Process Safety and Environmental Protection 130 (2019) 126–139

Contents lists available at ScienceDirect

Process Safety and Environmental Protection

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

An integrated hazard screening and indexing system for hydraulic

fracturing chemical assessment
Guangji Hu, Haroon R. Mian, Kasun Hewage, Rehan Sadiq ∗
School of Engineering, The University of British Columbia, Okanagan Campus, Kelowna, BC, V1V 1V7 Canada

a r t i c l e i n f o a b s t r a c t

Article history: Various chemicals used in hydraulic fracturing have raised environmental and human health (EHH) con-
Received 2 January 2019 cerns regarding water resources contamination, leading to the transition towards the use of chemicals
Received in revised form 12 June 2019 with minimum EHH hazards. Chemical hazard screening and indexing approaches have been used to
Accepted 2 August 2019
measure the chemical hazard of hydraulic fracturing, and each approach is associated with inherent
Available online 11 August 2019
advantages and limitations. In this study, the two chemical hazard assessment approaches were dis-
cussed, and an integrated chemical hazard screening and indexing system was developed to combine
Keywords:
the strengths of the two approaches. The integrated system was applied to assess the EHH hazards of
Hydraulic fracturing
Environmental and human health
representative hydraulic fracturing chemicals used in British Columbia, Canada. The hazard screening
Oil and gas chemical results showed that more than half of the ingredients and additives were classified into high hazard
Hazard screening groups. Moreover, the integrated system generated more critical hazard assessment results than two
Hazard indexing hazard indexing systems, revealing that using the individual hazard indexing approach could result in
Chemical hazard assessment underestimated EHH hazards for chemicals. The integrated system can significantly improve the data
confidence levels of hazard assessment results compared to a previously developed indexing system.
The integrated system can also help formulate fracturing fluids with low EHH hazards by identifying
ingredients of high hazard concerns.
© 2019 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction
Over the past decades, the unconventional natural gas produc-
tion has been rapidly increasing in Canada (NEB, 2017). The rapid
growth of the unconventional gas industry is mainly attributed
to the combined use of horizontal drilling and hydraulic fractur-
ing, which allows for the economic extraction of natural gas from
low-permeability formations such as gas-bearing shales and sand-
stones (Gallegos and Varela, 2014). Despite the promising resource
potential and economic benefits, the rapid expansion of the uncon-
ventional gas industry has triggered considerable public debate on
possible environmental and human health (EHH) impacts posed
by hydraulic fracturing (Boudet et al., 2014; Soeder et al., 2014;
Vengosh et al., 2014). The chemicals used in hydraulic fracturing
are of particular concern due to the potential contamination of
ground and surface water supplies and the associated health risks
∗ Corresponding author at: School of Engineering, The University of British
Columbia, Okanagan 3333 University Way, Kelowna, British Columbia, V1V 1V7,
Canada.
E-mail address: rehan.sadiq@ubc.ca (R. Sadiq).
to aquatic ecosystems and water resource users (Akob et al., 2016;
Kahrilas et al., 2014; Orem et al., 2017; Renock et al., 2016).
In hydraulic fracturing, various chemical additives are used to
improve fracturing performance and gas recovery. An additive typ-
ically consists of several ingredients at different concentrations.
According to the downhole functions, additives can be divided into
different categories such as gelling agents, friction reducers, and
crosslinkers (Hu et al., 2018a; Kahrilas et al., 2016; Stringfellow
et al., 2014). Different additives are mixed with water and prop-
pants (commonly quartz sands) to formulate a fracturing fluid,
which can be pumped into underground under high pressures to
initiate fractures in the low-permeability formations (FracFocus,
2014). A fracturing fluid may contain three to twelve additives,
depending on geological characteristics of the target formations
and requirements of the operators (Soeder et al., 2014). Additives
may only account for a small fraction (e.g., < 2%) of fracturing fluid;
however, the use of millions of gallons of fracturing fluid for a single
hydraulic fracturing operation still involves a substantial amount
of chemicals (All Consulting, 2012; Engle et al., 2014; Soeder et al.,
2014). More critically, some of the ingredients have been identified
as carcinogens, mutagens, and substances with acute and chronic
toxic effects on human health and aquatic ecosystems (Cozzarelli
et al., 2017; Hu et al., 2018a,2018b; Stringfellow et al., 2014),

https://doi.org/10.1016/j.psep.2019.08.002
0957-5820/© 2019 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
 G. Hu et al. / Process Safety and Environmental Protection 130 (2019) 126–139 127

2016). These chemical hazard assessment systems can generally

List of acronyms be divided into two approaches: hazard screening approach and
hazard indexing approach, and the two approaches are inherently
AhT acute human oral toxicity linked with different advantages and limitations. It is highly desir-
AHP analytical hierarchy process able to develop an integrated chemical hazard assessment system
AT aquatic toxicity (acute/chronic) that combines the strengths of the two approaches for more effec-
B bioaccumulation potential tive chemical hazard evaluation.
C carcinogenicity In this study, the advantages and limitations of hazard screening
CASRN chemical abstracts service registry number and indexing systems were discussed. Based on the discussion, an
ChT chronic human oral toxicity integrated chemical hazard screening and indexing system (ICH-
CTD chemical toxicological data SIS) was developed. The objective defining, parameters selection,
DCIE/H/A/F data confidence index for ingredient- data uncertainty analysis, and chemical hazard weighing, aggrega-
environmental health/ingredient-human tion, and classification of ICHSIS were elucidated. The integrated
health/additive/fracturing fluid system was used to assess the representative hydraulic fracturing
DCS data confidence score chemicals used in British Columbia, Canada, and the assessment
E endocrine disruptor results were compared with those from the previously developed
EHH environmental and human health HyFFGAS.
GHS globally harmonized system of classification and
labelling of chemicals
HGI/A/F hazard group for ingredient/additive/fracturing
2. Hazard screening and indexing systems
fluid
HII/A/F hazard index for ingredient/additive/fracturing
Both hydraulic fracturing chemical hazard screening and index-
fluid
ing systems are qualitative methodologies, either use descriptive
HS hazard score
terms or numerical rating scales to describe chemical hazards
HyFFGAS hydraulic fracturing fluid greenness assessment
(Ferrari et al., 2016). These systems share a common feature that
system
the assessment processes all begin with ingredients as they are the
HyFI/A/F hazard assessment results for ingredi-
essential components of additives/fracturing fluids. However, the
ent/additive/fracturing fluid from HyFFGAS
hazard screening and indexing systems use different methods to
ICHSIS integrated chemical hazard screening and indexing
present ingredients’ hazards and aggregate the hazards to addi-
system
tive/fluid levels. The assessment results from the two approaches
IES ingredient environmental health hazard score
are also associated with different hazard implications and data
HIS ingredient human health hazard score
uncertainties.
IHVI/A/F integrated hazard value for ingredi-
ent/additive/fracturing fluid
M mutagenicity 2.1. Hazard screening systems
P environmental persistence
R reproductive toxicity Chemical hazard screening aims to select an appropriate
hazard designation for a given chemical. The hazard designa-
tions are assigned based on qualitative hazard description and
increasing public concern over the chemical hazard of hydraulic potency consideration, rather than numerical scales. The Intrinsik
fracturing. Screening-level Assessment System and the GreenScreen System
Although there are various government regulations, industry are two representative chemical hazard screening systems (CPA,
codes-of-practices, and company standard operating procedures in 2016; Intrinsik, 2013). The two systems operate at screening levels
place to minimize the likelihood of unintended release of fractur- with a focus on the defined series of hazard endpoints (e.g., car-
ing fluids, the health risk posed by hydraulic fracturing chemicals cinogenicity, aquatic toxicity) relevant to the EHH hazard profile
to surrounding ecosystems and resource users cannot be neglected. of a chemical. The chemical toxicological data (CTD) of an ingredi-
The downhole performance and cost are two major criteria deter- ent is screened against the selected hazard endpoints to determine
mining the selection of hydraulic fracturing chemicals; When the whether the concerned hazard exists or not, and the severity of
two criteria are met, the use of chemicals with minimum EHH hazard if it exists. The resultant hazard profile is presented in quali-
effects should be encouraged by both the regulatory organizations tative hazard designations, such as the three hazard categories used
and industries for reasons of responsible production and public in the Intrinsik Screening-level Assessment System and the four
confidence (Brannon et al., 2012; CAPP, 2012; Thomas et al., 2019). hazard benchmarks used in the GreenScreen System (CPA, 2016;
The transition towards the use of more environmentally respon- Intrinsik, 2013). Different hazard designations represent different
sible chemicals has posed several challenges such as developing severity levels of EHH hazards. The concentrations of ingredients
frameworks and methodologies which can provide meaningful and within an additive/fluid are also screened against the cut-off con-
reliable chemical hazard assessment results. centrations of hazard endpoints to determine whether the hazard
As a response, various chemical hazard assessment systems is in-effect or not.
have been developed to systematically evaluate EHH hazards and Chemical hazard screening systems can generate descriptive
generate outcomes for informed decision making in hydraulic frac- hazard designations reflective of chemical hazards, without involv-
turing chemical management. The representative systems include ing any numerical conversion and aggregation algorithm. Thus,
the Quantitative Ranking Measure of Oil Field Chemical Envi- the results are relatively objective and easy for hazard communi-
ronmental Impacts (Jordan et al., 2010), Chemical Hazard Rating cation. Nonetheless, hazard screening systems are less applicable
System (Hepburn, 2012), Chemical Scoring Index (Verslycke et al., when comparing two chemicals that have the same hazard designa-
2014), Intrinsik Screening-level Assessment System (Intrinsik, tion. Also, the ingredient concentration evaluation mechanism (i.e.,
2013), Hydraulic Fracturing Fluid Greenness Assessment System the “cut-off” concentration) is binary in hazard screening systems,
(HyFFGAS) (Hurley et al., 2016), and GreenScreen System (CPA, neglecting the fact that the higher concentrations of hazardous
128 G. Hu et al. / Process Safety and Environmental Protection 130 (2019) 126–139
ingredients contained in an additive/fluid, the higher EHH risks
might be posed by the ingredients.
2.2. Hazard indexing systems
Various chemical hazard indexing systems have been devel-
oped to translate the hazard information of hydraulic fracturing
chemicals to a single measure (i.e., index, score) that reflects an
aggregated chemical hazard, allowing for comparing the EHH haz-
ards of different chemicals (Hepburn, 2012; Hurley et al., 2016;
Jordan et al., 2010; Verslycke et al., 2014). Hazard indexing systems
are composed of various hazard endpoints, scoring rules, and score
aggregation algorithms. The CTD of ingredients on the selected
hazard endpoints and their concentrations in an additive/fluid are
transformed to a numerical scale using specific sub-index func-
tions, scoring rule sets, or implicit rating curves (Hurley et al., 2016).
The resultant sub-indices or scores are weighted and aggregated to
produce a final index. Qualitative hazard descriptions are estab-
lished based on the scales of the final indices to facilitate hazard
interpretation and decision making on chemical selection.
When using indexing systems, a few issues can occur as a
result of abstracting information and data. Indexing systems are
not entirely successful in providing the true picture of the assessed
subject due to diverse types of input data and partly because they
are insufficient to aggregate diverse data properly (Sadiq et al.,
2010). The improper aggregation could generate eclipsed, exag-
gerated, and ambiguous results (Sadiq et al., 2010; Swamee and
Tyagi, 2000). For instance, eclipsing occurs when a chemical being
assessed is associated with critical EHH hazards, yet the derived
hazard index comes out at a moderate level, failing to show any
critical hazard due to improper aggregation. Moreover, weighing
sub-indices/scores is a subjective process depending on assessor
and system developers’ opinions. Thus, it is possible that different
hazard indexing systems generate different assessment results for
the same chemical (Hurley et al., 2016). There is a growing need to
develop an integrated system that can not only objectively reflect
the EHH hazard of a chemical for hazard monitoring but also com-
pare the EHH hazards of different chemicals for informed chemical
selection.
3. Integrated screening and indexing system
Informed by the advantages of chemical hazard screening and
indexing systems, ICHSIS was developed to characterize the EHH
hazards of hydraulic fracturing chemicals at ingredient, additive,
and fluid levels. In ICHSIS, EHH hazard is defined as the proper-
ties and characteristics of a chemical that can cause adverse effects
on EHH. The EHH hazards of hydraulic fracturing chemicals are pri-
marily evaluated through water exposures since there is substantial
concern regarding the potential for hydraulic fracturing operations
to contaminate water sources.
3.1. Framework
The framework of ICHSIS is outlined in Fig. 1. The assessment
process begins with chemical data acquisition, including identify-
ing the chemical abstracts service registry numbers (CASRN) and
concentrations of ingredients contained in an additive/fracturing
fluid and searching the CTD for the ingredients. The CTD and
concentration of each ingredient are processed through haz-
ard screening and indexing approaches to generate two hazard
assessment outcomes coupled with data confidence indicators.
An integrated hazard assessment outcome is generated for each
ingredient by amalgamating the hazard screening and indexing
outcomes. The ingredients’ hazard assessment outcomes are then
aggregated to generate a hazard assessment outcome for the addi-
tive/fracturing fluid. Based on the hazard assessment outcomes,
informed decisions on chemical use can be made for EHH hazard
mitigation.
3.2. Hazard endpoints and criteria
The hazard endpoints and criteria inclusive in ICHSIS are shown
in Table 1. The hazard endpoint denotes the type of adverse effects
on EHH, such as carcinogenicity, mutagenicity, and aquatic toxicity
(Exon, 2006). The hazard criteria indicate the severity of a specific
type of adverse effects, such as the Category 1–4 acute/chronic
aquatic toxicity for evaluating the severity of aquatic toxicity.
The definitions of the selected hazard endpoints and criteria can
be referred to the Globally Harmonized System of Classification
and Labelling of Chemicals (GHS) (UN, 2013). In addition to the
conventional hazard endpoints defined in the GHS, an emerging
hazard endpoint-endocrine disruptor (E), was included in ICHSIS
because there is a growing concern about the extent of risk posed
by endocrine disruptors to human and wildlife health (European
Commission, 2018; Kassotis et al., 2017).
The EHH hazard is assessed in the context of unintended releases
of hydraulic fracturing chemicals caused by spill accidents, equip-
ment failure, or loss of well-bore integrity. Thus, physical hazards
(e.g., flammability, explosiveness, corrosiveness) and health haz-
ards due to dermal and inhalation exposure are not assessed as
those hazards are more relevant to workplace safety. However, the
hazard endpoints and exposure routes considered in ICHSIS can be
modified to suit different assessors’ need. As shown in Table 1, each
hazard endpoint was assigned a cut-off concentration for determin-
ing whether the concentration of an ingredient within a mixture is
high enough to trigger the concerned hazard endpoint. The cut-off
concentrations are consistent with those used in other chemical
hazard classification systems, including the Health Canada’s Work-
place Hazardous Materials Information System and the GHS (Health
Canada, 2015; UN, 2013). Also, hazard scores (HS) ranging from 0 to
10 were assigned to the hazard criteria under each hazard endpoint
to differentiate and scale the hazard criteria. A higher HS indicates
a higher level of hazard for the respective endpoint.
3.3. Chemical toxicological data
Hazard screening and indexing rely on the CTD of ingredients.
The quality and availability of CTD greatly affect the data confidence
level of hazard assessment results. A variety of CTD sources, includ-
ing peer-reviewed chemical toxicity databases, material safety data
sheets, suitable ingredient analogs, and chemical toxicity model
simulations, are used in ICHSIS to maximize the availability of CTD
(Appendix I). As Fig. 2 shows, different data sources were divided
into four tiers based on the data confidence implication (CPA, 2016).
A data confidence score (DCS) was assigned to each tier of data
sources for indexing purpose. DCSs range from 0 to 10, where a
higher value indicates higher data certainty of the data source.
A CTD searching rule was established to ensure that assessment
results can be generated with the highest possible data confidence.
As Fig. 2 shows, tier 1 data sources are searched first after identi-
fying the CASRN for an ingredient. If CTD cannot be found in tier 1
data sources, then tier 2 data sources will be searched. Similarly,
tier 3 analog ingredient will be used if CTD lacks in tier 2 data
sources. Analog ingredients can be found using the Analog Identifi-
cation Methodology developed by the US Environmental Protection
Agency (USEPA, 2018). If CTD cannot be found in tier 1–4 data
sources, then a data gap will be identified for the target ingredient
concerning the hazard endpoint. A moderate-level hazard will be
assumed for the data-missing endpoint to generate an assessment
outcome due to the conservativeness of hazard assessment.
 G. Hu et al. / Process Safety and Environmental Protection 130 (2019) 126–139
Fig. 1. Flowchart of integrated hazard screening and indexing system for hydraulic fracturing chemical assessment.
3.4. Hazard screening
The acquired CTD is screened against the hazard endpoints to
generate a hazard screening result for the ingredient. As shown
in Table 2, four hazard groups (HG) were established as possible
results of chemical hazard screening. The HGs were developed in
light of the four benchmarks used by the GreenScreen System (CPA,
2016). Each HG has several hazard classification criteria, and each
criterion is the combination of different EHH hazards. For example,
if an ingredient is associated with high environmental persistence
(P) and high bioaccumulation potential (B), then this ingredient will
be classified into HG1. Numerical values (NHG ) were assigned to the
HGs for further integration with hazard indexing results.
The ingredient hazard screening process is shown in Fig. 3. Inor-
ganic ingredients are required to be assessed differently because
most of them are inherently environmentally persistent. For natu-
rally occurring inorganic substances, persistence is not necessarily
considered a negative characteristic (CPA, 2016). If an inorganic
ingredient is identified as having no significant EHH toxicity, then
it will still be classified into HG4 (CPA, 2016). Also, endpoint chronic
human oral toxicity (ChT) was selected to accommodate the pos-
129
sibility of long-term, repetitive exposure to hazardous ingredients
present in potable water resources as a result of spill accidents.
This endpoint is reserved for ingredients that are identified as
highly persistent in the environment and having the potential to
cause chronic hazard exposure (Intrinsik, 2013). Hence, rapidly and
inherently biodegradable organic ingredients are exempted from
the ChT screening.
As Fig. 4 shows, determining the HG for an additive is a hierar-
chical screening process starting with searching HG1 ingredients.
An additive will be classified into HG1 if it contains at least
one HG1 ingredient with a concentration higher than the cut-
off concentration of the concerned hazard endpoint (Table 1). If
an ingredient’s concentration is lower than the cut-off concen-
tration of a hazard endpoint, then the respective hazard will be
considered negligible (CPA, 2016; Intrinsik, 2013). However, there
is an exceptional situation: additives containing any ingredients
of high P and B hazards will be classified into HG1 regardless
of the cut-off concentrations screening results. This is because if
the additive is spilled, the high P and B ingredients may be long-
lasting in the environment and consequently accumulate in the
receptors’ bodies to cause adverse health effects (CPA, 2016). If
130 G. Hu et al. / Process Safety and Environmental Protection 130 (2019) 126–139

Fig. 2. Four tiers of chemical toxicological data sources and data searching rule (CASRN: chemical abstracts service registry number, DCS: data confidence score; target
ingredient and analog ingredient have different DCSs).

Fig. 3. Hazard screening process at the ingredient level (ChT: chronic human oral toxicity, P: environmental persistence, HG: hazard group).
 G. Hu et al. / Process Safety and Environmental Protection 130 (2019) 126–139 131

Table 1
Environmental and human health hazard endpoints, cut-off concentrations, hazard criteria, and hazard scores inclusive in integrated chemical hazard screening and indexing
system.

Environmental health hazard Human health hazard

Endpoints Cut-off conc. (%) Criteria HSa Endpoints Cut-off conc. (%) Criteria HSa

Rapidly/readily 10 Carcinogenicity (C), c

Group /Category 1d
10
Environmental mutagenicity (M),
1.0 biodegradable 0.1
persistence (P) reproductive toxicity
Inherently 5 Group/Category 5
biodegradable (R), and endocrine 2
Not 0 disruptor (E) Not 0
rapidly/inherently Group/Category
biodegradable 1 or 2
Bioaccumulation 1.0 High 10 Chronic human oral Yes 10
1.0
potential (B) Low 0 toxicity (ChT) No 0
Category 1b 10 Category 1e 10
Acute/chronic
Category 2 6 Acute human oral Category 2 6
aquatic toxicity 1.0 1.0
Category 3 3 toxicity (AhT) Category 3 3
(AT)
Category 4 0 Category 4 0
a
Hazard scores. Hazard scores ∈ [0, 10], and a higher hazard score indicates a higher hazard with respect to the hazard endpoint.
b
Based on acute or chronic LC50 , EC50 , or IC50 values for fish, algae, or daphnia (Category 1: ≤ 1 mg/L, Category 2: > 1 to ≤ 10 mg/L, Category 3: > 10 to ≤ 100 mg/L, and
Category 4: >100 mg/L).
c
Based on the Globally Harmonized System definitions (Group 1: known or presumed carcinogens, mutagens, or reproductive toxicants; Group 2: suspected carcinogens,
mutagens, or reproductive toxicants).
d
Based on the European Commission Endocrine Disruptor Strategy (Category 1: evidence of endocrine disrupting activity in animal tests; Category 2: in vitro evidence of
biological activity related to endocrine disruption).
e
Based on oral toxicity values (Category 1: < 5 mg/kg bodyweight; Category 2: > 5 to ≤ 50 mg/kg bodyweight; Category 3: >50 to ≤ 300 mg/kg bodyweight; Category 4: >
300 mg/kg bodyweight).

Fig. 4. Hazard screening process at additive/fracturing fluid levels (HG: hazard group, P: environmental persistent, B: bioaccumulation potential).

the additive does not contain any HG1 ingredients, then search
for HG2 ingredients and screen the concentrations of ingredients
using the same method. Screening ingredients from HG1 to HG4
and their concentrations to determine the suitable HG for the addi-
tive.
In ICHSIS, the hazard assessment of fracturing fluids is the same
as that of additives. This is because a fracturing fluid can be regarded
as an additive which contains a large number of ingredients diluted
in millions of gallons of water (Kargbo et al., 2010). The hazard
screening results of fracturing fluids are also represented by four
HGs. It is important to note that if a fluid consists of two or more
additives containing the same ingredient, then the total concen-
tration of this ingredient in the fluid will be screened against the
cut-off concentrations.
132 G. Hu et al. / Process Safety and Environmental Protection 130 (2019) 126–139

Table 2 endpoints on their relative importance (Table 3). Each element in

Four hazard groups as chemical hazard screening outcomes.
the lower triangle of the matrix is the reciprocal of an element in
HGa Classification criteria NHG b the upper triangle. The geometric mean of each row of the matrix is
HG 1 c
P : Inherently biodegradable AND B :d
10 calculated, and then the weight of each endpoint (wi ) can be derived
High AND ATe : Category 2 by normalizing the geometric means.
P: Not rapidly/inherently The importance values were assigned according to experts’
biodegradable AND B: High opinions, and they can be modified as required if better infor-
P: Not rapidly/inherently
mation becomes available. Endpoint AT was assigned the highest
biodegradable AND AT: Category 1 OR
C, M, R, or Ef : Group 1 OR AhTg : importance among the three environmental health hazard end-
Category 1 OR ChTh : Yes points since the acute aquatic toxic effect is lethal and immediate.
B: High AND AT: Category 1 OR C, M, R Endpoint B was given the second-high importance since a high B
or E: Group 2 OR AhT: Category 2 OR
ingredient can potentially be accumulated in receptors’ bodies and
ChT: Yes
C, M, R or E: Group 1 cause chronic adverse health effects. Endpoint P was assigned the
HG 2 P: Inherently biodegradable AND AT: 6 lowest importance because if a highly persistent ingredient with-
Category 3 OR C, M, R, or E: Group 2 OR out any significant AT or B effect is released into the environment,
AhT: Category 3 it will not be an immediate health hazard to the environment.
P: Inherently biodegradable AND B:
Among the human health hazard endpoints, endpoint C was
High
P: Not rapidly/inherently assigned the highest importance because it has a serious health
biodegradable AND AT: Category 3 OR hazard implication to the public. Endpoint AhT was assigned the
C, M, R or E: Group 2 OR AhT: Category second-high importance since the toxic effect is immediate and
3
lethal. Endpoints M and R were assigned moderate importance
B: High AND AT: Category 3 OR C, M, R
or E: Group 2 OR AhT: Category 3
because their effects are not lethal and immediate compared to
C, M, R or E: Group 2 C and AhT. Endpoint ChT was assigned relatively low importance
AT: Category 1 OR AhT: Category 1 OR since the adverse effect can only be triggered by repetitive chronic
ChT: Yes hazard exposure. Endpoint E was also assigned low importance
HG 3 P: Not rapidly/Inherently 3
because very few chemical toxicity databases have the data for its
biodegradable OR Inherently
biodegradable evaluation.
B: High An ingredient environmental hazard score (IES) and a human
AT: Category 2 OR 3 hazard score (IHS) are calculated through a weighted sum aggre-
AhT: Category 2 OR 3
gation, respectively:
HG 4 P: Rapidly biodegradable AND B: Low 0
AND AT: Category 4 AND C, M, R, and
E: Not Group 1 or 2 AND AhT: Category

m
IES or IHS = wi · HSi (1)
4 AND ChT: No
a
i=1
Hazard group.
b
Numerical value of hazard group. where wi and HSi are the weights and HS of hazard endpoint i,
c
Environmental persistence.
d respectively, and m is the total number of environmental health and
Bioaccumulation potential.
e
Acute/chronic aquatic toxicity. human health hazard endpoints, respectively. An ingredient hazard
f
Carcinogenic, mutagenic, reproductive toxic, and endocrine disruptive effects. index (HII ) is determined using the maximum operator function:
g
Acute human oral toxicity.
h
Chronic human oral toxicity. HII = Max (IES, IHS) (2)

The HII reflects the highest possible hazard of an ingredient to

3.5. Hazard indexing
A hazard indexing approach is used in combination with the
hazard screening approach. The conversion of multi-dimension
non-commensurate chemical hazard data into numerical indices
involves several steps, including scoring hazard criteria, weigh-
ing hazard endpoints, aggregating scores to generate an index, and
scaling and interpreting the derived index.
The HSs of hazard criteria (Table 1) are aggregated according to
the weights of hazard endpoints to generate a final hazard index. A
set of weights of m hazard
endpoints
m
can be written as W = (w1 , w2 ,
. . ., wi , . . ., wm ), where i=1
wi = 1. The analytical hierarchy pro-
cess (AHP) was used to assign weights (wi ) to hazard endpoints.
AHP can generate a weight for each hazard endpoint according
to pairwise comparisons of the relative importance of endpoints
(Saaty, 2008). A higher weight indicates higher relative importance
of the endpoint. As shown in Table 3, the pairwise relative impor-
tance comparison of two endpoints are measured according to a
numerical scale from 1 to 9.
In the indexing approach, an ingredient’s environmental health
hazard and human health hazard are assessed separately, enabling
assessors to know the most critical hazard more intuitively. As
a result, two matrices (JE and JH ) were established for pairwise
comparisons of environmental health and human health hazard
either environmental health or human health.
After hazard screening and indexing, a HG designation (HGI )
and a HII can be generated for an ingredient. HGI shows the
inherent EHH hazard objectively, while HII incorporates assessors’
judgments on the relative importance of different hazard end-
points. Both HGI and HII are integrated to generate a final hazard
assessment outcome for the ingredient. Because HG can reflect the
EHH hazard more objectively than HI, a higher weight should be
assigned to HG. Different pairwise mathematical weights (wHG ,
wHI ) were assigned to HG and HI under five scenarios: S1 (0.5, 0.5),
S2 (0.6, 0.4), S3 (0.7, 0.3), S4 (0.8, 0.2), and S5 (0.9, 0.1), for inte-
grating hazard screening and indexing results, where a higher wHI
suggests more influence of experts’ judgment on assessment out-
comes. Under each scenario, an integrated hazard value (IHV) can
be calculated:
IHV = wHG · NHG + wHI · HI (3)
where NHG is the numerical value of HG (Table 2). For an addi-
tive consists of n ingredients, the additive hazard index (HIA ) is
calculated:

n
HIA = HIIj · Cj (4)
j
 G. Hu et al. / Process Safety and Environmental Protection 130 (2019) 126–139 133

Table 3
Matrices of relevant importance of environmental health and human health hazard endpoints.

Matrix Pairwise comparison of endpoints wi Rank

P B AT
P 1.00 0.50 0.20 0.12 3
JE a
B 2.00 1.00 0.33 0.23 2
AT 5.00c 3.00 1.00 0.65 1
C M R AhT ChT E
C 1.00 5.00 5.00 3.00 5.00 5.00 0.44 1
M 0.20 1.00 3.00 0.33 3.00 3.00 0.14 3
b R 0.20 0.33 1.00 0.33 3.00 3.00 0.10 4
JH
AhT 0.33 3.00 3.00 1.00 3.00 3.00 0.22 2
ChT 0.20 0.33 0.33 0.33 1.00 1.00 0.05 5
E 0.20 0.33 0.33 0.33 1.00 1.00 0.05 5
a
Environmental health hazard endpoints importance matrix (consistency ratio = 0.4% < 10%, acceptable).
b
Human health hazard endpoints importance matrix (consistency ratio = 7.3% < 10%, acceptable).
c
Relative importance value: 1-two endpoints are equally important, 3-one endpoint is moderately more important than the other, 5-strongly more important, 7-very
strongly more important, 9-extremely more important; importance values of 2, 4, 6, 8 in-betweens. The example shows that hazard endpoint AT is 5 times (strongly) more
important than hazard endpoint P.

Table 4 ment results. At the ingredient level, DCI is presented separately

A scaling system for interpreting environmental and human health hazard levels
for environmental health (DCIE ) and human health (DCIH ) hazard
based on chemical hazard assessment outcomes.
assessment results. The data confidence index is calculated based
Hazard Hazard level Interpretation on the DCSs (Fig. 2) of different CTD sources for endpoint i using Eq.
assessment
(5):
outcome

(7, 10] Very high The chemical is a serious threat (e.g., 

m

immediate toxic and/or lethal effect) to DCSi

environmental and/or human health. i
Its use should be avoided. DCI = (5)
(5, 7] High The chemical is an environmental 
m

and/or human health hazard of high Max DCSi

concern (e.g., sub-lethal effect). It is not i
allowed for use unless chemicals with
lower hazards cannot be found. At the ingredient level, the maximum sum of DCS for environ-
(3, 5] Medium The chemical is of moderate mental health hazard is 30 and for human health hazard is 60. The
environmental and/or human health resultant DCI is in a range from 0 to 1, where a higher value denotes
hazards. It is allowed for use, but
opportunities exist for hazard
higher data confidence of assessment results. Similarly, the DCIA
mitigation by using chemicals with and DCIF can be calculated for additive/fluid hazard assessment
lower EHH hazards. results using Eq. (5), respectively. A DCI scaling system (Table 5)
(0, 3] Low The chemical is a potential hazard to was also established to interpret the data certainty of hazard assess-
environmental and/or human health
(e.g., the chronic adverse effects
resulted from long-term hazard Table 5
exposures), which is allowed for use A scaling system for evaluating data certainty/uncertainty levels of hazard assess-
with cautions. ment results.
0 No hazard The chemical is not a significant hazard
to environmental or human health, DCIa Level Interpretation
which is recommended for use.
(0.75, 1.00] High Signals that a substantial amount of
credible CTDb exists for the substance
across the EHH hazard endpoints.
where HIIj and Cj are the hazard index and the normalized max- Uncertainty with respect to the
assessment result is low.
imum concentration of the jth ingredient within the additive,
(0.50, 0.75] Medium-to- Signals a lower, but still appreciable
respectively. If an additive contains any undisclosed ingredients, high amount of CTD exists for the substance
then the undisclosed ingredients will be considered as having no across the EHH hazard endpoints. The
significant EHH hazards (CCOHS, 2018). Similarly, a fracturing fluid credibility of data is also lower. The
hazard index (HIF ) can be calculated using Eq. (4). Based on the uncertainty of the assessment result
remains relatively low.
determined HGA/F and HIA/F , an IHVA/F can also be calculated for
[0.25, 0.50) Low-to- Signals a lower amount of CTD exists
an additive/fracturing fluid using Eq. (3), respectively. As shown in medium for the substance across the EHH
Table 4, a scaling system was established for hazard assessment hazard endpoints. Also, the data
outcome interpretation. The scaling system was developed in light credibility is not high. Uncertainty
surrounding the assessment result is
of the environmental and health hazard scoring system used in
increased. Further review is
HyFFGAS (Hurley et al., 2016). recommended.
[0, 0.25) Low Signals both the amount of CTD and
3.6. Data confidence evaluation the data credibility are low for the
substance across the EHH hazard
endpoints. Uncertainty surrounding
It is important to evaluate the data confidence levels of assess- the assessment result is high. Further
ment results since they can greatly affect the decision making in review is strongly recommended.
chemical management. A data confidence index (DCI) is calculated a
DCI: data confidence index calculated for ingredients, additives, and fracturing
for each ingredient, additive (DCIA ), and fracturing fluid (DCIF ) as fluids.
b
a measurement of the data certainty/uncertainty of hazard assess- CTD: Chemical toxicological data.
134 G. Hu et al. / Process Safety and Environmental Protection 130 (2019) 126–139

Fig. 5. Ingredient hazard screening results.

ment results. The four data confidence levels used in the DCI scaling assessment. As a result, a total of 25 additives were selected. The
system were established in accordance with the data availability ingredient compositions of the selected additives are included in
measurements of the Intrinsik Screening-level Assessment System Appendix II.
(Intrinsik, 2013).

4.1. Ingredient hazard assessment

4. Application
The developed ICHSIS was applied to assess the representa-
tive hydraulic fracturing additives used in British Columbia. The
additive data was collected from the FracFocus database from
November 2011 to August 2014. Different additives were grouped
into 13 functional categories such as gelling agent, crosslinker, and
biocide according to their designed functions (Hu et al., 2018a).
Additives with a use percentage > 10% within the respective func-
tional category were considered representative and selected for
The selected additives comprise 43 different ingredients. Among
these ingredients, twelve were reported without CASRNs; hence,
analog ingredients were used to substitute the CASRN-missing
ingredients. As Fig. 5 shows, about 21% of the assessed ingredients
were classified into HG1, and these ingredients should be avoided
for use in hydraulic fracturing operations from a hazard mitigation
perspective. No special HG1 ingredient characterized by high P and
B hazards was identified. Nearly half of the assessed ingredients
were HG2 substances, suggesting that the supplementary hazard
 G. Hu et al. / Process Safety and Environmental Protection 130 (2019) 126–139
Fig. 6. Comparisons of ingredient hazard indexing results (HII ), integrated hazard values (IHVI ) under five scenarios (S1 to 5), and results from HyFFGAS (HyFI ).
indexing approach is desirable to aid in the comparison of ingredi-
ents within the same HG. Only 9% of the ingredients were identified
as non-hazardous HG4 ingredients.
Among the ingredients assessed, no confirmed or suspected
endocrine disruptor was found. Environmental persistence and
high aquatic toxicity are the main environmental health concerns
for the ingredients. This finding is generally consistent with the
results from the previous comprehensive chemical hazard assess-
ment, in which P (30%) and AT (27%) were confirmed as the causes
of high environmental health hazard (Hu et al., 2018a). About 20
to 25% of the assessed ingredients were associated with the GHS
Group 1 or 2 adverse human health effects (i.e., C, M, and R). AhT
was not identified as a significant hazard because the majority of
ingredients (80%) are associated with the GHS Category 4 acute
oral toxicity. Nevertheless, roughly 21% of the ingredients were
confirmed with ChT, which might cause long-term adverse health
effects.
The ingredients’ hazard indexing results (i.e., HII ) were com-
pared with the integrated hazard results (i.e., IHVI ) and the results
from HyFFGAS. The IHVs were calculated under five scenarios (S1
to S5) defined by different pairwise mathematical weights of HG
and HI. HyFFGAS generates ingredient greenness scores on a scale
from 0 to 10, where a higher greenness score indicates a lower level
of EHH hazard, so the greenness scores were subtracted by ten to
generate a hazard index (HyF) for comparison (Hurley et al., 2016).
Based on the results, the hazard levels of ingredients were deter-
mined and compared according to the hazard scaling system shown
in Table 4.
As Fig. 6 shows, there is a significant difference between the haz-
ard assessment results from the individual hazard indexing and
the integrated approaches. The HII show that about 35% of the
assessed ingredients fall within “high” and “very high” hazard lev-
els, while the IHVI indicate that higher percentages (40 to 68%) of
ingredients were categorized into “high” and “very high” hazard
levels under five weighing scenarios. The difference reveals that
the individual indexing approach could underestimate ingredients’
hazards. Moreover, the scenario-based assessments found that a
higher wHG could lead to more critical hazard assessment results.
The percentage of “high” hazard ingredients increased from 21 to
47% as wHG increases from 0.5 (S1) to 0.9 (S5), while the percentage
of “medium” hazard ingredients decreased from 37 to 9%. The per-
centages of ingredients with “no”, “low”, and “very high” hazards
were relatively insensitive to the change of wHG .
The comparison between the IHVI and HyFI also shows a differ-
ence. About 9% of the ingredients were categorized into the “very
high” hazard level based on the indexing results from HyFFGAS
(Fig. 6). This value is significantly lower than the percentage (21%)
identified by ICHSIS. A total of 20% of ingredients were catego-
rized into the “high” hazard level by HyFFGAS, which is also lower
than the percentage (30%) determined by ICHSIS under a moderate
135
weighting scenario (S3). The results further suggest that individual
hazard indexing systems could generate underestimated hazard
assessment results compared to the integrated system.
The underestimated EHH hazards by HyFFGAS can be attributed
to its hazard aggregation method, in which equal weights are
assigned to environmental health and human health hazard assess-
ment outcomes to generate a final EHH hazard score. For example,
ingredient Benzene, C10-16-alkyl derivatives (CASRN: 68648-87-
3) is a significant environmental health hazard concern because of
its high bioaccumulation potential (ECCC, 2018) and the GHS Cate-
gory 1 aquatic toxicity (ECHA, 2018); however, this substance is not
linked to any significant human health hazard. This ingredient was
classified into HG1 and a HII of 8.8 was calculated by using ICHSIS.
Under the least strict weighting scenario (S1), an IHVI of 9.4 was
determined, indicating that the ingredient is associated with “very
high” EHH hazard. In comparison, HyFFGAS generated an environ-
mental health hazard score of 9 and a human health hazard score
of 2 for this ingredient. An ingredient hazard score of 5.5 was cal-
culated by assigning equal weight to the two types of hazard. The
hazard score indicates that the ingredient can be categorized into
the “high” hazard level (Hurley et al., 2016). Thus, for the same
ingredient, the hazard assessment result of HyFFGAS is less critical
than that of ICHSIS.
The IHVI derived from a moderate weighting scenario (S3) were
selected for further comparison of hazard assessment and data
confidence results. The distribution of values from different ingre-
dient hazard assessment approaches are shown in Fig. 7a. Both the
median and mean values of IHVI -S3 are higher than those of HII
and HyFI , suggesting a more critical ingredient EHH hazard pro-
file. It is also noteworthy that the mean and median values of IES
are significantly higher (p < 0.05) than those of IHS, indicating that
environmental health hazard is more critical than human health
hazard at the ingredient level.
The data confidence performance of different ingredient haz-
ard assessment results is shown in Fig. 7b. Since HyFFGAS does
not have a function for data confidence evaluation, the DCIs of the
assessment results from HyFFGAS were calculated using the same
approach (Eq. 5) used in ICHSIS. It can be seen that the data confi-
dence performance was significantly (p < 0.05) improved by ICHSIS.
The ingredient assessment results from ICHSIS are associated with
“high” level of data confidence (Table 5), while the results from
HyFFGAS are associated with much lower data confidence. The high
data confidence can be attributed to the diverse CTD sources used
in ICHSIS. In comparison, HyFFGAS uses material safety data sheets
as the only CTD source, which is equivalent to the tier 2 data source
used in ICHSIS (Hurley et al., 2016). Using tier 1 chemical toxic-
ity databases not only increases the availability of CTD but also
improves data credibility. Moreover, ICHSIS uses analog ingredi-
ents to substitute the CASRN-missing ingredients, which can also
significantly reduce the data uncertainty.
136 G. Hu et al. / Process Safety and Environmental Protection 130 (2019) 126–139
Fig. 7. Comparisons of (a) ingredient hazard assessment results (IES: ingredient
environmental health hazard score, IHS: ingredient human health hazard score,
HII : ingredient hazard index, IHVI -S3: integrated hazard value of ingredients under
scenario 3, HyFI : ingredient hazard index from HyFFGAS) and (b) data confidence
indices (DCIE : data confidence index-ingredient environmental health hazard, DCIH :
data confidence index-ingredient human health hazard).
4.2. Additive hazard assessment
Among the additives assessed, about 28% were categorized into
HG1. These HG1 additives contain at least one HG1 ingredient at
a concentration higher than the cut-off values. The relatively large
percentage of HG1 additives indicates that the need for using addi-
tives with lower EHH hazards is significant. About 44% and 16% of
additives were identified as HG2 and HG3 chemicals, respectively.
The high percentage of HG2 additives also indicates that it is nec-
essary to use the hazard indexing approach to compare the EHH
hazards of additives within the same HG. Only 12% of the additives
were identified as having no significant EHH hazard.
As Fig. 8 shows, about 20% of the assessed additives were clas-
sified into “high” and “very high” hazard levels based on HIA . After
integrating the hazard screening results, the percentages of addi-
tives with “very high” and “high” hazards increased from 8 to 28%
Fig. 8. Comparisons of additive hazard indexing results (HIA ), integrated hazard values of additives (IHVA ) under five scenarios (S1 to 5), and results from HyFFGAS (HyFA ).
Fig. 9. Comparisons of (a) additive hazard assessment outcomes (HIA : additive haz-
ard index, IHVA -S3: integrated hazard values of additives under scenario 3, HyFA :
additive hazard index from HyFFGAS) and (b) data confidence indices (DCIA : data
confidence index-additive, DCIA -HyF: data confidence index-results from HyFFGAS).
and 12 to 24%, respectively. These percentages also increase as a
result of increasing wHG from S1 to 5. Nevertheless, the percentage
of additives identified without any significant hazard remains the
same from S1 to 5. On the other hand, the indexing results (i.e.,
HyFA ) from HyFFGAS indicate that a total of 20% of the additives
are associated with “very high” and “high” hazards, which is signif-
icantly lower than the result (52%) from ICHSIS under a moderate
weighting scenario (S3). The comparison shows that using individ-
ual hazard indexing methods could also generate underestimated
hazard assessment outcomes at the additive level.
The integrated additive hazard assessment results calculated
under S3 (i.e., IHVA -S3) were selected for comparing the distribu-
tions of values. As Fig. 9a shows, the mean and median values of
IHVA -S3 are higher than those of HIA and HyFA , suggesting a higher
overall EHH hazard at the additive level. As Fig. 9b shows, the DCIA
from ICHSIS are much higher than the DCIA -HyF from HyFFGAS, and
the improvement is significant (p < 0.05). The data confidence of the
 G. Hu et al. / Process Safety and Environmental Protection 130 (2019) 126–139 137

Table 6
Hazard assessment results of three hypothetical fracturing fluids.

Additive Ingredient CASRN Conc. (%) in Conc. (%) in fracturing fluid Assessment resultsa
additive

F1 F2 F3 Ingredient Additive Fracturing fluid

2-Mercaptoethanol 60-24-2 90 2.40E-03 2.40E-02 2.40E-03 (1, 7.7, 9.3)

Iron control agent Cupric chloride 7447-39-4 10 2.60E-04 2.60E-03 2.60E-04 (1, 7.7, 9.3) (1, 6.1, 8.8)
Monoethanolamide 141-43-5 30 8.00E-04 8.00E-03 8.00E-04 (3, 0.7, 2.3)
Alkyl benzene 68584-22-5 85 2.05E-03 2.05E-02 2.05E-02 (2, 1.0, 4.5)
sulphuric acid
Anti-sludge agent (1, 1.6, 7.5)
Methanol 67-56-1 10 2.41E-04 2.41E-03 2.41E-03 (3, 3.9, 3.3)
Benzene, 68648-87-3 5 1.20E-04 1.20E-03 1.20E-03 (1, 7.7, 9.3)
C10-16-alkyl
derivatives
Sulphuric acid 7664-93-9 5 1.20E-04 1.20E-03 1.20E-03 (3, 1.2, 2.5)
Methanol 67-56-1 50 5.00E-03 5.00E-02 5.00E-02 (2, 0.5, 4.4) F1: (4, 4.6, 1.4)
Activator (2, 4.0, 5.4)
Alcohols, C12-14 84133-50-6 70 8.00E-03 8.00E-02 8.00E-02 (2, 6.5, 6.2) F2: (1, 4.6, 8.4)
secondary, F3: (2, 2.5, 5.0)
ethoxylated
Ethylene glycol 107-21-1 60 8.29E-04 8.29E-03 8.29E-03 (2, 0.5, 4.4)
Scale control agent (2, 0.3, 4.3)
Non-hazardous – 60 8.29E-03 8.29E-02 8.29E-03 (4, 0.0, 0.0)
ingredients
Glutaraldehyde 111-30-8 20 1.95E-04 1.95E-03 1.95E-03 (2, 6.5, 6.2)
Biocide Methanol 67-56-1 10 1.60E-06 1.60E-05 1.60E-05 (2, 0.5, 6.0) (2, 1.4, 4.6)
Non-hazardous – 70 1.12E-05 1.12E-04 1.12E-04 (4, 0.0, 0.0)
ingredients
Ammonium 7727-54-0 5 4.24E-04 4.24E-03 4.24E-04 (3, 3.2, 3.1)
Breaker (3, 0.2, 2.1)
persulfate
Non-hazardous – 95 8.05E-03 8.05E-02 8.05E-03 (4, 0.0, 0.0)
ingredients
1,6-Hexandiamine, 6055-52-3 40 7.47E-03 7.47E-02 7.47E-02 (4, 0.0, 0.0)
Clay control agent (4, 0.0, 0.0)
dihydrochloride
Non-hazardous – 60 1.12E-02 1.12E-01 1.12E-01 (4, 0.0, 0.0)
ingredients
Phenol 9003-35-4 95 6.11E-02 6.11E-01 6.11E-02 (1, 7.7, 9.3)
Gelling agent (1, 7.4, 9.2)
formaldehyde resin
Phosphoric Acid 7664-38-2 5 3.21E-03 3.21E-02 3.21E-03 (3, 1.2, 2.5)
Monoethanolamide 141-43-5 60 8.75E-04 8.75E-03 8.75E-04 (3, 0.7, 2.3)
Crosslinker Boric acid 10043-35-3 13 1.17E-03 1.17E-02 1.17E-03 (1, 3.2, 8.0) (1, 0.8, 7.3)
Non-hazardous – 27 1.02E-03 1.02E-02 1.02E-03 (4, 0.0, 0.0)
ingredients
a
Assessment results are presented as (hazard group, hazard index, integrated hazard value-scenario 3) for ingredients, additives, and fracturing fluids.

results from ICHSIS is primarily at the “high” level, while the data
confidence of HyFFGAS assessment results mainly lies between the
“low-to-medium” and “medium-to-high” levels. The high data con-
fidence of additive hazard assessment results from ICHSIS can be
attributed to the high data confidence of ingredient hazard assess-
ment results.
4.3. Fracturing fluid hazard assessment
Three hypothetical fracturing fluids (i.e., F1, F2, and F3) were
designed for hazard assessment at the fluid level. As Table 6 shows,
the fracturing fluids contain the same additives/ingredients from
different functional categories, but the concentrations of ingre-
dients are different. F1 contains the lowest concentrations of
ingredients among all the three fluids. The ingredients’ concen-
trations in F2 are ten times higher than the concentrations of the
respective ingredients in F1. F3 contains several additives such as
iron control agent, activator, and biocide at high concentrations,
while the concentrations of the remaining additives are the same
to those in F1. The total concentration of ingredients is < 1% in each
fracturing fluid, which is reasonable as chemicals normally only
account for less than 2% of fracturing fluid (All Consulting, 2012;
Soeder et al., 2014). The IHVF of the three fracturing fluids were
calculated under a moderate weighting scenario (S3).
The hazard screening results (Table 6) show that F1 can be cate-
gorized into HG4, which means that no significant EHH hazard was
determined in F1 despite the fact that it contains several HG1 ingre-
dients. This is because the concentrations of ingredients in F1 are
lower than the cut-off concentrations of various hazard endpoints.
The IHVF of F1 was calculated as 1.4, reflective of a “low” hazard
level according to the hazard scaling system (Table 4). In compar-
ison, F2 was categorized into HG1 due to the high concentrations
of the HG1 ingredients. Accordingly, the IHVF of F2 (8.4) is much
higher than that of F1, indicating a “very high” level EHH hazard.
Hence, from an EHH hazard mitigation perspective, F2 needs to be
reformulated by using alternative ingredients with lower EHH haz-
ards or lowering the concentrations of the HG1 ingredients (i.e.,
< the cut-off concentrations). Nonetheless, the individual hazard
indexing result suggests that F2 is associated with a “medium” level
EHH hazard, which is allowed for use.
F3 was categorized into HG2, suggesting that its EHH hazard
lies between F1 and F2. The concentrations of all the HG1 ingredi-
ents in F3 are lower than the cut-off values, so the HG2 ingredients
were screened following the fluid screening hierarchy (Fig. 4). The
concentrations of HG2 ingredients, such as alkyl benzene sulphuric
acid and methanol, exceed the cut-off values, resulting in a positive
HG2 designation for F3. The IHVF of F3 (5.0) indicates that the fluid
has a “medium” level EHH hazard, in which the HG2 ingredients
are recommended to be used at lower concentrations or substi-
tuted by HG4 alternatives for hazard mitigation. In comparison,
the individual hazard indexing approach generated an underesti-
mated hazard (i.e., a “low” level hazard based on a HIF of 2.5) for
F3. The results once again show that the individual hazard indexing
approach could result in eclipsed EHH hazard at the fluid level.
138 G. Hu et al. / Process Safety and Environmental Protection 130 (2019) 126–139
5. Conclusions
Different chemical hazard assessment methods have been
developed to measure the hazard profiles of hydraulic fracturing
chemicals. The existing methods can be divided into hazard screen-
ing and indexing approaches. By reviewing the advantages and
limitations of the two approaches, ICHSIS was developed to assess
the EHH hazard of hydraulic fracturing chemicals used at ingredi-
ent, additive, and fracturing fluid levels. The integrated system was
applied to the representative chemicals used in British Columbia.
The results from the individual hazard indexing, ICHSIS, and
the previously developed HyFFGAS were compared. The hazard
screening results show that more than half of the ingredients and
additives can be grouped into high EHH hazard designations such
as HG1 and 2, suggesting that the need for hazard mitigation is
necessary. More critically, the comparison of results from different
approaches indicates that the individual hazard indexing approach
could generate underestimated EHH hazard assessment outcomes
at different chemical use levels, and thus an integrated hazard
assessment approach is required for more realistic chemical hazard
assessments. The comparison also shows that the data confidence
level of the results was significantly improved by ICHSIS. The devel-
oped ICHSIS represents an improved chemical hazard assessment
framework, which can promote progress toward more sustainable
unconventional gas production.
Acknowledgments
The authors would like to thank the Shale Water Steering and
Technical Committee of Canadian Association of Petroleum Pro-
ducers (CAPP), British Columbia Oil and Gas Commission (BCOGC),
British Columbia Oil and Gas Research and Innovation Society (BC
OGRIS), and Mitacs Accelerate Program for their financial and tech-
nical support for this study. The authors would also like to thank
the editor and anonymous reviewers for their help in improving
the quality of manuscript.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in
the online version, at doi:https://doi.org/10.1016/j.psep.2019.08.
002.
References
Akob, D.M., Mumford, A.C., Orem, W., Engle, M.A., Klinges, J.G., Kent, D.B., Cozzarelli,
I.M., 2016. Wastewater disposal from unconventional oil and gas development
degrades stream quality at a West Virginia injection facility. Environ. Sci. Tech-
nol. 50, 5517–5525.
All Consulting, 2012. The Modern Practices of Hydraulic Fractur-
ing: A Focus on Canadian Resources. Petroleum Technology
Alliance Canada and Science and Community Environmental
Knowledge Fund, Tulsa, Oklahoma, Accessed 20 Sept 2018 www.all-
llc.com/publicdownloads/ModernPracticesHFCanadianResources.pdf.
Boudet, H., Clarke, C., Bugden, D., Maibach, E., Roser-Renouf, C., Leiserowitz, A.,
2014. “Fracking” controversy and communication: using national survey data to
understand public perceptions of hydraulic fracturing. Energy Policy 65, 57–67.
Brannon, H.D., Daulton, D.J., Post, M.A., Hudson, H.G., Jordan, A.K., 2012. The Quest to
Exclusive Use of Environmentally Responsible Fracturing Products and Systems.
SPE 152068, Presented at the SPE Hydraulic Fracturing Technology Conference.
Society of Petroleum Engineers (SPE), Woodlands, USA, pp. 6–8, Feb 2012.
CAPP, 2012. CAPP’s Guiding Principles and Operating Practices for Hydraulic
Fracturing. Canadian Association of Petroleum Producers (CAPP), Cal-
gary, Alberta, Accessed 20 Sept 2018 http://www.capp.ca/canadaindustry/
naturalGas/ShaleGas/Pages/default.aspx#operating.
CCOHS, 2018. Health and Safety Fact Sheets, WHMIS 1988 - Material Safety
Data Sheets (MSDSs): Creating. Canadian Center for Occupational Health and
Safety (CCOHS), Accessed 16 Sept 2018 https://www.ccohs.ca/oshanswers/
legisl/msds prep.html.
Cozzarelli, I.M., Skalak, K.J., Kent, D.B., Engle, M.A., Benthem, A., Mumford, A.C., Haase,
K., Farag, A., Harper, D., Nagel, S.C., Iwanowicz, L.R., Orem, W.H., Akob, D.M.,
Jaeschke, J.B., Galloway, J., Kohler, M., Stoliker, D.L., Jolly, G.D., 2017. Environ-
mental signatures and effects of an oil and gas wastewater spill in the Williston
Basin, North Dakota. Sci. Total Environ. 579, 1781–1793.
CPA, 2016. GreenScreen® For Safer Chemicals Hazard Assessment Guidance. Version
1.3, March 2016. Clean Production Action (CPA), Somerville, Massachusetts.
ECCC, 2018. Environment and Climate Change Canada (ECCC), the Canadian
Environmental Protection Act, Searching Engine for the Results of Domestic
Substances List (DSL) Categorization, Accessed 20 Sept 2018 https://pollution-
waste.canada.ca/substances-search/Substance?lang=en.
ECHA, 2018. Inventory Substance Information Database. European Chemicals
Agency (ECHA), Helsinki, Finland, Accessed 20 Sept 2018 https://echa.europa.
eu/information-on-chemicals.
Engle, A.M., Cozzarelli, I.M., Smith, B.D., 2014. USGS Investigations of Water Produced
During Hydrocarbon Reservoir Development. U.S. Geological Survey Fact Sheet
2014–3104, United States Geological Survey, Virginia, US, http://dx.doi.org/10.
3133/fs20143104.
European Commission, 2018. European Commission Environment Strategy-
endocrine Disruptors, Annex 1-Candidate List of 553 Substances, Accessed 19
Sept 2018 http://ec.europa.eu/environment/archives/docum/pdf/bkh annex
01.pdf.
Exon, J.H., 2006. A review of the toxicology of acrylamide. J. Toxicol. Environ. Health
B Crit. Rev. 9, 397–412.
Ferrari, F., Giacomini, A., Thoeni, K., 2016. Qualitative rockfall hazard assess-
ment: a comprehensive review of current practices. Rock Mech. Rock Eng. 49,
2865–2922.
FracFocus, 2014. Ground Water Protection Council and Interstate Oil and Gas Com-
pact Commission, FracFocus Chemical Disclosure Registry, Accessed 19 Sept
2018 http://fracfocus.ca.
Gallegos, T.J., Varela, B.A., 2014. Trends in Hydraulic Fracturing Distributions
and Treatment Fluids, Additives, Proppants, and Water Volumes Applied to
Wells Drilled in the United States From 1947 Through 2010-data Analy-
sis and Comparison to the Literature. The U.S. Geological Survey, Reston,
Virginia.
Health Canada, 2015. Guidance: Disclosure of Ingredient Concentrations and Con-
centration Ranges on Safety Data Sheets. Health Canada, Ottawa, Ontario, July
31, 2015, http://whmis.org/documents/HPR Concentration ranges guidance
2015 final en.pdf Accessed 19 Sept 2018.
Hepburn, K., 2012. Development and Practical Application of a Chemical Hazard
Rating System. SPE 160548, Presented at the SPE Annual Technical Conference
and Exhibition. Society of Petroleum Engineers (SPE), San Antonio, USA, pp. 8–10,
Oct 2012.
Hu, G., Liu, T., Hager, J., Hewage, K., Sadiq, R., 2018a. Hazard assessment of hydraulic
fracturing chemicals using an indexing method. Sci. Total Environ. 619–620,
281–290.
Hu, G., Kaur, M., Hewage, K., Sadiq, R., 2018b. Fuzzy clustering analysis of hydraulic
fracturing additives for environmental and human health risk mitigation. Clean
Technol. Environ. Policy., http://dx.doi.org/10.1007/s10098-018-1614-3.
Hurley, T., Chhipi-Shrestha, G., Gheisi, A., Hewage, K., Sadiq, R., 2016. Characteriz-
ing hydraulic fracturing fluid greenness: application of a hazard-based index
approach. Clean Technol. Environ. Policy 3, 647–668.
Intrinsik, 2013. A Screening-level Assessment System for Categorizing Hydraulic
Fracturing Fluid Additives According to Potential Human Health and Environ-
mental Risks. Calgary, Alberta.
Jordan, A., Daulton, D., Cobb, J.A., Grumbles, T., 2010. Quantitative Ranking Measures
Oil Field Chemicals Environmental Impact. SPE 135517SPE 84576-MS, Presented
at the SPE Annual Technical Conference and Exhibition. Society of Petroleum
Engineers (SPE), Florence, Italy, pp. 19–22, Sept 2010.
Kahrilas, G.A., Blotevogel, J., Stewart, P.S., Borch, T., 2014. Biocides in hydraulic frac-
turing fluids: a critical review of their usage, mobility, degradation, and toxicity.
Environ. Sci. Technol. 1, 16–32.
Kahrilas, G.A., Blotevogel, J., Corrin, E.R., Borch, T., 2016. Downhole transformation of
the hydraulic fracturing fluid biocide glutaraldehyde: implications for flowback
and produced water quality. Environ. Sci. Technol. 50, 11414–11423, http://dx.
doi.org/10.1021/acs.est.6b02881.
Kargbo, D.M., Wilhelm, R.G., Campbell, D.J., 2010. Natural gas plays in the mar-
cellus shale: challenges and potential opportunities. Environ. Sci. Technol. 44,
5679–5684, http://dx.doi.org/10.1021/es903811p.
Kassotis, C.D., Tillitt, D.E., Davis, J.W., Hormann, A.M., Nagel, S.C., 2017. Estrogen and
androgen receptor activities of hydraulic fracturing chemicals and surface and
ground water in a drilling-dense region. Endocrinology 155, 897–907, http://dx.
doi.org/10.1210/en.2013-1697.
NEB, 2017. Canada’s Role in the Global LNG Market. Energy Market Assessment. July
2017. National Energy Board (NEB), Ottawa, ON, Canada.
Orem, W., Varonka, M., Crosby, L., Haase, K., Loftin, K., Hladik, M., Akob, D.M., Tatu,
C., Mumford, A., Jaeschke, J., Bates, A., Schell, T., Cozzarelli, I., 2017. Applied
geochemistry organic geochemistry and toxicology of a stream impacted by
unconventional oil and gas wastewater disposal operations. Appl. Geochem. 80,
155–167.
Renock, D., Landis, J.D., Sharma, M., 2016. Reductive weathering of black shale and
release of barium during hydraulic fracturing. Appl. Geochem. 65, 73–86, http://
dx.doi.org/10.1016/j.apgeochem.2015.11.001.
Saaty, T.L., 2008. Decision making with the analytic hierarchy process. Int. J. Serv.
Sci. 1, 83–98.
Sadiq, R., Haji, S.A., Cool, G., Rodriguez, M.J., 2010. Using penalty functions to evaluate
aggregation models for environmental indices. J. Environ. Manage. 3, 706–716.
Soeder, D.J., Sharma, S., Pekney, N., Hopkinson, L., Dilmore, R., Kutchko, B., Stewart,
B., Carter, K., Hakala, A., Capo, R., 2014. An approach for assessing engineering
 G. Hu et al. / Process Safety and Environmental Protection 130 (2019) 126–139
risk from shale gas wells in the United States. Int. J. Coal Geol. 126, 4–19, http://
dx.doi.org/10.1016/j.coal.2014.01.004.
Stringfellow, W.T., Domen, J.K., Camarillo, M.K., Sandelin, W.L., Borglin, S., 2014.
Physical, chemical, and biological characteristics of compounds used in
hydraulic fracturing. J. Hazard. Mater. 275, 37–54, http://dx.doi.org/10.1016/
j.jhazmat.2014.04.040.
Swamee, P.K., Tyagi, A., 2000. Describing water quality with aggregate index. J.
Environ. Eng. 5, 451–455.
Thomas, L., Tang, H., Kalyon, D.M., Aktas, S., Arthur, J.D., Blotevogel, J., Carey, J.W.,
Filshill, A., Fu, P., Hsuan, G., Hu, T., Soeder, D., Shah, S., Vidic, R.D., Young, M.H.,
2019. Toward better hydraulic fracturing fluids and their application in energy
production: a review of sustainable technologies and reduction of potential
environmental impacts. J. Petrol. Sci. Eng. 173, 793–803, http://dx.doi.org/10.
1016/j.petrol.2018.09.056.
UN, 2013. Globally Harmonized System of Classification and Labelling of Chemi-
cals (GHS), 5th edn. United Nations, New York http://www.unece.org/fileadmin/
DAM/trans/danger/publi/ghs/ghs rev05/English/ST-SG-AC10-30-Rev5e.pdf.
139
US EPA, 2018. Predictive Models and Tools for Assessing Chemicals Under the
Toxic Substances Control Act (TSCA), Analog Identification Methodology (AIM)
Tool. The United States Environmental Protection Agency (EPA), Washington,
D.C, Accessed 20 Sept 2018 https://www.epa.gov/tsca-screening-tools/analog-
identification-methodology-aim-tool.
Vengosh, A., Jackson, R.B., Warner, N., Darrah, T.H., Kondash, A., 2014. A critical
review of the risks to water resources from unconventional shale gas devel-
opment and hydraulic fracturing in the United States. Environ. Sci. Technol. 15,
8334–8348.
Verslycke, T., Reid, K., Bowers, T., Thakali, S., Lewis, A., Sanders, J., Tuck, D., 2014.
The chemistry scoring index (CSI): a hazard-based scoring and ranking tool
for chemicals and products used in the oil and gas industry. Sustainability 6,
3993–4009.