Volume 23

Number 24
21 December 2021

Green
Pages 9707-10172

Chemistry
Cutting-edge research for a greener sustainable future
rsc.li/greenchem

ISSN 1463-9262

PAPER
Javier Pérez-Ramírez, Gonzalo Guillén-Gosálbez et al.
Planetary metrics for the absolute environmental
sustainability assessment of chemicals
 Green Chemistry
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Planetary metrics for the absolute environmental

Cite this: Green Chem., 2021, 23,
sustainability assessment of chemicals†
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9881
Victor Tulus, Javier Pérez-Ramírez * and Gonzalo Guillén-Gosálbez *

Environmental assessments in green chemistry often rely on simplified metrics that enable comparisons
between alternative routes but fail to shed light on whether they are truly sustainable in absolute terms,
viz. relative to the Earth’s ecological capacity. To expand our currently limited knowledge of the extent to
which chemicals are environmentally sustainable, here we analyse 492 chemical products through the
lens of seven planetary boundaries representing critical biophysical limits that should never be exceeded.
We found that most of them transgress these environmental guardrails, mainly the ones strongly con-
nected to greenhouse gas emissions (i.e., climate change, ocean acidification and biosphere integrity).
However, their levels of transgression fail to correlate with their carbon footprints, currently the focus of
most studies, implying that chemicals entailing higher greenhouse gas emissions are not necessarily less
environmentally sustainable in absolute terms. Our work points towards the need to embrace absolute
sustainability criteria in current environmental assessments, which will require agreeing on how to allocate
shares of the planet’s ecological capacity among anthropogenic activities, including chemicals’ pro-
duction. This work’s absolute environmental sustainability assessment (AESA) method, which could
Received 22nd July 2021, complement standard life cycle assessment approaches, might help experimental researchers working in
Accepted 26th October 2021
green chemistry develop truly ‘green’ products. The AESA method should be taken as a starting point to
DOI: 10.1039/d1gc02623b devise holistic approaches for quantifying the absolute environmental impact of chemicals to guide
rsc.li/greenchem research and policymaking more sensibly.

Introduction continuous advances in the field and the inherently complex

nature of the chemical routes.6 Accordingly, the current trend
The chemical industry faces the challenge of transitioning is to replace single-factor metrics by multi-factor indicators to
towards more sustainable production patterns while keeping provide evidence of a significant advance in green chemistry,
its competitive edge. Emerging trends towards this overarching which should be applied in any experimental work.7 Among
goal include shifting to renewable carbon (e.g., via carbon the indicators available, those based on life cycle assessment
capture and utilisation [CCU]1 or biomass use2), adopting cir- (LCA) have been recommended and are gaining broad interest
cular economy principles for emissions and waste reduction in the community.7 However, which specific LCA indicators
(e.g., recycling of plastics waste3 and CO2 utilisation), and elec- should be employed in green chemistry and how to interpret
trifying process units, among others.4 Realising this sustain- them are still open questions.
ability transition will require suitable key performance indi- LCA is a tool that quantifies the environmental impacts and
cators to effectively screen low-carbon technologies and resources used throughout a product’s life cycle, from raw
develop optimal pathways. materials acquisition through production, storage, transpor-
For many years, experimental work in green chemistry was tation, and final use and disposal. In the past decades, strong
guided by general principles and associated metrics, like the methodological developments in LCA have led to a range of
E-factor, atom economy or other mass-based metrics.5 life cycle impact assessment (LCIA) methods.8 These LCIA
However, these single-factor metrics started showing practical methods provide multi-factor metrics that quantify the
limitations evaluating the greenness of a chemical due to the damage on three main areas of protection—i.e., human
health, ecosystem quality, and resources—from the life cycle
inventory of feedstocks, energy use, emissions, and waste.
Institute for Chemical and Bioengineering, Department of Chemistry and Applied Examples of such methods include the Eco-indicator 99,9 CML
Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1, 8093 Zürich, Switzerland.
2001,10 IMPACT 2002+,11 TRACI 2.1,12 EPS2015,13 and ReCiPe
E-mail: [email protected], [email protected]
† Electronic supplementary information (ESI) available. See DOI: 10.1039/ 2016,14 currently implemented in software packages like
d1gc02623b GaBi,15 SimaPro,16 openLCA,17 Umberto18 and CMLCA.19

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Interpreting multi-factor LCIA results is often challenging, mental, economic and social perspectives combined—remain
especially when burden-shifting occurs, i.e., some impacts open.30 These challenges will be addressed by the newly
improve at the expense of worsening others.20 Multi-criteria formed Earth Commission (EC), which is planning to expand
decision-support tools were used to simplify the analysis by the PBs framework by exploring a safe and just corridor for
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aggregating indicators based on weights, derived via systematic humanity.31 The EC will focus on defining more relevant
approaches21 or expert elicitation.9 However, such weights are control variables and more accurate boundaries’ ranges at
often subjective and can be controversial, being implausible global and regional scales.31 Additional research efforts aim to
that any consensus will ever be reached on their values. quantify the interactions between the PBs to understand
In recent years, LCIA methods and their aggregated variants complex feedback loops potentially amplifying anthropogenic
have become widely used in industrial ecology and process impacts on the Earth system.32
Open Access Article. Published on 27 October 2021. Downloaded on 2/6/2022 2:06:09 PM.

systems engineering, making LCA the predominant approach Even though the work related to the PBs concept is still in
to quantify the environmental burdens of products and ser- its infancy, the benefits of AESA methods33,34 for LCA devel-
vices,8 including chemicals and fuels.4,22–24 In green chemistry oped within this framework are unfolding new avenues for
applications, LCIA methods can be used to screen alternative evaluating the environmental pillar of sustainability in indus-
synthesis routes for chemicals displaying the same (or compar- trial systems. As a proof-of-concept, Ryberg et al. applied a
able) functionalities and identify critical hotspots in the novel AESA method to assess the EU laundry washing sector.35
chemicals’ supply chain. Ryberg and colleagues also assessed the absolute environ-
However, standard LCIA methods, besides being hard to mental sustainability level of a Danish utility company.36
interpret, cannot quantify the chemicals’ absolute environ- Furthermore, capitalising on existing AESA methods,
mental sustainability level accurately, i.e., the extent to which González-Garay et al. quantified the absolute environmental
chemicals could contribute to safely operating our planet, con- sustainability level of several CCU routes for green methanol
sidering its finite carrying capacity. This limitation stems from production.37 In more recent work, Galán-Martín et al.
the lack of environmental thresholds establishing maximum extended this analysis to the main building blocks in the pet-
allowable impact limits within which a system could be rochemical industry, proposing a new method to quantify the
deemed sustainable.25 For example, we may know that chemi- impact on biosphere integrity.34 D’Angelo et al. evaluated low-
cal A’s global warming potential (GWP, also referred to as carbon ammonia synthesis routes through the lens of seven
carbon footprint) is larger than chemical B’s. Nevertheless, PBs,38 while Samaroo et al. investigated how to achieve absol-
this information is insufficient to establish whether they are ute environmental sustainability across integrated industrial
sustainable in absolute terms due to the absence of environ- networks for ammonia production considering a set of PBs-
mental thresholds (i.e., are A’s and B’s carbon footprint scores based metrics.39 Li et al. explored a possible route for China’s
admissible?).26 carbon neutrality for the combined production of electricity,
The need to define environmental thresholds has recently methanol and ammonia, focusing on the climate change PB.40
emerged in the LCA literature, leading to the concept of absol- Valente et al. analysed whether multiple green hydrogen pro-
ute environmental sustainability assessments (AESA), which duction routes could become environmentally sustainable sub-
quantify impacts relative to some global limits. For example, stitutes for heavy road transportation fuels considering the
thresholds were defined for terrestrial acidification based on PBs.41 Moreover, Wheeler et al.42 and Ehrenstein et al.43
the Earth’s carrying capacity to interpret the impact results in embedded the PBs concept into optimisation models to design
this category.27 More recently, AESA methods based on the sustainable bioethanol and hydrogen supply chains,
Planetary Boundaries (PBs) concept started to emerge. respectively.
The PBs framework—initially introduced by Rockström AESA methods could provide a sound multi-factor evalu-
et al.28 and later updated with slight modifications by Steffen ation framework to assess emerging and existing chemical
and colleagues29—identifies a set of biophysical limits within routes. Moreover, they could generate valuable insight into the
which humanity should operate our planet safely. The nine environmental sustainability footprints of current chemicals,
interlinked Earth-system processes, all essential for maintaining uncovering their major global impacts. Certainly, there seems
the Earth’s resilience, include (1) climate change, (2) strato- to be a general agreement that shifting to renewable carbon
spheric ozone depletion, (3) ocean acidification, (4) biogeo- should be a priority in the chemical sector. However, to our
chemical flows, (5) land-system change, (6) freshwater use, (7) knowledge, no previous study quantified the percentage
change in biosphere integrity, (8) atmospheric aerosol loading, reduction in carbon footprint needed in chemicals to operate
and (9) introduction of novel entities. For most of the Earth- within the safe operating space. Likewise, whether chemicals
system processes, one or more control variables were identified, could potentially pose a threat to other critical Earth-system
and quantitative thresholds (global boundaries) were defined processes remains unclear. Hence, shedding light on whether
that delimit a safe operating space (SOS) for humanity, which (and by how much) current chemicals exceed their share of the
should never be exceeded to preserve the planet’s stability. Earth’s ecological capacity could help to guide research more
The PBs concept, in its current state, only focuses on the sensibly and develop more effective regulations.
well-being of the planet Earth and multiple challenges towards Here we apply a multi-factor AESA method based on the
the road of true absolute sustainability—i.e., from the environ- PBs concept for assessing chemical technologies, and use it to

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evaluate 492 chemicals, providing clear guidelines for inter- compare each chemical with an ideal environmentally sustain-
preting the multi-dimensional results. We find that most of able counterpart, which would display an impact equal to the
these chemicals heavily transgress the climate change, ocean share of the global ecological budget assigned to it.
acidification and change in biosphere integrity PBs, while Accordingly, we determine each chemical’s transgression level
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some also exceed the biogeochemical flow (nitrogen) PB. We (i.e., the ratio of impact score to the share of ecological
also show how the carbon footprint, widespread in single- budget), as explained in Phase 4: Interpretation, enabling the
factor environmental assessments, fails to correlate with the comparison of each chemical against its ‘ideal’ absolute sus-
absolute environmental sustainability level of chemicals. tainable analogue.
Overall, our results highlight the benefits of applying multi- The dataset of chemicals focuses on divisions 33–36 of the
factor AESA methods for assessing chemicals and guiding United Nations Central Product Classification (CPC) v2.1.46
Divisions 33 to 36 – as part of section 3 of CPC, ‘Other trans-
Open Access Article. Published on 27 October 2021. Downloaded on 2/6/2022 2:06:09 PM.

research and regulations more sensibly.

portable goods, except metal products, machinery and equip-
ment’ – encompasses the following categories: ‘Coke oven pro-
Methods ducts; refined petroleum products; nuclear fuel’ (33), ‘basic
chemicals’ (34), ‘other chemical products; man-made fibres’
To illustrate the potential of applying AESA methods to evalu- (35), ‘rubber and plastics products’ (36). Finally, chemicals in
ate chemicals, we carried out a systematic absolute environ- these four categories were reorganised for convenience into
mental sustainability assessment of 492 chemicals following three groups, i.e., organic, inorganic, and other (non-classifi-
the four LCA phases described in the ISO 14040 and 14044 able) chemicals. Further details are elaborated in section 1 of
standards44,45 (Fig. 1), as detailed below. the ESI.†

Phase 1: Goal and scope definition Phase 2: Inventory analysis

The main goal of this study is to quantify the absolute environ- Ecoinvent database. We gathered all the inventory data from
mental sustainability level of a set of chemicals currently pro- ecoinvent v3.547 using the ‘Allocation at the point of substi-
duced at an industrial scale. The analysis quantifies the tution’ (APOS) system model version of the database, based on
impact of each chemical relative to its share of the safe operat- an attributional approach. As seen in Fig. 1, the database was
ing space, which defines a maximum threshold above which queried to identify products with a FU of ‘one kg of chemical
the chemical should be deemed environmentally generated in a market-type activity (with any geographical
unsustainable. location) belonging to any of the four CPC divisions (33–36)’.
As shown in Fig. 1, the functional unit (FU) is set to one kg As a result, 467 unique chemicals from global market activities
of the reference product (chemical) of a specific global market. and 412 non-unique chemicals from regional market activities
Usually, a global market combines multiple regional markets, were retrieved. The latter were aggregated into 201 unique
each encompassing several plants operating within a geo- pseudo-global market activities using mass allocation, leading
graphical region and implementing one or multiple standard to an extended dataset of 668 unique chemicals.
technologies. The analysis adopts a cradle-to-gate scope cover- Unfortunately, this dataset contained some generic chemicals
ing all the upstream inputs from the technosphere and nature, (e.g., ‘chemical, organic’, ‘cyclic N-compound’), representing
contributing to the plants as part of their supply chains. The families of similar products. Hence, these were removed from
main motivation for this choice is that we prefer to avoid the dataset as explained next. Additional information on the
making assumptions concerning the use phase of the chemi- database filtering criteria is provided in sections 1 and 2 of the
cals (not reported in the database), which would add signifi- ESI.†
cant uncertainties to the analysis. PubChem database. To remove all the generic compounds
Focusing on global markets enables the evaluation of the from the extended dataset, we cross-checked that the chemi-
average burden of a chemical manufactured by the predomi- cals were available in the PubChem database,48 matching
nant technologies rather than by marginal processes. them either by their CAS number (if provided) or by their
Moreover, reducing the granularity of the data avoids assessing name (or list of alternative names). The matched chemicals—
duplicated chemicals produced at regional scales, which could 73.7% (492 chemicals)—remained in the refined dataset and
shift the global distribution of impact values, as discussed were complemented with additional metadata extracted from
later in the article. Chemicals lacking a global production PubChem, i.e., information about the properties and structure
market were aggregated into one global market using mass of the compounds, while the others were dismissed.
allocation, mimicking the procedure implemented in the Consequently, the final refined dataset included (1) organic
ecoinvent database. chemicals (e.g., ethylene, propylene, benzene, and methanol),
It should be noted that each chemical in the dataset has its (2) inorganic chemicals (e.g., hydrogen, chlorine, fluorine, sul-
own FU (i.e., a relative reference unit to which the input and furic acid), (3) petroleum-derived chemicals (e.g., petrol, diesel,
output data are normalised). This FU should not be used to kerosene), (4) fertilisers, (5) pesticides, (6) plastics and rubber,
carry out direct comparisons between chemicals because they (7) pharmaceutical products, and (8) perfumes. Some of these
show different functionalities. However, it is possible to chemicals, e.g., basic and petroleum-derived chemicals, are

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Fig. 1 Overview of the methodology used in this study. Four phases of a standard LCA, shown in separate dash line delimited boxes, are followed:
(1) goal and scope definition, (2) inventory analysis, (3) impact assessment with the implementation of the PB-LCIA method, (4) interpretation of
results and recommendations. Pairs of thick arrows represent the interconnections between the different LCA phases, and thin arrows indicate the
general flow of the method.

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produced at large volumes (i.e., >1000 t per year) and often where IMPbc denotes the impact of chemical c in the CV of PB
lead to tight profit margins. In contrast, fine and speciality b and sosbc denotes the downscaled SOS assigned to the
chemicals are often high-value products (or intermediates for chemical c in CV b. If the TL is above one, the chemical
them), e.g., perfumes, drugs and pesticides, produced at lower should be deemed environmentally unsustainable as it
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volumes (i.e., <1000 t per year). Therefore, our dataset covers a exceeds its ecological budget and would be considered sustain-
wide range of chemicals sitting at different synthesis levels in able otherwise. A chemical that is sustainable in all the PBs
the chemical value chain that transforms mainly fossil feed- simultaneously can be regarded as absolute sustainable.
stocks into intermediate and final products via multiple steps. Hence, a key point is how to define fair quotas of the SOS, as
discussed next.
Note that our method provides a range of LCA metrics in
Phase 3: Impact assessment
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the form of transgression levels. However, these are easier to

The life-cycle impact assessment method connected to the PBs interpret than standard LCA indicators, as transgression levels
framework (PB-LCIA) translates flows of inventory entries to above one indicate that the chemical is unequivocally environ-
impacts expressed in the units of the control variables (CV) of mentally unsustainable. Hence, a new experimental route
the Earth-system processes. We quantify the impact in seven should be deemed appealing if it outperforms the business-as-
out of nine Earth-system processes (also referred to as PBs), usual alternative and at the same time shows transgression
discarding the ‘atmospheric aerosol loading’ and the ‘intro- levels below one in all the PBs. Certainly, being better than the
duction of novel entities’ PBs, since the former has no defined current technology is not enough if the new route exceeds the
global boundary, and the latter lacks a control variable yet. PBs. If trade-offs arise between categories, priority should be
The PB-LCIA method used in this study relies on the given to the climate change and biosphere integrity PBs, cur-
characterisation factors (CFs) of Ryberg et al.33 (CFs for six rently regarded as core boundaries through which the others
PBs) and those proposed by Galán-Martín et al.34 (CFs for bio- operate.29
sphere integrity PB), as follows: Equity principles and allocation approaches. Shares of the
X SOS can be established according to equity principles. These
IMPbc ¼ LCIec CFeb 8b [ B; c [ C ð1Þ
e[E principles are consistent with concepts of distributive fairness
such as sovereignty, equality, responsibility, capability or cost-
where IMPbc is the impact in the CV of PB b for chemical c, effectiveness.49 Allocation approaches can be roughly separ-
LCIec is the life cycle inventory entry e associated with chemi- ated into rights-based or duty-based. The latter, encompassing
cal c, and CF is the characterisation factor that links the inven- responsibility, capability, or cost-effectiveness principles, are
tory entry e with its impact in the CV b. B is the set of nine CVs often applied to allocate only the currently transgressed PBs.
for all the PBs (the climate change and biogeochemical flows On the other hand, the rights-based allocation approaches
PBs have two CVs each), and C is the set of chemicals. Further consider sovereignty and equality to set the basis for sharing
details regarding the LCIA methods used in this study are pro- the resources and environmental burdens. Our analysis
vided in section 3 of the ESI.† implements two rights-based allocation approaches, i.e., equal
per capita and grandfathering.
Phase 4: Interpretation Equal per capita (EPC) is based on the equality principle
stating that every person has the same moral right to access
Eqn (1) provides the impact of a chemical in the CVs of the
the Earth’s ecological budget (the SOS). Translating one’s per-
PBs. Similarly, a standard multi-factor LCIA method would
sonal share of the SOS to a specific activity, i.e., the production
provide the impact in a set of categories without further pro-
of a chemical, requires an additional upscaling method.50
cessing the results. However, impact values as such cannot
Here, we used the upscaling method based on the economic
shed light on whether the chemical is environmentally sustain-
value of the chemical, as in Ryberg et al.35 and other
able. To address this fundamental question, here we go
works,51,52 assuming that it may be used as a proxy for human
beyond standard multi-factor LCIA methods to compute a
wellbeing,53 i.e., higher economic value promotes further well-
transgression level (TL) metric that relates the impact of the
being and should result in larger shares of the SOS. Hence, in
chemical with the share of the safe operating space (SOS) allo-
the EPC approach, the share of the SOS of a chemical c
cated to it (Fig. 1 and eqn (2)). The PBs define an SOS for
(sosEPC
bc ) is determined as follows:
humanity, which should not be exceeded by all the anthropo-
genic activities jointly. Hence, to quantify the transgression
SOSb GVAc
bc ¼
sosEPC 8b [ B; c [ C ð3Þ
level, we first allocate a share of this global ecological budget popc
popTOT GVATOT
to the chemical and then evaluate whether its impact exceeds
this quota.
where SOSb is the total SOS for CV b, popTOT is the total popu-
In mathematical terms, the transgression level of chemical
lation of the world sharing the SOSb, popc is the population
c in the CV of PB b, denoted by TLbc, is computed as follows:
benefitting from consuming chemical c (directly or indirectly),
IMPbc GVAc is the gross value added (GVA) associated with chemical
TLbc ¼ 8b [ B; c [ C ð2Þ
sosbc c, and GVATOT is the total GVA of the world. Hence, we first

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allocate the SOS equally among the world’s population and activity. All data related to the calculation of TLs is available in
then further upscale each individual’s budget to a specific section 4 of the ESI.†
chemical. The second step assumes that all the global popu- Detection of outliers. To draw more meaningful con-
lation indirectly benefits from using each chemical produced clusions, after computing each chemical’s TL, we removed
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by global market activities. Thus, popc = popTOT. potential outliers following a multivariate detection method
By contrast, the grandfathering (GF) approach is based on based on a minimum covariance determinant and robust
the sovereignty principle. According to this principle, the Mahalanobis-type distance (rMD) approach. rMD is assumed
share allocated to each anthropogenic activity should be pro- to follow a chi-squared distribution with k = 9, i.e., nine
portional to its current contribution to the global pressure degrees of freedom (one for the TLs in each CV of its respective
exerted on the environment (eqn (4)). The downside of this PB) and a significance level of 5%. Chemicals with rMDs above
Open Access Article. Published on 27 October 2021. Downloaded on 2/6/2022 2:06:09 PM.

approach is that it allocates shares of the SOS only among the critical value were labelled as outliers, i.e., rejecting the
already existing activities without applying any moral criteria null hypothesis. The detection method was applied to the TL
for differentiation. scores of the 492 chemicals in all nine dimensions of the PBs
simultaneously, resulting in 26 outliers, i.e., a dataset with 466
IMPbc chemicals was used in Fig. 2 and 3. Further details on the
bc ¼ SOSb
sosGF 8b [ B; c [ C ð4Þ
IMPTOT
b detection method and the list of outliers can be found in
section 5 and Table S-3 of the ESI.†
where IMPTOTb is the total anthropogenic impact in the CV of
the PB b.
Eqn (3) requires the GVA of chemical c—defined as gross
output (revenues) less intermediate consumption and net Results and discussion
indirect taxes—, a piece of information often unavailable in Quantifying the absolute environmental sustainability level of
the public domain. To overcome this limitation, we compute chemicals
an upper bound on the GVA of chemicals, accounting only for We start by analysing the TL of the chemicals (Fig. 2), finding
the revenues generated from their global sales at basic prices that the overwhelming majority of them (99.4%) transgress at
(GVAc < pricecDEMc). Here, the idea is to follow a conservative least one PB, while none of them transgresses all the PBs sim-
approach to overestimate the share assigned to the chemical ultaneously. Hence, only three of the 466 chemicals evaluated
and underestimate the transgression levels. Following this (0.6%) respect their ecological budget and, thus, should be
approach and combining eqn (2) and (3), a lower bound on deemed absolute sustainable (according to the EPC sharing
the transgression level of the chemical from the EPC perspec- principle applied), i.e., hexamethyldisilazane (HMDS), sel-
tive (TLEPC
bc ) can be computed as: enium and trimesoyl chloride. These chemicals show relatively
low impact scores and, at the same time, high unitary prices
IMPbc impbc DEMc impbc GVATOT
bc ¼
TLEPC > ¼ (154, 76 and 1421 USD2018 per kg, respectively) that grant them
sosEPC
bc
pricec DEMc
SOSb GVATOT SOSb pricec ð5Þ a large ecological budget.
8b [ B; c [ C Most of the chemicals heavily transgress the GHG-related
PBs, i.e., climate change (CC) – CO2 concentration and energy
where impbc is the unitary impact of chemical c in the CV of imbalance (99.4% of the chemicals with TL > 1), ocean acidifi-
PB b, pricec is the unitary price of chemical c and DEMc is the cation (OA) (98.5%) and change in biosphere integrity (CBI)
total global demand of chemical c. (92.3%). These results are consistent with the fact that the
According to eqn (5), the TL of a chemical could be reduced chemical industry is a hard-to-abate sector that consumes
by decreasing its impact and/or increasing its price. Impacts large amounts of fossil resources (1.12 Gt) and generates about
could be decreased (to some extent) through appropriate strat- 2.0 Gt CO2eq cradle-to-gate emissions.1
egies implemented across the chemical supply chain. In con- In contrast, chemicals display weaker links with other
trast, global markets in a free economy dictate the prices, so Earth-system processes. Notably, only 0%, 1.5%, 7.1%, and
they cannot be controlled at will by the producer, at least for 4.9% of the chemicals transgress the land-system change
general chemicals. (LSC), freshwater use (FWU), stratospheric ozone depletion
Similarly, combining eqn (2) and (4), the transgression level (SOD) and biogeochemical (BGC) flow of phosphorous (P),
of the chemical from the GF perspective (TLGF b ) is computed as respectively—all of them more strongly connected to the agri-
follows: cultural sector. 126 chemicals (27%) exceed the nitrogen (N)
flow quota, some of them to a large extent, e.g., TL = 128.9 for
IMPbc IMPbc IMPTOT monoethanolamine. From the chemicals transgressing the
b ¼
TLNE GF ¼ IMPb c ¼ 8b [ B ð6Þ
b
sosbc SOSb IMPTOT SOSb BGC flow of N, only 14 are fertilisers or pesticides, ten of
b
which fixate N in their chemical structure. Similarly, other 38
Note that the GF approach leads to the same transgression chemicals that exceed the N flow budget also fixate N in their
levels for all the chemicals. Hence, it fails to discriminate chemical structure, while the rest consume N upstream in
among them and, in general, among any anthropogenic their supply chain.

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Fig. 2 Frequency distributions (histograms) and cumulative distribution functions (CDF) of transgression levels (TLs) of chemicals in the PBs. The
left y-axis shows the frequency of the data (i.e., chemicals) appearing in a range specified by the thickness of each bar (i.e., range of TLs shown on
the x-axis); the right y-axis shows the probability of the associated cumulative distribution function (one per each category of chemicals), i.e., prob-
ability of a chemical having a TL below the value displayed in the x-axis. Each category of chemicals (i.e., organic, inorganic, other, or all) is given by
a coloured curve of the CDF. The vertical red dotted line in the subplots represents the transgression level derived from applying the grandfathering
sharing principle (TLGF). The threshold above which a chemical is deemed unsustainable (TL = 1) is depicted with a vertical black dotted line. The ver-
tical blue dotted line shows the median of the dataset, while additional statistical information is given in the text box (one per subplot), where n is
the number of samples (chemicals), min/max are the minimum and maximum values across all the chemicals, x̄ is the mean, and cv is the coefficient
of variation of the dataset. The notation for the PBs is as follows: climate change (CC) with control variables of CO2 concentration (CO2 conc.) and
energy imbalance (Energy imb.), stratospheric ozone depletion (SOD), ocean acidification (OA), biogeochemical (BGC) flows with control variables
of phosphorus (P) and nitrogen (N), land-system change (LSC), freshwater use (FWU), change in biosphere integrity (CBI) with control variable of loss
of biodiversity intactness index (BII loss).

All the chemicals operate within the SOS defined for LSC lithium carbonate, vinyl chloride, toluene diisocyanate, propy-
(maximum TL of 0.02), and only seven slightly transgress the lene, ethylene, and butadiene. These negative scores, very low
FWU PB. Uranium hexafluoride (UF6), used for uranium in absolute value (−1 × 10−7 to −1 × 10−3), could be explained
enrichment, transgresses the latter category the most (TL = by some small LCI entries of ‘land transformation to the
2.3). Four enriched uranium elements with different concen- forest’ (higher in absolute value than the positive entries
trations, used in the fuel for light-water nuclear reactors, also labelled as ‘land transformation from the forest’), which are
exceed the FWU PB (by 1.2–1.4 times). These molecules, associated with the disposal of waste materials in landfills.
together with UF6, consume large amounts of freshwater, yet The TL scores of the chemicals are highly scattered, with
their high prices (841 USD2018 per kg U) offset their high the minimum and maximum TLs differing in as much as five
impacts, resulting in moderate TLs. orders of magnitude in the SOD, BGC flows and FWU PBs, and
Nine chemicals show negative TLs in the LSC PB, i.e., pot- three orders in the others. This is also observed in the coeffi-
assium chloride, potassium sulfate, potassium hydroxide, cients of variation (cv), particularly high in the SOD, BGC

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Fig. 3 Global warming potential (GWP) of chemicals versus their transgression levels (TLEPC) in the PBs. The chemicals, represented by bubbles –
whose size denotes the molecular weight –, are grouped into three categories, ‘inorganic’ (orange), ‘organic’ (blue) and ‘other’ (green). We indicate
the Spearman’s rank correlation coefficient (rs) between the TLs (in a specific PB) and GWP scores on the top right of the scatter plot. Rug plots on
the sides of each scatter plot show the individual distribution of the chemicals according to their category. The notation for the PBs is as follows:
climate change (CC) with control variables of CO2 concentration (CO2 conc.) and energy imbalance (Energy imb.), stratospheric ozone depletion
(SOD), ocean acidification (OA), biogeochemical (BGC) flows with control variables of phosphorus (P) and nitrogen (N), land-system change (LSC),
freshwater use (FWU), change in biosphere integrity (CBI) with control variable of loss of biodiversity intactness index (BII loss). Note that 21 chemi-
cals with GWP scores ranging from 48 to 3907 kg CO2eq per kg of chemical are omitted here (for visualisation purposes) but are shown in Table S-4
of the ESI.†

flows, FWU and LSC PBs (at most 500% for BGC flow of P). Comparing the EPC and GF sharing approaches, we find
The cv of the latter PB is additionally affected by the near-zero that in the GHG-related PBs, the former often leads to higher
mean and the negative values already discussed (recall that cv TLs (89.9%, 90.3%, 89.9% and 73.2% probability of TLEPC >
is given by the ratio of the standard deviation to the mean). TLGF in CC – CO2 conc., CC – Energy imb., OA and CBI PBs,

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respectively). In contrast, the opposite occurs in the SOD, BGC a petroleum refinery. The latter two, naphtha and LPG, serve
flows, LSC and FWU PBs—8.2%, 1.9% (P flow), 13.7% (N flow), as raw materials in the steam cracking process to produce
0% and 3% probability of TLEPC > TLGF, respectively. Note that ethylene and propylene. Additionally, through catalytic reform-
TLEPC > TLGF implies that the share of the SOS allocated to the ing, naphtha and LPG can yield benzene, toluene, and xylene.
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chemical based on economic considerations is lower than the Moreover, these platform chemicals are used as precursors of
share resulting from the grandfathering approach, i.e., sosEPC other chemicals. For example, ethylene is used to produce
< sosGF. However, qualitatively, both approaches tend to lead ethylene oxide and acetaldehyde via direct oxidation and can
to the same outcome (i.e., when one share is transgressed also be polymerised to obtain polyethylene. Furthermore,
according to a principle, it is also transgressed with the other ethylene is indirectly involved in the production of polyvi-
and vice versa). This holds for all the PBs except for the BGC nylchloride and 1-propanol. Finally, Fig. 4 also shows other
Open Access Article. Published on 27 October 2021. Downloaded on 2/6/2022 2:06:09 PM.

flows of P and N and LSC PBs, which are transgressed only by chemicals widely used in the chemical sector, e.g., hydrogen or
some chemicals (or none in the case of LSC PB) with the EPC sulfuric acid.
principle based on economic criteria and by all with the GF The chemicals shown in Fig. 4 are ordered by their TLs in
approach. CC – energy imbalance PB, regarded as the most stringent CV
of the core PBs,29 the other two being the CVs of CO2 concen-
Is GWP a good proxy of absolute environmental sustainability tration (CC PB) and loss of biodiversity intactness index (CBI
level? PB).54 Consistent with our previous results and focusing on
We next study the relationship between the TL and the GWP, the most heavily transgressed PBs (i.e., the GHG-related ones:
finding that larger GWP values do not necessarily lead to CC, OA and CBI), we find again that the TLs of these selected
larger TLs—Spearman’s rank correlation coefficients (rS) in the chemicals do not correlate with the GWP. For example, sulfuric
range (−0.11, 0.16), see Fig. 3. Said differently, a molecule A acid shows the lowest GWP (0.15 kg CO2eq per kg) but ranks
with a larger carbon footprint than that of B is not necessarily 26th out of 34 chemicals in terms of TL in the CC PB.
less sustainable in absolute environmental terms than the Similarly, fluorine shows the largest GWP (12.1 kg CO2eq per
latter. This poor correlation is explained by two main obser- kg) but displays only the 20th largest TL in the CC PB. This
vations: (1) not all the PBs impacts correlate with GWP poor correlation further reinforces the observation that the
(Fig. S-1 in the ESI†), and (2) the price of the product, which carbon footprint should not be taken as a proxy of absolute
dictates its ecological budget (i.e., more expensive chemicals environmental sustainability level.
are allowed to pollute more), does not correlate either with the The mismatch between the TLs in the GHG-related PBs and
carbon footprint (Fig. S-2 in the ESI†). Notably, from eqn (5), the carbon footprint is due to the poor correlation between the
TLEPC is directly proportional to the impacts in the PBs and carbon emissions and the prices, which affect the quotas (lower
inversely proportional to the unitary price of the chemical. prices lead to tighter ecological budgets). Hence, while a
Hence, at least in the GHG-related PBs, the TL should correlate pattern seems to emerge from the analysis of the GWP, the
with the GWP because the carbon footprint drives the impact same is not true for the TLs. Notably, chemicals sitting down-
in these PBs. However, this does not occur because the unitary stream in the synthesis tree require more production steps and,
price fails to correlate with the GWP. Furthermore, the other therefore, tend to lead to larger scores in GWP. However, they
TLs also fail to correlate with the GWP because neither the also tend to have larger prices, which results in larger quotas
impact on their PBs nor the price correlates with the carbon and, therefore, lower TLs. Whether one factor (larger impacts
footprint. due to more complex production routes) offsets the other
Note that there are 21 chemicals with high GWP scores, (higher prices and quotas) depends on the specific case. For
e.g., lithium (48.1 kg CO2eq per kg), previously mentioned, UF6 example, the GWP of 1 kg of pyridine is 3.9 times that of 1 kg of
(146.7 kg CO2eq per kg), and uranium enriched at 4.2% ammonia. Still, its price is 29.2 times higher, which results in a
(3907.2 kg CO2eq per kg), which are not outliers but were smaller TL of pyridine in the GHG-related PBs relative to its pre-
omitted in Fig. 3 to ease the visual analysis of the data (com- cursor, ammonia. Conversely, the GWP of 1 kg of ammonium
plete list of these chemicals is provided in Table S-4 of the nitrate is 3.8 times greater than that of ammonia, but its price
ESI†). is only 18% higher, resulting in a higher TL with respect to
ammonia. Furthermore, comparing chlorine with hydrogen,
Absolute environmental sustainability level of selected both involved in the production of many chemicals (either
relevant chemicals directly in their synthesis or elsewhere in their supply chains),
We next select 34 chemicals for a more in-depth discussion we find that hydrogen shows a much lower TL in the GHG-
based on their relevance, focusing on analysing their TLEPC related PBs (at most 13.2 vs. 120.7 for chlorine), despite having
and GWP scores and prices (Fig. 4). These chemicals sit at a much higher carbon footprint (2.37 vs. 1.02 kg CO2eq per kg).
different levels in the synthesis tree of the chemical industry. These disparities are due to the high hydrogen price (3.85 vs.
In Fig. 4, the network of connections qualitatively represents 0.21 USD2018 per kg for chlorine), which grants hydrogen a
the direct or indirect uses of chemicals in producing other larger ecological budget, leading to a 10-fold difference in TLs.
chemicals. For instance, petrol, diesel, kerosene, naphtha, and Polymerisation (e.g., propylene to polypropylene), oxidation
liquefied petroleum gas (LPG) are produced from crude oil in (e.g., methanol to formaldehyde) or ammoxidation (e.g., propy-

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Fig. 4 List of selected chemicals sorted by their TL score in CC – energy imbalance PB. The first nine columns show the TLs of the chemicals in
every control variable of the PBs. The tenth column depicts the unitary prices for each of the chemicals, and in the last column, the GWP score for
each chemical is given. The grey rows indicate that the chemical is detected as an outlier. The network depicts a qualitative representation of mul-
tiple interactions between the different chemicals. The notation is as follows: circles with inwards pointing arrows represent a direct input (direct
use as raw material), while arrows pointing to a square denote an indirect use at some point in the production chain; circles with outwards pointing
arrows represent an output. The colours of the network are arbitrarily selected to ease the visualisation. The notation for the PBs is as follows:
climate change (CC) with control variables of CO2 concentration (CO2 conc.) and energy imbalance (Energy imb.), stratospheric ozone depletion
(SOD), ocean acidification (OA), biogeochemical (BGC) flows with control variables of phosphorus (P) and nitrogen (N), land-system change (LSC),
freshwater use (FWU), change in biosphere integrity (CBI) with control variable of loss of biodiversity intactness index (BII loss).

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lene to acrylonitrile) tend to increase the TLs because the price to assign shares of the SOS to them, which will allow setting
increment is insufficient to counteract the impact increase. priorities to make the chemical sector more sustainable.
Notably, focusing on the CC – energy imbalance PB, when pro- Second, it follows that the carbon footprint (or any other
pylene (TL = 29.1, GWP of 1.50 kg CO2eq per kg and price of single-factor metric) should not be the only metric of concern,
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1.08 USD2018 per kg) is oxidised in the presence of ammonia to although fossil chemicals show the highest transgression
acrylonitrile via the Sohio process, the GWP increases 2-fold, levels in the carbon-related PBs. Notably, a fair and insightful
while the price remains almost the same, resulting in a much assessment of chemicals and their labelling as ‘green’ would
higher TL (i.e., 68.7). require transgression metrics that consider both a range of
The TLs in the other PBs, i.e., the ones not directly linked impact levels and their associated thresholds.
to GHG emissions, are always relatively low, excluding some The AESA method presented herein should complement
high TLs in the BGC – N flow (e.g., nylon 6–6, para-phenylene-
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the studies of experimental researchers working in the area of

diamine, or chlorotoluron), and to a lesser extent, in the BGC – green chemistry, who already use mass-based metrics and
P flow (e.g., nylon 6–6 or glyphosate). We clarify that due to the LCA. This method benefits from the integration of life-cycle
inverse modelling and the cradle-to-gate scope of the analysis, principles and goes beyond standard LCIA metrics by explicitly
our calculations underestimate the impact in the BGC – N flow comparing the impact scores against Earth-sytem’s thresholds.
PB (see section 7 of the ESI†), so the TLs could be higher in Ideally, sustainability assessments should also cover the econ-
this category. We finally note that a cradle-to-grave scope cover- omic and social dimensions, linking to the sustainable devel-
ing the use phase of the chemicals could lead, in some cases, opment goals (SDGs). This will require further progress in the
to significantly different results. For example, fuels show rela- PBs framework to define other control variables, which would
tively low carbon footprints on a cradle-to-gate basis, com- allow to explore a safe and just corridor for humanity. Further
pared to some platform chemicals (e.g., 0.56 kg CO2eq per kg research should also focus on regionalised assessments and
of diesel vs. 0.67 kg CO2eq per kg of methanol). However, social indicators tailored to chemicals production.
expanding the scope to the ‘grave’ would increase the overall Overall, this work aims to raise awareness of the need to go
GWP score (and, consequently, the TL values in the GHG- beyond standard multi-factor LCAs in green chemistry studies
related PBs) by roughly 3.1 kg CO2eq per kg of fuel. to embrace absolute sustainability criteria based on the
Earth’s ecological capacity. This holistic approach will allow
identifying pathways that outperform the current technologies
Conclusions and outlook and do so in a way that is entirely consistent with the Earth’s
biophysical limits. Assessments similar to the one presented
Here we discussed the use of absolute environmental sustain- herein will help guide research more sensibly and allocate
ability methods for assessing chemical technologies, quantify- resources more judiciously to produce more sustainable
ing the impact of 492 chemicals through the lens of seven PBs, chemicals.
all essential to maintaining the stability of the Earth system.
We found that an overwhelming majority of them (99.4%) are
environmentally unsustainable due to the transgression of at Conflicts of interest
least one PB, exceeding in some cases the allowable budget by
more than 200 times. The transgression levels are exception- There are no conflicts to declare.
ally high in the carbon-related PBs (i.e., climate change, ocean
acidification, and change in biosphere integrity). In contrast,
they are almost negligible or very moderate in the remaining Acknowledgements
ones. This publication was created as part of NCCR Catalysis, a
Our results also show that GWP is not a good proxy of National Centre of Competence in Research funded by the
absolute environmental sustainability performance in chemi- Swiss National Science Foundation.
cals, as it fails to correlate with their transgression level. This
is because the environmental sustainability level of chemicals
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