). As expected, gasoline showed the greatest
mass emissions, but also was depleted the quickest, with diesel having
the lowest rate of emissions. Based on the assessment 4–6 Tg is the
estimated cumulative carbon emission across fine and coarse soil
10
Science of the Total Environment 907 (2024) 168039
formations, recognising that many sources of petroleum hydrocarbons
are yet to be well documented or identified. We note however that the
assessment here assumes no active remediation has been conducted at
sites, i.e. assuming only NSZD processes. The methodology is also rele­
vant to addressing other anthropogenic sources of soil contamination
that contribute significantly to global warming (King and Durham,
2017).
We note that about one-third of global methane emissions arise from
methanogenesis in soils, with a substantial portion being anthropogenic,
including incidents of LNAPL releases (Bossio et al., 2020). A more
extensive inventory of oil-contaminated lands distributed globally
would provide a more reliable estimate of GHG as a fraction of global
carbon emissions. The research presented here contributes to this
ongoing effort.
As a practical outcome, the nomographs that depict volumetric losses
over time (Figs. 5–7) can be used as guidelines to estimate NSZD at
contaminated sites over long durations and for various fuel types. This
enables better decision making on trade-offs between continuing active
remediation (and associated emissions) and NSZD.
Limitations of the study are outlined. As the main intention was to
move towards developing a representative methodology to estimate
NSZD and GHG emissions from petroleum contaminated lands, a full
sensitivity analysis (climate conditions, specific LNAPL mass, more di­
versity in soil types and ranges of parameters) was beyond the scope of
this study.
CRediT authorship contribution statement
Kaveh Sookhak Lari: Conceptualization, Data curation, Methodol­
ogy, Software, Writing – original draft. Greg B. Davis: Conceptualiza­
tion, Methodology, Data curation, Writing – original draft. Trevor
Bastow: Data curation, Writing – original draft. John L. Rayner:
Conceptualization, Data curation, Writing – original draft.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Public data, Ref. provided
Acknowledgement
Support from BP is appreciated in encouraging the reliable quanti­
fication of NSZD process, and in particular BP Australia staff and man­
agement. The first author would like to thank Venous Sheydaei for her
helps and support.
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