Trends in Analytical Chemistry, Vol.

37, 2012 Trends

Analytical Eco-Scale for assessing

the greenness of analytical
procedures
Agnieszka Gałuszka, Piotr Konieczka, Zdzisław M. Migaszewski,
Jacek Namieśnik

We propose the analytical Eco-Scale as a novel comprehensive approach to evaluating the greenness of analytical methodology. It
is based on assigning penalty points to parameters of an analytical process that are not in agreement with the ideal green analysis.
This approach compares different parameters and different steps of the analytical process.
Traditional green chemistry metrics (e.g., Atom Economy, E-factor and Reaction Mass Efficiency), which were introduced for
organic preparations, do not usually fit the purposes of green analytical chemistry. Existing databases for evaluation of green
analytical methods refer to known procedures and instruments, and do not encourage new, more environmentally-friendly
equivalents.
As an alternative to traditional green chemistry metrics, the analytical Eco-Scale can be a good, semi-quantitative tool.
ª 2012 Elsevier Ltd. All rights reserved.

Keywords: Analytical Eco-Scale; Analytical procedure; Eco-Scale; Environment friendly; Green analytical chemistry; Green chemistry metrics;
Greenness; Method selection; Penalty point; Twelve principles of green chemistry

1. Introduction numerous scientific articles [7–9], but

Agnieszka Gałuszka, Zdzisław some of the important issues still require
M. Migaszewski The concept of green chemistry emerged detailed explanation. One such problem is
Geochemistry and the
at the beginning of the 1990s and can be green analytical metrics.
Environment Div., Institute of
Chemistry, Jan Kochanowski perceived as a contribution of chemists to The canons of green chemistry are the
University, 15G Świe˛tokrzyska the idea of sustainable development [1,2]. 12 principles proposed by Anastas and
St., 25-406 Kielce, As stated in the most popular definition of Warner [10]. The analytical consequences
Poland green chemistry proposed by Anastas [1], of these principles, related directly to six of
the principal objectives of green chemistry them (principle number 1, 5, 6, 8, 11 and
Piotr Konieczka,
Jacek Namieśnik* are reduction and elimination of the use 12), have been discussed elsewhere [5,11].
Department of Analytical and the generation of hazardous sub- Generally, the conformity of different
Chemistry, Chemical Faculty, stances. The branch of chemistry that analytical issues with the 12 principles of
Gdańsk University of contributes most to the use and the gen- green chemistry refers to reagents, energy,
Technology (GUT),
eration of hazardous substances is organic waste and methods (Fig. 1). Method selec-
11/12G Narutowicz St.,
80-233 Gdańsk, synthesis. For this reason, green organic tion is crucial and controls other issues. In
Poland synthesis has dominated green chemistry modern analytical laboratories, different
for almost a decade. methods and techniques can be used for
In 1999, the term ‘‘green analytical determination of a single analyte. Metro-
chemistry’’ was proposed [3] and, in the logical quality of the results [i.e. accuracy,
same year, the father of green chemistry, precision, selectivity, limits of detection
Anastas, drew attention to the need to (LODs)], cost of analysis, and specific
develop green analytical methodology [1]. standard procedures that are recom-
Since that time, interest in implementing mended for environmental, medical or
green chemistry principles in analytical other purposes are usually taken into
*
Corresponding author. chemistry has grown dramatically. This account when selecting analytical meth-
Tel.: +48 58 347 10 10; interest has resulted in recent publication odologies. However, this approach does not
Fax: +48 58 347 26 94;
of three books on this subject [4–6] and consider the green chemistry principles.
E-mail: [email protected]

0165-9936/$ - see front matter ª 2012 Elsevier Ltd. All rights reserved. doi:http://dx.doi.org/10.1016/j.trac.2012.03.013 61
Trends Trends in Analytical Chemistry, Vol. 37, 2012

Figure 1. Analytical consequences of the 12 principles of green chemistry.

In this article, we propose a new, comprehensive tool Another difficulty of green analytical methodology is
for semi-quantitative evaluation of analytical method- the multi-step character of the analytical process. Each
ologies that will make possible comparison and selection of the steps should be considered in relation to develop-
of the greenest alternative, and will enable the greenness ment of greener analytical procedures (Fig. 2). Tobi-
of new or modified methods to be tested. szewski et al. [7] pointed out that the least green step in
the analytical process is sample preparation. The best
approach is to eliminate this stage by applying a direct
2. Green chemistry metrics analytical method. In general, four aspects can be dis-
tinguished when developing new, greener analytical
The evaluation of analytical methodologies in the con- procedures, which are also called ‘‘Sustainable Analyti-
text of green chemistry is very difficult because of the cal Procedures’’ [14]:
large number and the diversity of analytes and analyti- (1) method-oriented [12,15,16];
cal methods, the complexity of sample matrices and the (2) analyte-oriented [17];
special analytical criteria that need to be considered (3) process-oriented [18]; and,
(e.g., precision, accuracy and LODs). We should stress (4) a combination of two or three of the approaches
that, in some cases, it is impossible to meet certain green mentioned above [19].
chemistry criteria in analytical methodology. In this The principal question that can be asked when
situation, efforts are needed to improve the method. A searching for a green analytical method is: ‘‘How to
good example of this approach is minimization of the use evaluate different procedures in order to choose the
of reagents that cannot be eliminated or substituted by greenest one?’’ There are general guidelines for green
using flow-injection systems [12] or miniaturizing ana- procedures, which usually consider only one aspect of a
lytical systems [13]. given method, {e.g., selection of a greener solvent

Figure 2. Comparison of the green chemistry criteria for three key steps in an analytical process.

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Trends in Analytical Chemistry, Vol. 37, 2012 Trends

[20,21]}. Recently, an application of green analytical 3. Green chemistry in analytical procedures

chemistry in a chromatography laboratory was dis-
cussed [16]. However, most of current approaches to In many analytical procedures, it is impossible to reduce
evaluating green methodology are based on a priori the use of reagents. There are some practices that can
judgment (i.e. not based on a scientific approach, but on make such analyses greener. Toxic reagents should be
instinctive selection of an analytical method). However, replaced by their safer equivalents, alternative solvents
it may sometimes lead to bias [e.g., the use of high- should be preferred and the hazard of analytical wastes
performance liquid chromatography (HPLC) and super- should be ameliorated. This last task can be achieved by
critical fluid chromatography (SFC) in pharmaceutical on-line decontamination of wastes (recycling, degrada-
industry]. Unexpectedly, the first method was found tion and passivation) [18].
greener on the basis of life-cycle assessment [16]. We Every analytical procedure comprises several steps, the
need a more quantitative approach to selecting a green number of which strongly depends on the sample prop-
analytical method. erties and the analytical method. Generally, the greater
The application of traditional green chemistry metrics the number of steps involved, the less green the analyt-
in green analytical chemistry is limited. The most ical procedure is (due to increased energy use and larger
popular parameters {e.g., E-factor [22], Atom Economy volume of waste). Thus, an ideal approach to green
[23], Reaction Mass Efficiency [24] and the Eco-Scale analytical methodology would be to reduce the number
[25]} were introduced for the purposes of organic of stages in a given analytical procedure. However, some
synthesis. of the steps are inevitable. The role of green analytical
Koel and Kaljurand [6] tried to adopt the Atom Econ- chemistry is to search for more environmentally benign
omy to analytical procedures. However, this approach analytical methodology. In this section, we discuss the
requires knowledge of the number of molecules of the most important issues in the green chemistry approach
analyte that gives a measurable analytical signal, which to multi-stage analytical procedures.
it is not always possible to obtain.
One of the most comprehensive ways to assess the 3.1. Sample collection, preservation, transport and
greenness of analytical methods used for environmental storage
purposes is a free Internet-searchable database – The first step of every analytical procedure is sample
National Environmental Methods Index (NEMI) – which collection. In some specific cases, analysis can be per-
can be found at the website http://www.nemi.gov. The formed directly on-site, without transport of sampled
rating of the existing methods is done on the basis of four material to the instrument (e.g., using a portable XRF
criteria that refer to properties of reagents or wastes used device). This type of sample collection is called in-line
in this method [26]: sampling [7] and can be considered the greenest
(1) persistent, bioaccumulative, toxic; approach to this step of the analytical procedure.
(2) hazardous; The time delay between sampling and obtaining
(3) corrosive (pH <2 or >12); and, analytical results is crucial for the greenness of analyti-
(4) volume (mass) of waste is >50 mL(g). cal procedure. In this respect, on-line and at-line
Another example of an Internet database that can be sampling represent a medium-green approach, and,
helpful in selecting a green analytical method is the according to Tobiszewski et al. [7], off-line sample col-
Green Chemical Alternatives Wizard (http://ehs.mit.edu/ lection should be avoided. The greenness of sample col-
greenchem/) developed by Massachusetts Institute of lection can also be discussed in terms of the energy use
Technology. This database is oriented towards chemicals (some sampling instruments need a power supply) and
and processes that can be changed to reduce the volume resources used (e.g., sample packaging and filters). In
of hazardous wastes in laboratories. general, the more items used in this step, the less green is
A very interesting approach to green organic the procedure.
synthesis evaluation, named Eco-Scale, was proposed Many samples (e.g., environmental, biological and
by Van-Aken et al. [25], who assumed that an ‘‘ideal’’ food) need preservation because of physical and chemi-
reaction, which has a score of 100 in the Eco-Scale, uses cal changes that may occur during sample collection,
inexpensive compounds, and is conducted at a room transport, storage and preparation. Preservation is very
temperature with a 100% yield, and is safe for both the important for the overall quality of analysis, because it
operator and the environment. For each of the para- assures the representativeness of the sample. There are
meters that differs from ‘‘the ideal value’’, penalty points different techniques used for sample preservation and
are assigned, lowering the total score. The higher the their application depends on analyte and sample types.
score, the greener and more economical organic prepa- Detailed description of sample-preservation techniques is
ration is. This concept can be adapted to evaluate green beyond the scope of this article and is given elsewhere
analytical methods. [27]. In general, these techniques can be divided

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Trends Trends in Analytical Chemistry, Vol. 37, 2012

Figure 3. Green alternatives for different steps of analytical procedure.

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Trends in Analytical Chemistry, Vol. 37, 2012 Trends

into: physical (chilling, freezing, and filtration) and months) usually needs chemical preservation. From the
chemical (acidification, alkalization, addition of preser- point of view of green analytical chemistry, this option is
vation agents). Sample preservation is not a green step in the least favorable.
an analytical procedure, because it requires energy and/
or the use of chemicals. The best option for green ana- 3.2. Sample preparation
lytical methodology is to avoid sample preservation, if As mentioned above, sample preparation is a critical step
possible. for the greenness of analytical procedure. It usually
The next important issue regarding preliminary steps comprises several operations in which non-green re-
of an analytical procedure is sample transport. Its agents (e.g., organic solvents and strong acids) are often
incompatibility with green chemistry principles results required. There are analytical procedures in which
from energy use [i.e. vehicle fuel and specific conditions sample preparation is unnecessary or is minimized to
for sample storage (e.g., chilling)]. This step could be routine activities (e.g., weighing, grinding, and sieving).
avoided by applying field analysis (field screening), The most important operations in a sample-preparation
which has a few advantages, as it: step are dry ashing, digestion, extraction, post-extraction
(1) allows real-time analysis; clean-up and derivatization.
(2) requires no, or little, sample preparation; Determination of trace elements in solid samples by
(3) uses portable instruments [28]; the majority of instrumental methods requires the sam-
(4) uses minimal energy and reagents; and, ple to be decomposed. The most common techniques of
(5) is cost effective [6]. solid-sample decomposition are dry ashing and wet
If transport is unavoidable, the distance between digestion. Dry ashing and subsequent dissolution of ash
sampling site and analytical laboratory should preferably in acids is often referred to as mineralization. In dry
be as short as possible. ashing, a sample is heated in a crucible placed in a
Sample storage is an optional step in an analytical muffle furnace at a temperature in the range 400–
procedure, and usually depends on laboratory capacity 800C. After ashing, the residues are dissolved in acids.
for performing analysis. Samples can be stored under Digestion is another type of solid-sample decomposition
ambient conditions (room temperature, dark, well-aer- for trace-element determinations, which also uses re-
ated room) or under special conditions (frozen or cooled). agents (usually mineral and oxidizing acids) and large
Sample storage for an extended period of time (weeks or amounts of energy. Hydrochloric, sulfuric, nitric,

Table 1. The penalty points (PPs) to calculate analytical Eco-Scale

Reagents
Sub-total PP Total PP
Amount <10 mL (g) 1 Amount PP · Hazard PP
10–100 mL (g) 2
>100 mL (g) 3
Hazard (physical, environmental, health) [45]* None 0
Less severe hazard 1
More severe hazard 2

Instruments
Energy [39] 60.1 kWh per sample 0
61.5 kWh per sample 1
>1.5 kWh per sample 2

Occupational hazard Analytical process hermetization 0

Emission of vapors and gases to the air 3

Waste None 0
<1 mL (g) 1
1–10 mL (g) 3
>10 mL (g) 5
Recycling 0
Degradation 1
Passivation 2
No treatment 3
*
PPs are assigned to each of hazard category posed by a reagent. Each reagent can have more than one hazard category, thus the sub-total PP
value for a single reagent may be greater than 2.

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Trends Trends in Analytical Chemistry, Vol. 37, 2012

perchloric and hydrofluoric (HF) acids are the acids most extracts. According to the eighth principle of green
commonly used to decompose samples [29]. They can be chemistry [10], derivatization should be avoided. How-
applied individually or in mixtures. Acid digestion can be ever, in some cases, derivatization may be an alternative
performed in open vessels using hot-plate or commercial to sample preservation [30]. Preparation of samples of
sample-digestion devices, but, in many laboratories, organic compounds for determination is time consuming
microwave-digestion systems are used for accelerating (it takes about 61% of the time of analysis) [31] and
and making the preparation step safer. Unfortunately, it reagent consuming. This step of analytical procedure
is impossible to make dry ashing and digestion greener, offers many options [32], which certainly should aim to
and, for many samples (e.g., soil and geological samples), make the analysis greener.
the use of HF is recommended. The greatest progress in making analytical procedures
The only green way to avoid decomposition of solid greener has been achieved in the field of extraction. The
samples for trace-element determinations is to use direct greenest option for preparing samples for determinations
analytical methods, but they may not always be of organic compounds comprises solventless techniques
applicable due to higher LODs (XRF) or a lack of [33–36]. If it is impossible to apply a solvent-free tech-
matrix-matched standards and reference materials [laser nique, the green alternative is reduction using a solvent
ablation inductively coupled plasma mass spectrometry or replacing organic solvents with ‘‘green solvents’’. The
(LA-ICP-MS)]. first goal can be achieved by applying shorter, smaller
The most problematic aspect in determination of or- diameter chromatographic columns [16,37] or using
ganic compounds is use of organic solvents that leads to selected types of extraction {e.g., solid-phase extraction
generation of hazardous waste. The source of large (SPE), pressurized fluid extraction (PFE), microwave-
quantities of wastes in organic analysis particularly in- assisted extraction (MAE), liquid-phase microextraction
cludes: derivatization, extraction and clean-up of the (LPME), or single-drop microextraction (SDME)

Table 2. The examples of penalty points (PPs) for hazards and energy of selected reagents and analytical techniques

Reagent Number of pictograms Signal word Penalty points

Acetic acid (glacial) 2 Danger 4
Acetic acid (30%) 1 Danger 2
Acetylene 2 Danger, Warning 3
Ammonia solution (25%) 3 Danger 6
Benzoic acid 1 Warning 1
Dichloromethane 1 Warning 1
Hydrochloric acid (30%) 2 Danger 4
Hydrogen peroxide (30%) 2 Danger 4
n-Hexane 4 Danger 8
Nitric acid (65%) 2 Danger 4
Potassium dichromate 5 Danger 10
Sodium hydroxide (30%) 1 Danger 2
Sulfuric acid (25%) 1 Danger 2

Technique Energy used

FTIR <0.1 kWh per sample 0
Immunoassay
Spectrofluorometry
Titration
UPLC
UV-Vis Spectrometry

AAS 61.5 kWh per sample 1

GC
ICP-MS
LC

NMR 1.5 kWh per sample 2

GC-MS
LC-MS
X-ray diffractometry

FTIR, Fourier transform infrared spectroscopy; UPLC, Ultra-performance liquid chromatography; AAS, Atomic absorption spectrometry; GC, Gas
chromatography; ICP-MS, Inductively coupled plasma mass spectrometry; LC, Liquid chromatography; NMR, Nuclear magnetic resonance
spectroscopy; GC-MS, Gas chromatography-mass spectrometry; LC-MS, Liquid chromatography-mass spectrometry.

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Trends in Analytical Chemistry, Vol. 37, 2012 Trends

Figure 4. Analytical procedure for a determination of copper in a brass sample by titration.

Table 3. The penalty points (PPs) for Cu determination by titration Table 4. The penalty points (PPs) for electrogravimetric Cu deter-
in a brass sample mination in a brass sample
Reagents Reagents
Penalty points Penalty points
HNO3: 10 mL 8 HNO3: 10 mL 8
NH3(aq.): 2 mL 6 NH3(aq.) 6
CH3COOH: 10 mL 2 H2SO4: 2 mL 2
KI: 2 g 0 NH4NO3: 2 g 1
Na2S2O3 0 P
17
Starch 0
KSCN: 2 g 1
P Instruments
17
Penalty points
Instruments
Heater 2
Penalty points
Occupational hazard 3
Heater 2 Waste 5
P
Occupational hazard 3 10
Waste 8 Total penalty points: 27
P
13 Analytical Eco-Scale total score: 73
Total penalty points: 30
Analytical Eco-Scale total score: 70

[34,36]}. Supercritical fluids, subcritical water, ionic column), and they are based on different mechanisms
liquids are examples of ‘‘green solvents’’ [7]. (e.g., adsorption, size-separation, partitioning, or oxida-
Post-extraction clean-up of organic compounds aims tion-reduction) [38].
to minimize the influence of interfering compounds on In the context of green analytical chemistry, clean-up
the detection of the analyte. Several methods are avail- of the extracts is an additional step in an analytical
able (e.g., alumina column, Florisil column, or silica-gel procedure, which uses extra reagents and resources,

Figure 5. Analytical procedure for an electrogravimetric determination of copper in a brass sample.

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Trends Trends in Analytical Chemistry, Vol. 37, 2012

Figure 6. Analytical procedure for a determination of copper in a brass sample by atomic absorption spectrometry.

generates extra waste, and, if possible, it should be determining a single analyte. The selection of analytical
avoided. method is commonly made on the basis of its accuracy,
precision, selectivity and LODs. According to green
3.3. Analysis analytical chemistry, it should also consider the envi-
Sample analysis requires using various analytical meth- ronmental and health impact [39]. There are several
ods and usually more than one technique is capable of classifications of analytical techniques. One of them, based
on the need for sample preparation, is especially important
for green analytical chemistry. In this classification, two
Table 5. The penalty points (PPs) for Cu determination by AAS in a
brass sample types of analytical technique are distinguished:
(1) direct, requiring no sample preparation; and,
Reagents (2) indirect, needing sample preparation.
Penalty points Garrigues and de la Guardia [40] provided a compre-
HNO3: 10 mL 8 hensive review of the direct methods. They divided direct
Cu standard solutions 3 methods into remote sensing, and methods without and
Acetylene 3
P with sample damage. The non-destructive measurement
14
techniques for solid-sample analysis include NIR spec-
Instruments troscopy, Raman spectroscopy, X-ray fluorescence and
nuclear magnetic resonance. Direct analysis with sample
Penalty points
damage is possible using electrothermal atomic absorp-
Heater 2 tion spectrometry (ETAAS), arc and spark optical emission
Spectrometer 2
spectrometry, laser ablation (with ICP-OES or ICP-MS),
Occupational hazard 3
Waste 8
glow discharge (with ICP-OES or ICP-MS), laser-induced
P breakdown spectroscopy (LIBS) and desorption electro-
15
Total penalty points: 29 spray ionization mass spectrometry (DESI-MS).
Analytical Eco-Scale total score: 71 Other analytical methods that allow direct analysis
encompass neutron activation, thermogravimetric and

Figure 7. Analytical procedure for a determination of mercury in an animal tissue by cold-vapor atomic absorption spectrometry.

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Trends in Analytical Chemistry, Vol. 37, 2012 Trends

Table 6. The penalty points (PPs) for Hg determination by CVAAS

the use of toxic reagents and a resulting decrease in
in an animal tissue waste generation [44].

Reagents 3.4. Calibration and validation

Penalty points Calibration and validation of analytical methods are very
Additives M and B 0
important for quality assurance. They are prerequisites
Hg standard solutions 2 for quantitative analysis. However, the use of calibration
P
2 solutions, internal/external standards, standard refer-
ence materials or isotope dilution contribute to enhanced
Instruments reagent consumption and waste generation. This step of
Penalty points analytical procedure is not always considered in evalu-
Freeze-drying instrument 2
ation of the greenness of analytical methodologies, but
Hot-plate 2 its contribution to waste generation should not be
Spectrometer 2 underestimated.
Occupational hazard 0
Waste 2
P
8 4. The concept of the analytical Eco-Scale
Total penalty points: 10
Analytical Eco-Scale total score: 90 The short discussion of analytical procedures in the
context of green chemistry presented in the previous
electrochemical methods, and immunoassays [30]. Of the section shows that there are more or less green alterna-
direct methods, real-time electrochemical monitoring tives for each step of the procedure (Fig. 3). On the basis
[41] and vibrational spectroscopy (FTIR, NIR, and of the data presented in Fig. 3, features of the ideal green
Raman) [42] are considered promising green analytical analysis can be deduced. This ideal green analysis will be
tools. a key parameter in our analytical Eco-Scale concept.
A modern trend in instrumental analysis, which meets
the needs of green analytical chemistry, is miniaturiza- 4.1. The ideal green analysis
tion of analytical methods [43]. The most important The ideal green analysis can be characterized by elimi-
advantages of analytical instrument miniaturization for nation or minimal use of reagents, minimal energy use,
the greenness of analytical procedures include reducing and no waste generation. These criteria are met only by

Figure 8. Analytical procedure for determination polychlorinated biphenyls in sewage sludge by gas chromatography coupled to mass
spectrometry.

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Trends Trends in Analytical Chemistry, Vol. 37, 2012

Table 7. The penalty points (PPs) for PCB determination in sewage

The sum of penalty points for the whole procedure
sludge by GC-MS should be included in the Eco-Scale calculation,
according to the following formula:
Reagents
Analytical Eco-Scale ¼ 100  total penalty points
Penalty points
Cu powder: 1.5 g 1
The result of calculation is ranked on a scale, where
HCl: 2 mL 3 the score:
Na2SO4 (drying agent): 4.5 g + 1 g 0 >75 represents excellent green analysis,
Isotopically labeled PCBs standard mixture 4 >50 represents acceptable green analysis,
Activated Al2O3: 1 g 0 <50 represents inadequate green analysis.
n-Hexane: 15 mL + 45 mL 16
Assignment of penalty points to categories of hazard
Acetone: 15 mL 8
Isooctane: 2 mL 8 and energy needs a detailed explanation. For assessing
Acidic silica (98% of H2SO4: 20 mL) 4 the hazard of reagents used in analytical procedures,
PCBs standard solution 4
P different classifications of hazardous substances can be
48 applied. For example, the NEMI database uses EPA
(Environmental Protection Agency) Toxic Release
Instruments
Inventory, Clean Water Act and Clean Air Act for
Penalty points environmental hazard assessment, and NFPA (National
Sampler 1 Fire Protection Association) classification for health and
Transport 1 safety hazard assessment, respectively [26]. We propose
Freeze-drying instrument (50C, 0.025 mbar) 2 to evaluate physical, environmental and health hazards
ASE extractor (1500 hPa, 125C) 2
on the basis of the Globally Harmonized System of
Rotary evaporator 2
Oven (for acidic silica preparation) 2 Classification and Labeling of Chemicals (GHS), which is
GC-MS 3 the most comprehensive, up-to-date classification of
Occupational hazard 0 chemicals [45]. For convenience and simplicity, we
Waste 4 propose that pictograms and signal words should be
P included in evaluation of the hazards posed by reagents
Total penalty points: 65 17
Analytical Eco-Scale total score: 35 used in an analytical procedure. Each reagent can be
characterized by one or more of the nine pictograms
(flame, flame over circle, corrosion, gas cylinder, skull
a few methods, which do not need sampling, sample and crossbones, exclamation mark, environment and
transport, preservation, and preparation (i.e. based on health hazard). For each pictogram, penalty points are
direct measurements). There are examples of these assigned. Two signal words are used in GHS: ‘‘danger’’
analytical methods in sub-section 3.3. In determination (more severe hazard, category 1 and/or 2) and ‘‘warn-
of many analytes, there is no direct method available, so ing’’ (less hazard, other categories). We propose the fol-
we propose that the ideal analysis should have the fol- lowing system of penalty point assignment to hazards:
lowing characteristics: none (no pictogram) = 0 penalty points
(1) reagents do not pose hazards (physical, environ- less severe hazard = 1 penalty points
mental, health); more severe hazard = 2 penalty points.
(2) less than 0.1 kWh of energy per sample is con- Penalty points for energy use will be assigned
sumed; and, according to the values proposed by Raynie and Driver
(3) no waste is produced. [39]. The least energy-consuming laboratory practices
and instruments (<0.1 kWh per sample) are, e.g.,
4.2. Components of the Eco-Scale immunoassays, titration, hot-plate solvent evaporation
The basis for our concept of an analytical Eco-Scale is (<10 min), needle evaporator, sonicator, and UV-Vis
that the ideal green analysis has a value of 100. This spectrophotometer [39]. The most energy-consuming
approach is analogous to the Eco-Scale proposed by Van techniques are NMR, GC-MS, LC-MS, X-ray diffraction,
Aken et al. for evaluating the greenness of organic hot-plate solvent evaporation (>2.5 h).
synthesis [25]. For each of analytical procedure para- Examples of penalty points assigned to reagents for
meters (amount of reagents, hazards, energy and waste), hazards and to analytical techniques for energy use are
penalty points are assigned if it departs from ideal green given in Table 2.
analysis (Table 1). Because the influence of hazardous
substances depends on their amount, we propose that 4.3. Examples of analytical Eco-Scale calculation
the total penalty points should be calculated by multi- In this sub-section, we evaluate several examples of
plying the sub-total penalty points for a given amount analytical procedures for their greenness using the
and hazard. analytical Eco-Scale. These examples present both

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Trends in Analytical Chemistry, Vol. 37, 2012 Trends

instrumental and wet-chemistry methods applied for analytical processes to enable the search for the weakest
determination of organic (PCBs) and inorganic (Cu, Hg) points, which could be improved in order to meet green
analytes in different matrices (sewage sludge, brass, and chemistry requirements. Existing green analytical eval-
biological material). uation tools (e.g., NEMI database) allow selection of one
The procedures are covered as follows: of the known procedures. This approach does not
(1) Cu determination in a brass sample by titration is encourage the adoption of new methodologies.
presented in Fig. 4, and the details about assigning The proposed analytical Eco-Scale can be a good semi-
penalty points are given in Table 3, quantitative tool for laboratory practice and educational
(2) Cu determination in a brass sample by an electro- purposes. It is simple and fast to use, has well-defined
gravimetric method is presented in Fig. 5, and the criteria of evaluation and can be applied to any known
details about assigning penalty points are given in and new methodologies. We believe that all these fea-
Table 4, tures will influence wide application of the analytical
(3) Cu determination in a brass sample by an AAS Eco-Scale in analytical laboratories.
method is presented in Fig. 6, and the details about We are aware that the proposed concept has its limi-
assigning penalty points are given in Table 5, tations. Some of analytical methods and techniques may
(4) Hg determination by CV-AAS in an animal-tissue not achieve the best ranking on the analytical Eco-Scale,
sample is presented in Fig. 7, and the details about despite their certain benefits for determination of a given
assigning penalty points are given in Table 6, analyte group. For example, determination of organic
(5) PCB determination in sewage sludge by GC-MS is compounds is usually much more complicated and
presented in Fig. 8, and the details about the pen- multi-stage than determination of trace elements, which
alty points are given in Table 7. results in much higher number of penalty points and
All the three methods of Cu determination in a brass lower rank in the Eco-Scale. Thus, application of the
sample have similar Eco-Scale values. Of these methods, analytical Eco-Scale will be especially important for the
electrogravimetry has the highest rank (73 in Eco-Scale) search for new, greener methodologies, because it clearly
and is followed by AAS (71 in Eco-Scale). Surprisingly and evidently indicates the weakest points in analytical
enough, titration has quite a high rank in the analytical procedures.
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