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Abstract

In the past twenty years, green analytical chemistry has gained more and more attention. However, quantification of the environmental impacts of analytical methods has never been estimated. The purpose of this work is to apply life cycle assessment (LCA) to the preparation of one sample using SBSE and SPE techniques and to show that LCA is a suitable framework to quantitatively assess the environmental impacts of a sample preparation. The amounts of consumables, chemicals and energy needed to prepare a sample with both techniques were determined with the literature and lab measurements. We converted this data into environmental impacts through the use of a life cycle inventory (LCI) database (ecoinvent 3.7.1) and a life cycle impact assessment method (ReCiPe 2016 Midpoint). The results of the LCA (baseline scenario) showed that the SBSE induces less overall environmental impacts than the SPE because it uses less chemicals to prepare one sample. The impacts of both techniques could be reduced by reusing the vial and vial caps which are the largest contributors. The spatial location of the laboratory (and its associated electricity mix) also plays a significant role for the SBSE process as it uses more electricity than the SPE process. This study paves the way for the application and standardization of LCA to whole chemical analysis, composed of the sample collection, preparation, analysis and the data analysis.
Advances in Sample Preparation 1 (2022) 100009
Contents lists available at ScienceDirect
Advances in Sample Preparation
journal homepage: www.elsevier.com/locate/sampre
Life cycle assessment of sample preparation in analytical chemistry: a case
study on SBSE and SPE techniques
Bastien Raccary
a
,
b
, Philippe Loubet
a
,
, Christophe Peres
c
, Guido Sonnemann
a
a
Univ. Bordeaux, CNRS, Bordeaux INP, ISM, UMR 5255, F-33400, Talence, France
b
Analytiss, 89 rue des Poissonniers, 75018, Paris, France
c
Le Labo Durable, 89 rue des Poissonniers, 75018, Paris, France
Keywords:
Environmental impacts
Green analytical chemistry
LCA
Carbon footprint
In the past twenty years, green analytical chemistry has gained more and more attention. However, the environ-
mental impacts of analytical methods have never been quantied. The purpose of this work is to apply life cycle
assessment (LCA) to the preparation of one sample using SBSE and SPE techniques and to show that LCA is a
suitable framework to quantitatively assess the environmental impacts of a sample preparation. The amounts of
consumables, chemicals and energy needed to prepare a sample with both techniques were determined with the
literature and lab measurements. We converted this data into environmental impacts through the use of a life
cycle inventory database (ecoinvent 3.7.1) and a life cycle impact assessment method (ReCiPe 2016 Midpoint).
The results of the LCA (baseline scenario) showed that the SBSE induces less overall environmental impacts than
the SPE because it uses less chemicals to prepare one sample. The impacts of both techniques could be reduced
by reusing the vial and vial caps which are the largest contributors. The spatial location of the laboratory (and
its associated electricity mix) also plays a signicant role for the SBSE process as it uses more electricity than the
SPE process. This study paves the way for the application and standardization of LCA to whole chemical analysis,
composed of the sample collection, preparation, analysis and the data analysis.
1. Introduction
Sample preparation is an essential step in chemical analysis. Over
the past years, “green ” extractions techniques have been developed to
limit energy, solvents and consumables use. In 2009, Tobizewski et al.
[1] considered that sample preparation was potentially the most pollut-
ing step of analysis. However, there is no scientic consensus on how to
measure the environmental impacts of these “greener ” extraction tech-
niques.
Several “greenness ” assessment tools have been developed in the re-
cent years, but are not giving quantitative estimation of the environmen-
tal impacts of a chemical analysis [2] [3] Life cycle assessment (LCA)
could be complementary to these tools as it is a holistic methodology to
assess the environmental impacts of the dierent stages of an analytical
method, in particular the sample preparation step. LCA is a normalized
[4] methodology and has been used for years in several elds of indus-
try, including organic chemistry [5] and the process industry [6] .
As a way to introduce the application of LCA to sample preparation,
we propose to analyse and compare the environmental impacts of two
Corresponding author: Dr. Philippe Loubet, Bordeaux INP, France
E-mail address: philippe.loubet@u-bordeaux.fr (P. Loubet).
well-known sample preparation techniques: stir bar sorptive extraction
(SBSE) [7] and solid phase extraction (SPE) [8] .
Modern approaches for sample preparation are relying on solventless
extraction methods, and miniaturization. SBSE is growing in popularity
due to its ease of use, high sensitivity, and reproducibility and is reg-
ularly introduced as a “green extraction technique [9] . Regarding the
latter, we wanted to challenge this assumption by comparing it to an-
other extraction technique, more “classical ”, in a particular case. Indeed,
the principle of SPE is similar to that of liquid-liquid extraction (LLE),
and is more solvent-intensive and relatively expensive [10] .
The aim of the proposed study is to determine which analytical pro-
cedure generate the least overall environmental impacts and provide
guidance on eco-design considerations. We propose to conduct the LCA
of SPE and SBSE sample preparation techniques applied to organochlo-
ride pesticides analysis in freshwater. We base our LCA on two analytical
procedures:
(i) SBSE parameters are taken from a publication of Grossi et al. [10]
(ii) SPE parameters are taken from the standard NF EN 16693 [11]
https://doi.org/10.1016/j.sampre.2022.100009
Received 1 December 2021; Received in revised form 28 January 2022; Accepted 6 February 2022
2772-5820/© 2022 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
( http://creativecommons.org/licenses/by-nc-nd/4.0/ )
B. Raccary, P. Loubet, C. Peres et al. Advances in Sample Preparation 1 (2022) 100009
Fig. 1. Boundaries of system considered for
the life cycle assessment of sample preparation
This paper follows the four phases of the LCA methodology as de-
ned by ISO 14040-44 standards [4] :
-Goal and scope denition: the objectives of the study are clearly
stated and the boundaries of the two systems are dened accord-
ingly.
-Life cycle inventory (LCI) analysis: the inputs and outputs of the sys-
tem are collected. The inventory entails the quantication of eco-
nomic ows within the technosphere (energy, materials, etc.) and
elementary ows from and to the ecosphere (natural resources,
and emissions to air, soil and water).
-Life cycle impact assessment (LCIA): following the inventory, the
dierent ows are converted into environmental impacts.
-Interpretation: the results are analysed and lead to the identication
of environmental hotspots and to recommendations to improve
the environmental performance of the process. It also enables to
compare the impacts of dierent systems.
2. Materials and methods
2.1. Goal and scope
The aim of the study is to investigate and compare the environ-
mental impacts of two sample preparation techniques (SBSE, SPE). The
function of the system is the preparation of a sample for the analysis
of 11 organochloride pesticides ( 𝛼HCH, 𝛽HCH, 𝛾HCH, ΔHCH, Aldrin,
𝛼Endosulfan, DDE, Dieldrin, Endrin, DDD, DDT). The corresponding
functional unit is “to prepare 1 sample of freshwater for the quanti-
cation of 11 organochloride pesticides ”.
The analysis only includes the sample preparation stage, because the
other stages of the chemical analysis are considered similar in both sys-
tems ( Fig. 1 ). For the sample preparation, we include in the boundaries
of both systems:
–lab consumables (with their production, transport, and end-of-life)
–SBSE/SPE support media: stir bar and cartridge (with their produc-
tion, transport, and end-of-life)
Table 1
ReCiPe 2016 midpoint (H) impact categories and list of abbrevia-
tions
Impact category Abbreviations Unit
Global warming GW kg CO
2
eq
Stratospheric ozone depletion SOD kg CFC11 eq
Ionizing radiation IR kg Co-60 eq
Ozone formation, Human health OF kg NOx eq
Fine particulate matter formation FPMF kg PM2.5 eq
Terrestrial acidication TA kg SO
2
eq
Freshwater eutrophication FEut kg P eq
Terrestrial ecotoxicity TE kg 1,4-DCB eq
Freshwater ecotoxicity FE kg 1,4-DCB eq
Marine ecotoxicity ME kg 1,4-DCB eq
Human carcinogenic toxicity HCT kg 1,4-DCB eq
Human non-carcinogenic toxicity HNCT kg 1,4-DCB eq
Marine eutrophication MEP kg N-Eq
Land use LU m
2
a crop eq
Mineral resource scarcity MRS kg Cu eq
Fossil resource scarcity FRS kg oil eq
Water consumption WC m
3
–chemicals (with their production, transport, and end-of-life)
– electricity use
The production and end-of-life of lab devices (pump, stirrer, etc.)
have been excluded from the study because of lack of data. Also, it
is common that LCA case studies exclude infrastructures in the system
boundaries.
Resource use and emissions related to the background processes were
retrieved from the ecoinvent 3.7.1 database [12] . The study has been
made in the French context: all the data used are considered most accu-
rate for the French situation. When French data is not available, Euro-
pean data have been selected.
The environmental impacts are then characterized using the ReCiPe
2016 Midpoint (H) [13] life cycle impact assessment method ( Table 1 )
selected as one of the most up-to-date method for the European context.
2
B. Raccary, P. Loubet, C. Peres et al. Advances in Sample Preparation 1 (2022) 100009
Table 2
Inventory data for 1 sample preparation with SBSE, and their associated ecoinvent 3.7.1. processes. EoL: end-of-life
Elements Quantity Unit Source of data Ecoinvent process
Lab consumables
Vial Glass production 15.3 g Direct weighting
1 market for glass tube,
borosilicate | GLO
Glass EoL 15.3 g = m
Glass Production market for waste glass | FR
Vial cap Aluminium
production
1 g Direct weighting
1 market for aluminium,
wrought alloy | GLO
Aluminium EoL 1 g = m
Aluminium production market for waste aluminium
| GLO
TFE production 0.7 g Direct weighting
1 tetrauoroethylene
production | RER
TFE EoL 0.7 g = m
TFE production market for waste plastic,
mixture | FR
Stir bar Glass production 0.13/200 g Direct weighting
1
/ Number of
use
market for glass tube,
borosilicate | GLO
PDMS
production
0.023/200 g Direct weighting
1
/ Number of
use
polydimethylsiloxane
production | GLO
Magnet
production
0.01/200 g Direct weighting
1
/ Number of
use
permanent magnet
production, for electric
motor | GLO
Electricity
Stirring Electricity, low
voltage
4.57 Wh Direct measurement
2 market for electricity, low
voltage | FR
Water bath Electricity, low
voltage
101 Wh = Power(kW)
time(h)
Chemicals
Drying NaCl production 4.5 g Data from the analytical
procedure
sodium chloride production,
powder | RER
Back-extraction Acetonitrile
production
0.939 g Data from the analytical
procedure
Sohio process | RER
Toluene
production
0.26 g Data from the analytical
procedure
market for toluene, liquid |
RER
Evaporation of chemicals
in the lab
Acetonitrile
evaporation
Toluene
evaporation
0.01
0.003
g = 0.01
m
Acetonitrile
= 0.01
m
Toluene
direct emission of chemicals to
the air (that generates toxicity
impacts)
End-of-life of chemicals Acetonitrile
incineration
Toluene
incineration
0.93
0.26
g = 0.99
m
Acetonitrile
= 0.99
m
Toluene
specific modelling from Doka
[15]
Transport
Chemicals 2.28 kg
km =
(m
NaCl
+ m
Acetonitrile
+ m
Toluene
)
distance
transport, freight, lorry, all
sizes, EURO4 to generic
market for transport, freight,
lorry, unspecied | RER
Vial cap 0.136 kg
km = (m
Aluminum
+ m
TFE
)
distance
Vial 6.13 kg
km = m
Glass
distance
1 Measured with a Mettler Toledo XP204 balance (United States)
2 Measured with an Elgato EVE Energy Smart Plug (Germany)
We used Activity Browser [14] , a graphical user interface for the
LCA software Brightway2 to determine the impacts of each background
processes from ecoinvent 3.7.1. Then, a spreadsheet using these impact
results was used to compute the total impacts of both systems, as shown
in supplementary information (SI).
2.2. Life cycle inventory
The SPE and SBSE processes are explained in sections 2.2.1 and 2.2.2.
The associated lab consumables, electricity, chemicals, transport quan-
tities related to both processes are summarized in Table 2 and Table 3 ,
along with the sources of data and the associated ecoinvent processes
that are used to model the production, use or end-of-life of the dierent
elements. The transport distance for lab consumables and chemicals is
supposed to be 400 km. We also assumed in both systems that 1% of the
chemicals used are directly evaporated in the laboratory and potentially
exposed to the analytical chemist. We considered that chemicals are in-
cinerated at their end-of-life. Emissions to air and supporting services
(energy, chemicals, treatment of residues) for incineration are estimated
based on the model developed by Doka [15] which is commonly used in
LCA. The model provides specic inventories depending on the element
(C, N, P, Cl, Fe) that goes through incineration. From this model, the in-
ventory for incineration of each chemical is retrieved from its elemental
composition.
Full inventory and results are provided in SI.
2.2.1. Product system 1 –SBSE process [10]
First, the sample is placed in a 20mL headspace vial capped with
PTFE-coated septa. The SBSE extraction is realized by holding the bar
suspended in the headspace ( Fig. 2 ) and the vial is placed in a water bath
(power of 100W) at 85°C during the sampling process. The magnetic
stirring is conducted at 600rpm during 85min. After extraction, the bar
is desorbed in 1.5mL of back-extraction solvent into a 1.5mL glass vial
with toluene/ACN 20:80. 2µL is sampled and injected into the GC-MS.
We consider that:
-the stir bar can be used 200 times as recommended by Gerstel,
-the vial and vial cap are used once.
2.2.2. Product system 2 –SPE extraction process
[11]
First, the pH value of the sample is adjusted if it is below (5 ± 0.2)
or above (9 ± 0.2). Hydrochloric acid, sulfuric acid or sodium hydroxide
are used for this step. The SPE disk is then preconditioned with 10
2 mL
of acetone thanks to a vacuum device (power of 40W). Then, 10
2 mL of
3
B. Raccary, P. Loubet, C. Peres et al. Advances in Sample Preparation 1 (2022) 100009
Table 3
Inventory data for 1 sample preparation with SPE, and their associated ecoinvent 3.7.1. processes
Elements Quantity Unit Source of data Ecoinvent process ( in italic:
specific modelling)
Lab consumables
Vial Glass production 1.53 g Direct weighting
1 market for glass tube, borosilicate
| GLO
Glass EoL 1.53 g = m
Glass Production market for waste glass | FR
Vial cap Aluminium
production
1 g Direct weighting
1 market for aluminium, wrought
alloy | GLO
Aluminium EoL 1 g = m
Aluminium production market for waste aluminium |
GLO
TFE production 0.7 g Direct weighting
1 tetrauoroethylene production |
RER
TFE EoL 0.7 g = m
TFE production market for waste plastic, mixture
| FR
SPE cartridge
SPE lter Activated silica
production
0.15 g Direct weighting
1 market for activated silica | GLO
Cartridge plastics Polypropylene
production
2 g Direct weighting
1 market for polypropylene,
granulate | GLO
Polypropylene EoL 2 g = m
Propylene production market for waste plastic, mixture
| FR
Electricity
Pump Electricity, low
voltage
2 Wh = Power
time market for electricity, low
voltage | FR
Chemicals
Preconditioning Deionised water 38 g Data from the analytical procedure market for water, deionised |
Europe without Switzerland
Extraction Acetone 26.7 g Data from the analytical procedure market for acetone, liquid | RER
Concentration Nitrogen 142 g Direct measurement market for
nitrogen, liquid | RER
Evaporation of
chemicals in the
lab
Acetone
evaporation
0.3 kg = 0.01
m
Acetone
direct emission of acetone to the air
(that generates toxicity impacts)
End-of-life of
chemicals
Acetone
incineration
26.4 kg = 0.99
m
Acetone
specific modelling from Doka [15]
Wastewater
treatment
38 g = m
Deionised water market for wastewater, average |
Europe without Switzerland
Transport
Chemicals 82.72 kg
km
(m
Deionized water
+ m
Acetone
+ m
Nitrogen
)
distance
transport, freight, lorry, all sizes,
EURO4 to
generic market for transport,
freight, lorry, unspecied | RER
Vial cap 0.136 kg
km (m
Aluminum
+ m
TFE
)
distance
Vial 6.13 kg
km m
Glass
distance
1 Measured with a Mettler Toledo XP204 balance (United States)
Fig. 2. Schematic representation of HS-SBSE apparatus
deionized water is passed through the SPE disk. 1000 mL of the sample
is passed through the conditioned disk at a ow rate of 50 mL/min.
The sample bottle is rinsed twice with 9 mL of deionized water. The
disk is then dried with a vacuum device supported by a stream of dry
nitrogen for about 15 min. 10 mL of acetone is passed through the disk.
The eluate is collected by passing it through the disk. 8 mL of acetone
is passed through the disk. The eluate is collected by passing it through
the disk. This step is repeated twice. We consider that the vial and vial
cap are used once ( Fig. 3 ).
2.2.3. Sensitivity analysis
Reuse of vial and vial cap: As we expect high impacts due to the
manufacturing of cap and vial cap (due to their mass), we studied the
inuence of their reuse on overall impacts.
We estimate that the vial can be reused up to 100 times and the vial
cap up to 5 times. Therefore, the vial/vial cap masses associated to one
sample preparation are divided by their number of use, and a washing
step is included (5 mL acetone and 10 mL deionised water).
It is to be noted that the life time of cap and vial cap can be updated
in the SI (tab SBSE, SPE).
Electricity: As electricity is expected to contribute to impacts of
SBSE, we studied dierent electricity mixes, in particular the Polish,
Spanish and Indian (eastern grid) mixes that are more carbon-intensive
than the French mix.
3. Results and discussion
In this section, the LCIA results of the SPE and SBSE are both pre-
sented in Fig. 4 and Fig. 5 .
3.1. Analysis of the SBSE process
For SBSE, the results ( Fig. 4 ) show that, the majority of the impacts
results from the vial and the vial cap production because of their single
use and their relative high mass compared to other consumables and
chemicals.
4
B. Raccary, P. Loubet, C. Peres et al. Advances in Sample Preparation 1 (2022) 100009
Fig. 3. Schematic representation of the SPE
process
Fig. 4. Contribution analysis of the SBSE pro-
cess (ReCiPe2016 Midpoint H). Abbreviation
denitions are available in Table 1 .
The large contribution of the vial cap manufacturing on the global
warming (GW) impact is due to the tetrauoroethylene (TFE) septum be-
cause the production of 1kg of TFE has a GW impact of 135 kgCO
2
eq/kg
which is high in comparison with other materials. The large contribu-
tion of the vial cap manufacturing to the stratospheric ozone depletion
(SOD) impact is also due to TFE because its manufacturing emits HFC
and CFC molecules.
Two exceptions can be noticed concerning the marine eutrophica-
tion and the ionizing radiation. The ionizing radiation (IR) impact is
mainly due to the electricity used during the process because of the ma-
jority of the French electricity is composed of nuclear energy. Indeed,
the extraction of the nuclear fuel and the operation of the nuclear plants
induces the emission of radionuclides (such as Radon-222). The marine
eutrophication (MEut) impact is due to the use of acetonitrile during the
back-extraction step. Indeed, the use of ammonia during the Sohio Pro-
cess (industrial process for the production of acetonitrile) induces the
release of ammonium which causes nutrient enrichment in the marine
environment leading oxygen depletion, anoxia and ‘dead zones’ which
is one of the most widespread cause of marine ecosystems disturbance.
[13]
The stir bar has low contribution on all impact categories because of
its small mass and the fact than it can be reused 200 times (as recom-
mended by Gerstel).
3.2. Analysis of the SPE process
For SPE, the results ( Fig. 5 ) also show that the majority of the im-
pacts results from the vial and the vial cap, as found for the SBSE. The
chemicals are also large contributors to the impacts because the proce-
dure requires acetone, deionised water and large quantity of nitrogen.
Impacts associated with chemicals are mainly generated during their
production. Incineration of acetone at the end of life contributes to cli-
mate change (because of CO
2
emissions) and to terrestrial ecotoxicity.
The evaporation of chemicals (acetone) in the lab generate low toxicity
impacts (contribution of less than 1%) due to the low emission mass and
the relatively low toxicity of acetone. Details on the impact related to
the evaporation and end-of-life of chemicals can be found in the SI (SPE
tab).
Compared to the SBSE procedure, more transport is needed, because
of the larger volume of chemicals and this is why it has a greater inu-
ence on the overall impacts.
The SPE process only needs the use of a vacuum manifold for few
minutes so electricity has only a small contribution to the impacts, even
for the ionizing radiation.
The SPE cartridge, has a low contribution to the overall impacts even
if it used only one time because of its low mass. However, it has a greater
contribution to the overall impacts than the stir bar in the SBSE process.
5
B. Raccary, P. Loubet, C. Peres et al. Advances in Sample Preparation 1 (2022) 100009
Fig. 5. Contribution analysis of the SPE pro-
cess (ReCiPe2016 Midpoint H). Abbreviation
denitions are available in Table 1 .
Table 4
Comparison of the absolute impacts of SBSE and SPE processes (1 use of vial
and vial cap).
3.3. Comparison between SBSE and SPE extraction
Comparison between the SBSE extraction and the SPE extraction is
provided in Table 4 (comparison with absolute impact results for one
sample preparation) and in Fig. 6 (relative comparison).
The SBSE extraction results in lower impacts for 15 out 17 cate-
gories. This is mainly due to the extended use of chemicals (acetone
and nitrogen to dry the cartridge) for SPE compared to the SBSE pro-
cess. SBSE generates signicantly more impacts than SPE concerning the
ionizing radiation and marine eutrophication. As mentioned before, this
is because of the higher electricity consumption for SBSE (that leads to
ionizing radiation) and to the use of acetonitrile (that leads to marine
eutrophication).
Concerning the global warming absolute impact, one sample pre-
pared with SBSE is equivalent to 169 gCO
2
eq while one prepared with
SPE is equivalent to 331 gCO
2
eq.
3.4. Influence of the reuse of vials and vial caps
A sensitivity analysis on vials and vial caps has been carried out, as
shown in Fig. 7 for the global warming impact category (results for all
impact categories can be found in SI). The reuse of the vial (100 times)
and the vial cap (5 times) induces a reduction of the overall impacts for
SPE and SBSE. Indeed, the increase of the impact due to the washing step
(represented by a higher contribution from chemicals) has less inuence
on the results than the decrease of impacts due to the reuse of the vial
and the vial cap.
The SPE process (with vial reuse) impact on global warming is in the
same order of magnitude as the SBSE process (with 1 use of vial).
3.5. Influence of the electricity mix
The results of the sensitivity analysis on the electricity mix is shown
in Fig. 8 for the global warming impact (results for all impact categories
can be found in SI).
SBSE uses more electricity than SPE. Therefore, the choice of the
electricity mix has more inuence on the results for SBSE. Spatial loca-
tion has almost no inuence on the impacts of the SPE process because
of low electricity use. We can also notice that SBSE and SPE processes
have equivalent global warming impacts when considering the Indian
(eastern) electricity mix.
4. Discussion
4.1. Comparison of results with the literature
The aim of the publication was to compare the environmental im-
pacts induced by two extractions of organochloride pesticides in a fresh-
water sample. The study showed that the SBSE process induced less im-
pacts than the SPE in most categories. We also assessed the absolute
impact of both techniques for one sample. Since none LCA has been con-
ducted in the eld of sample preparation, it is not possible to compare
these results with the literature.
Therefore, we show orders of magnitude of CO
2
eq emissions related
to other products or services to help rationalizing the absolute results
of each sample preparation in Table 5 . It is important to point out that
these products or services cannot be compared from an LCA point of
view because they do not full the same functional unit.
On the basis of 10 analyses per working day (250 days), the GW
impact of SBSE preparation for one year is 423kgCO
2
eq which is ap-
proximately
1
4
of the amount of CO
2
eq that should be allowed to emit
6
B. Raccary, P. Loubet, C. Peres et al. Advances in Sample Preparation 1 (2022) 100009
Fig. 6. Environmental impacts comparison be-
tween SBSE and SPE extractions of pesticides in
freshwater (ReCiPe2016 Midpoint H). Abbrevi-
ations denitions are available in Table 1 .
Table 5
Orders of magnitude of CO2eq emissions for common products and services
One sample prepared with
SBSE (169 g CO2 eq)
One sample prepared with
SPE (331 g CO2 eq)
is equivalent to: Source of data Emission factor
1.9 3.7 km with a Renault Clio 4
(direct emissions only)
Renault data 90 g CO2 eq/km
1.5 3.0 kWh produced in France ecoinvent 3.7.1 110 g CO2 eq/kWh
0.2 0.3 kWh produced in Poland ecoinvent 3.7.1 1025 g CO2 eq/kWh
70.4 137.9 g of acetone produced in
Europe
ecoinvent 3.7.1 2.4 g CO2 eq/kg
Fig. 7. Inuence of the reuse of the vial and the vial cap for both SBSE and SPE
extractions on Global Warming (GW) impact category (ReCiPe2016 H Midpoint)
per person and per year to limit GW to 1.5°C objective
1
at horizon 2050
(Paris climate accord) [16] .
As mentioned in the introduction, several methodological tools have
been developed to assess the “greenness ”of analytical methods. We se-
lected the Green Analytical Procedure Index (GAPI) [17] and applied
the tool to both sample preparation procedures ( Table 6 ).
The GAPI is made of ve pentagrams to assess the greenness of dier-
ent steps of analytical method with a specic colour code: green for low
“inuence ”on the environment, yellow for medium and red for high.
The parameters and the layout of the GAPI are detailed in SI.
1 2 tons of CO
2
eq per capita per year.
Table 6
GAPI evaluation results for the SPE and the SBSE procedure
GAPI evaluation of the SPE procedure GAPI evaluation of the SBSE procedure
The SPE procedure results in worse indicators than the SBSE for
several categories because it is a macro-extraction (SBSE is a micro-
extraction), it requires solvent evaporation, more reagents, and gener-
ates more waste than the SBSE procedure. The SBSE has worse indicators
than the SPE concerning the highest toxicity of toluene compared to the
solvents used for the SPE, and because it uses more energy.
Both procedures have the same number of green elds (3) and SPE
has more red elds than SBSE, which is in accordance with the LCA
results.
In conclusion, GAPI gives fast and eective comparison of both ex-
tractions and key point of interests that can be deepen with the calcula-
tion of environmental impacts. The results of methodological tools and
of LCA calculations are thus complementary.
4.2. Eco-design strategies
The vial and the vial cap have the largest impacts on the environ-
ment. As shown by the sensitivity analysis, the reuse and the washing
of the vials and of the vial caps should be chosen for both procedures
in order to decrease the impacts. We considered that the vial is reused
100 times and the vial cap 5 times, but these parameters could even be
7
B. Raccary, P. Loubet, C. Peres et al. Advances in Sample Preparation 1 (2022) 100009
Fig. 8. Sensitivity analysis on 4 electricity
mixes for SBSE and SPE extractions on Global
Warming (GW) impact category (ReCiPe2016
(H) Midpoint)
increased to further reduce the impacts. In the SPE and SBSE tabs of the
SI, it is possible to modify the number of use of the vial, vial cap and
SBSE bar in order to compute the impacts of new scenario.
In terms of material selection, the vial cap is made of tetrauoroethy-
lene which manufacturing has a high impact on environment. The use
of another material for the vial cap could be examined.
Apart from the vial (and cap), SBSE impacts are dominated by the
use of electricity. As shown in section 3.5, the electricity mix of the
country have an inuence on the SBSE impacts and the geographical
context of the laboratory should be considered before choosing the most
sustainable solution for routine analysis of organochloride pesticides in
freshwater.
Conversely, SPE impacts are mostly dominated by the use of chemi-
cals. As a result, limiting the amount of acetone, nitrogen and deionized
water could signicantly reduce the impacts (associated to their produc-
tion, transport, and end-of-life).
4.3. Limitations and perspectives
For both studied processes, the manufacturing of the electrical de-
vices were not taken into account in the calculation. Background data
for the manufacturing and the end-of-life of the devices that are specic
to analytical chemistry is also lacking. Infrastructure usually contributes
to few impacts in LCA, but as analytical chemistry rely on high-cost de-
vices, this should be studied in the future [2] . An eort should be done
along with the manufacturers to build inventory data for these devices
in order to carry the most precise and exhaustive LCA.
For SPE, it is noteworthy that vials and vial caps (when used once)
and chemicals generate the same magnitude of impacts whereas chem-
icals are usually seen as more harmful for human health and the en-
vironment. We have to bear in mind that LCA takes into account the
impacts associated with the full supply chain of materials (raw material
extraction, fabrication, transport, end-of-life). Production of glass is en-
ergy intensive and usually generates high impacts when it is used only
once. These impacts do not occur at the laboratory when they are used
but rather during the production phase.
The direct emissions of chemicals in the laboratory and their associ-
ated impacts to chemists have been assessed considering 1% evaporation
rate and the toxicity characterization factors (CF) from ReCiPe2016. It
results in low contribution to toxicity impacts. However, the toxicity
characterization model from ReCiPe are not covering well the exposure
and eect of chemicals emitted indoor. Exposure measurements should
be performed to evaluate the environmental risks linked to the emis-
sions of chemicals. Integrating these parameters to LCA, as it has been
done for indoor air pollutant exposure in households [18] , would ensure
a more holistic accountability of health impacts.
The data used for the calculation of environmental impacts come
from generic ecoinvent datasets that might not give exact estimations
of the impacts of resources and processes needed to achieve the manu-
facturing of high purity chemicals or the quality of consumables needed
for the specicity of analytical chemistry. It has been shown that ne
chemicals manufacturing for pharmaceutical use had much higher im-
pacts than basic chemicals production [19] , we can suppose that the
same results would be obtained with the high purity chemicals used
in analytical chemistry. Some impacts could thus have been underes-
timated because further steps might be needed to get high purity and
quality materials (example: the activated silica of the SPE cartridge, or
high purity nitrogen).
Also, the number of reuses of the vial and the vial cap, or the amount
of chemicals used for the washing step are based on eld experience but
could vary depending on the laboratory practices.
5. Conclusion
The aim of the article was to apply LCA to two sample preparation
techniques (SBSE and SPE), in order to analyse and compare their envi-
ronmental impacts. The overall results show that the SPE process gener-
ates more environmental impacts than SBSE because SPE requires more
chemicals to prepare one sample. For both processes, the vial and vial
cap manufacturing are responsible for most of the impacts.
The sensitivity analysis shows that the reuse of the vial and the vial
cap signicantly reduced the overall impacts, which could be reduced
even more by investigating dierent materials for the septum (based on
TFE).
As the SBSE process rely on more electricity use than the SPE pro-
cess, variation of the electricity mix has a strong inuence on the SBSE
process induced impacts. As a consequence, spatial localisation of the
process should be taken into account before making eco-design choices.
The application of LCA to these two sample preparations allowed us
to show that LCA is an adequate methodology to quantify environmental
impacts of analytical chemistry, and that it could be further applied to
compare standard and novel approaches. However, inventory data is
still missing to increase the accuracy of the results.
This study paves the way for the application and standardization
of LCA to whole chemical analysis, composed of the sample collection,
preparation, analysis and the data analysis.
Supplementary data
Supplementary information (SI) to this article includes an Excel le
containing 8 tabs. The rst two tabs are the calculation sheets of the
environmental impacts of the SPE and SBSE process. These two tabs
include parameters (the number of uses of the vial and the vial cap, the
8
B. Raccary, P. Loubet, C. Peres et al. Advances in Sample Preparation 1 (2022) 100009
distance to the supplier and the electricity mix) that can be modied.
The third tab is the comparison of all selected impact categories for both
processes. The fourth and fth tabs report the two sensitivity analysis
(vial and vial cap reuse / electricity mix). The sixth and seventh tabs
are composed of the ecoinvent processes used for the LCI of both sample
preparations. The eighth tab includes the GAPI evaluation criteria.
Declaration of Competing Interest
The authors declare that they have no known competing nancial
interests or personal relationships that could have appeared to inuence
the work reported in this paper.
Acknowledgements
The authors acknowledge the support of the French National Asso-
ciation for Technical Research (CIFRE Convention 2019/1357 ).
Supplementary materials
Supplementary material associated with this article can be found, in
the online version, at doi:10.1016/j.sampre.2022.100009 .
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9
... It is noted that glass is considered highly recyclable as it can be reprocessed an indefinite number of times without requiring additional mineral resources. However, laboratory glassware when used only once generates waste, which can impact the environment [10] . In this direction, washing the glassware and reusing it, should be preferred over considering it as a single-use item. ...
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