Challenges in green analytical chemistry

Kraus, Iowa State University, USA Andrzej Stankiewicz, Delft University of Technology, The Netherlands Peter Siedl, Federal University of Rio de Janeiro, Brazil Titles in the series: 1:

Challenges in Green Analytical Chemistry2nd Edition

Green Chemistry Series

Editor-in-chief:

James H Clark, Department of Chemistry, University of York, UK

Series editors:

George A Kraus, Iowa State University, USA

Andrzej Stankiewicz, Delft University of Technology, The Netherlands

Peter Siedl, Federal University of Rio de Janeiro, Brazil

Titles in the series:

1: The Future of Glycerol: New Uses of a Versatile Raw Material

2: Alternative Solvents for Green Chemistry

3: Eco-Friendly Synthesis of Fine Chemicals

4: Sustainable Solutions for Modern Economies

5: Chemical Reactions and Processes under Flow Conditions

6: Radical Reactions in Aqueous Media

7: Aqueous Microwave Chemistry

8: The Future of Glycerol: 2nd Edition

9: Transportation Biofuels: Novel Pathways for the Production of Ethanol,Biogas and Biodiesel

10: Alternatives to Conventional Food Processing

11: Green Trends in Insect Control

12: A Handbook of Applied Biopolymer Technology: Synthesis, Degradationand Applications

13: Challenges in Green Analytical Chemistry

14: Advanced Oil Crop Biorefineries

15: Enantioselective Homogeneous Supported Catalysis

16: Natural Polymers Volume 1: Composites

17: Natural Polymers Volume 2: Nanocomposites

18: Integrated Forest Biorefineries

19: Sustainable Preparation of Metal Nanoparticles: Methods and

Applications

20: Alternative Solvents for Green Chemistry: 2nd Edition

21: Natural Product Extraction: Principles and Applications

22: Element Recovery and Sustainability

23: Green Materials for Sustainable Water Remediation and Treatment24: The Economic Utilisation of Food Co-Products

25: Biomass for Sustainable Applications: Pollution Remediation and Energy26: From C-H to C-C Bonds: Cross-Dehydrogenative-Coupling

27: Renewable Resources for Biorefineries

28: Transition Metal Catalysis in Aerobic Alcohol Oxidation

29: Green Materials from Plant Oils

30: Polyhydroxyalkanoates (PHAs) Based Blends, Composites and

Nanocomposites

31: Ball Milling Towards Green Synthesis: Applications, Projects, Challenges32: Porous Carbon Materials from Sustainable Precursors

33: Heterogeneous Catalysis for Today’s Challenges: Synthesis,

Characterization and Applications

34: Chemical Biotechnology and Bioengineering

35: Microwave-Assisted Polymerization

36: Ionic Liquids in the Biorefinery Concept: Challenges and Perspectives37: Starch-based Blends, Composites and Nanocomposites

38: Sustainable Catalysis: With Non-endangered Metals, Part 1

39: Sustainable Catalysis: With Non-endangered Metals, Part 2

40: Sustainable Catalysis: Without Metals or Other Endangered

Elements, Part 1

41: Sustainable Catalysis: Without Metals or Other Endangered

Elements, Part 2

42: Green Photo-active Nanomaterials

43: Commercializing Biobased Products: Opportunities, Challenges,Benefits, and Risks

44: Biomass Sugars for Non-Fuel Applications

45: White Biotechnology for Sustainable Chemistry

46: Green and Sustainable Medicinal Chemistry: Methods, Tools andStrategies for the 21st Century Pharmaceutical Industry

47: Alternative Energy Sources for Green Chemistry

48: High Pressure Technologies in Biomass Conversion

49: Sustainable Solvents: Perspectives from Research, Business and

International Policy

50: Fast Pyrolysis of Biomass: Advances in Science and Technology

51: Catalyst-free Organic Synthesis

52: Hazardous Reagent Substitution: A Pharmaceutical Perspective

53: Alternatives to Conventional Food Processing: 2nd Edition

54: Sustainable Synthesis of Pharmaceuticals: Using Transition MetalComplexes as Catalysts

55: Intensification of Biobased Processes

56: Sustainable Catalysis for Biorefineries

57: Supercritical and Other High-pressure Solvent Systems: For Extraction,Reaction and Material Processing

58: Biobased Aerogels: Polysaccharide and Protein-based Materials

59: Rubber Recycling: Challenges and Developments

60: Green Chemistry for Surface Coatings, Inks and Adhesives: SustainableApplications

61: Green Synthetic Processes and Procedures

62: Resource Recovery from Wastes: Towards a Circular Economy

63: Flow Chemistry: Integrated Approaches for Practical Applications64: Transition Towards a Sustainable Biobased Economy

65: Transportation Biofuels: Pathways for Production: 2nd Edition

66: Challenges in Green Analytical Chemistry: 2nd Edition

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Challenges in Green Analytical Chemistry

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The concept of green analytical chemistry originated in the 1990s as anebulous idea of using less harmful solvents in sample preparation thanacetonitrile, which was the customary extraction agent in analytical practice

at that time It appeared to some to be an opportunistic way for the cipline to hitch its wagon to the rising star of green chemistry However, itsoon became obvious, owing to the efforts of the editors of this book andother analytical chemists, including Namies´nik, Koel and Raynie, that theconcept was in itself a solid science, with its own topics, problems andcontents

dis-Analytical chemistry is much more than a set of tools supporting otherbranches of chemistry Among other aims, it plays a significant role in set-ting limits to growth by identifying the boundaries within which technologycan be applied without endangering the sustainable functioning of humansociety In this role, green analytical chemistry now directly influences thegreenness of analytical chemistry As an information science, analyticalchemistry requires an information carrier One of the features by which theprogress of information science is measured is the reduction of the size ofthe carrier The big mainframe computers of the 1960s and 1970s have beenreplaced by smartphones, which are more powerful and execute many moretasks than foreseen at the beginning of the Internet era Analytical chemistryshares this requirement of information science to reduce the bulkiness ofthe information carrier While this goal still remains to be achieved, greenanalytical chemistry studies methods and teaches practitioners how to attain

it Therefore, a vital topic of green analytical chemistry is the miniaturization

of analytical equipment and the simplification of analytical procedures,including sample collection, processing and measurement Portability is adesirable feature that can be accomplished via miniaturization and micro-fluidics and modern sensor technology In addition, the discipline advocates

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the revival of earlier analytical methods such as colorimetry that takeadvantage of existing advanced technology such as smartphones The ul-timate goal of green analytical chemistry is the democratization of analyticalchemistry This idea, first proposed by de la Guardia, and the many ways ofachieving it, are a central theme of this book Democratization makes ana-lytical measurements available to everyone who desires to understand andcontrol their environment: the quality of food, air and water, in addition todata pertaining to a subject’s health.

This book makes an important contribution to the topics and aims listedabove The editors have assembled a remarkable team of authors and expertswho discuss the topics in depth I strongly recommend this work to allpractitioners of analytical chemistry, decision-makers in the fields of scienceand government and students and teachers of chemistry

I congratulate the editors, Salvador Garrigues and Miguel de la Guardia,and all of the outstanding contributors for the valuable perspective on greenanalytical chemistry contained in this book As it covers a wide range ofchallenges and successes ranging from emerging instrumental analyses tonovel approaches to sample preparation, new separation techniques, andthe rise of real-time sensors, this book provides insights into the evolution ofthe discipline over the past decade

Mihkel KaljurandTallinn, Estoniamihkel.kaljurand@taltech.ee

Preface to the Second Edition

The publication in 2008 of our review paper ‘Green Analytical Chemistry’ inTrends in Analytical Chemistry was motivated by the fact that, at that time,many authors had rediscovered the previously called clean analytical orenvironmentally friendly methods Hence, based on the international suc-cess of the green chemistry paradigm, proposed by Paul Anastas, it wasnecessary to redefine the objectives and practices involved in this sustain-able and environmentally friendly analytical chemistry movement The re-view was well accepted by the analytical community (so far it has receivedmore than 620 citations, as indicated in Google Academics) and has at-tracted the attention of major publishers such as Elsevier, the Royal Society

of Chemistry and John Wiley & Sons

Our research team accepted the invitations of these prestigious publishers

to produce three books on the subject of green analytical chemistry and in

2011 our authored book was published by Elsevier, followed also in 2011 bythe first edition of this book edited by us and published by the Royal Society

of Chemistry, and a further edited book published by Wiley in 2012, movingfrom a personal discussion of the objectives and tools of green analyticalchemistry to extended contents regarding different fields of application and,most important, taking into account the points of view of other researchteams in our country and others

However, it must be acknowledged that the first book to be published ongreen analytical chemistry was that written by Mihkel Koel and MihkelKaljurand, of Tallin University of Technology, Estonia At the time when wewere working on the books for Elsevier and the Royal Society of Chemistry,

we discovered that these authors were writing their own textbook This wasnot at all an unexpected situation in science in the twenty-first century andthere were reasons to expect that other active research teams, such as thatled by Professor Jacek Namies´nik, of Gdansk University of Technology, and

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the group of Professor Farid Chemat, at the Universite´ d’Avignon, could alsowrite a book on the same subject, owing to their active research in the field.Many researchers do not feel comfortable sharing their field of applicationand discovering that other authors have published a book in their fieldbefore them Obviously, this was not so in our case, and we found in Mihkeland Mihkel, and also in Farid and Jacek and his co-workers, such as MarekTobiszewski and Justyna P"otka-Wasylka, excellent friends and good col-laborators in many of our editorial and research activities Thus once againthe active workers in green analytical chemistry decided to continue to worktogether and contribute to the extension or their research from basic andapplied perspectives.

Eleven years after the publication of our review and eight years after thepublication of the book by Koel and Kaljurand, a new book has been pub-lished concerning green laboratory practices by Arabinda Das, a new bookedited by Justyna and Jacek has been published by Springer, the Royal So-ciety of Chemistry has published a new edition of the Mihkels’ pioneeringbook and Dunod published Farid Chemat’s new book on green extraction,E

´co-extraction du Ve´ge´tal All this provides clear evidence that the field ofgreen analytical chemistry is very much alive and the dynamic of developingsustainable methods has been spread all around the world, and every yearnew colleagues join the research on the principles of green analyticalchemistry and contribute to enlarging our knowledge of the sustainableperspectives of analytical methods

The present book is an update of our previous edition of Challenges inGreen Analytical Chemistry Taking into account the advances in this field inrecent years, we chose to look at a number of new topics that have emergedand incorporate new researchers’ voices Hence the reader will have theopportunity to find new authors, such as Jacek Namies´nik’s group, FaridChemat, Yukihiro Ozaki and Manel del Valle, and new subjects such aschemometrics, sensors and green solvents Thus we have made great efforts

to provide the reader with as complete as possible picture of the toolsavailable today for greening analytical methods

The reasons for continuing our efforts in green analytical chemistry comefrom the facts that this emerging field of research has been highly pro-ductive in creating new ideas and tools and that the social movement,concerning the third industrial revolution and the deleterious effects ofclimate change, encourages researchers to look for sustainable tools in allfields Additionally, as Jacek suggested in one of his recent papers, greenanalytical chemistry is also important in providing an equitable chemistrythat could widen the benefits of analytical methods to developing countriesand, as evidenced by our own publications in the clinical field, move in thedirection of a democratic analytical chemistry

Finally, we would like to dedicate this new book to the memory of JacekNamies´nik, a great scientist and close friend who contributed to enlargingthe horizon of green analytical chemistry from both sides, theoretical de-velopment and the incorporation of new tools for greening laboratory

practices We have lost a friend and one of the most prominent scientists inthe field However, we are happy that his work will be continued by thegeneration of analytical chemists that he encouraged to move in the greendirection and thus Jacek will always remain in our minds.

Salvador GarriguesMiguel de la Guardia

Preface to the First Edition

The general public worldwide has a poor opinion of chemistry Almost everyday the mass media broadcast bad news about environmental damagecaused by uncontrolled industrial practices and accidents Chemical elem-ents or compounds are identified as being responsible for the pollution ofair, water or soil, and also for the deaths of humans, animals and plants

In such a doom-laden scenario it can be difficult to convince our leagues and students of the benefits of chemistry We believe that thechemistry community should adopt a new style of communication in order

col-to promote the idea that chemistry is our best weapon col-to combat illness, andthat chemical methods can solve pollution problems caused by the incorrectuse of materials, or by the accumulation and transport of dangerous sub-stances in inappropriate conditions There is not bad chemistry and goodchemistry: there are only bad and good uses of chemistry The truth is thatthe advancement of chemistry is a good indicator of the progress ofhumanity However, we must look for a new paradigm that can help to buildbridges between the differing perspectives of chemists and the generalpublic

In our opinion ‘green chemistry’ now represents not only the rightframework for developments in chemistry but also the best approach toinforming the general public about advances in the subject The term wasfirst introduced in 1990 by Clive Cathcart (Chemistry & Industry, 1990, 21,684–687) and the concept was elaborated by Paul Anastas in his 12 prin-ciples Briefly, green chemistry provides a way to predict the possible en-vironmental downsides of chemical processes rather than solving them afterthe fact It provides a series of recommendations for avoiding the deleteriousside effects of chemical reactions, the use of chemical compounds and theirtransport, as well as a philosophy for improving the use of raw materials inorder to ensure that our chemical development is sustainable The principles

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of green chemistry build on the efforts made in the past to improve chemicalprocesses by improving the experimental conditions, but pay greater atten-tion to the use of hazardous materials, the consumption of energy and rawmaterials, and the generation of residues and emissions This is consistentwith recent regulations that have come into effect in different jurisdictionsrelating to the registration, evaluation, authorization and restriction ofchemical substances, especially the REACH norms established by theEuropean Union.

Within the framework of green chemistry, green analytical chemistry tegrates pioneering efforts to develop previously known clean methods ofanalysis, the search for highly efficient digestion systems for sample prep-aration, the minimization of analytical determinations, their automation,and the online treatment of analytical wastes These efforts have improvedthe figures of merit of the methodology previously available, helped to re-duce the cost of analysis and improved the speed with which analytical in-formation can be obtained Along with all these benefits there have beenimprovements in the safety of methods, both for operators and for the en-vironment It is therefore not surprising that green analytical chemistry isnow a hot topic in the analytical literature

in-Two books on green analytical chemistry have appeared in the last year:one by Mihkel Koel and Mihkel Kaljuran, published by the Royal Society ofChemistry, and one by Miguel de la Guardia and Sergio Armenta, published

by Elsevier These books help to clarify the present state of green analyticalchemistry and the relationship between the relevant publications in theanalytical literature However, until now there has been no multiauthor book

by specialists in the different fields of our discipline describing the variousdevelopments made in green analytical chemistry The present book is anattempt to make such an approach to recent advances in sample prepar-ation, miniaturization, automation and also in various analytical methods,ranging from electroanalysis to chromatography, in order to contribute tothe identification of the green tools available in the literature and to dis-seminate the fundamentals and practices of green analytical chemistry

We hope that this book will be useful both for readers working in theindustrial field, in order to make their analytical procedures greener, andalso for those who teach analytical chemistry in universities, to help themsee their teaching and research activities in a new light and find ways ofmaking our discipline more attractive to their young students

This book has been made possible by the enthusiastic collaboration ofseveral colleagues and good friends who have written excellent chapters ontheir respective fields The editors would like to express their gratitude forthe extra effort involved in this project, generously contributed by peoplewho are continually active in the academic, entrepreneurial and researchfields During the development of this project we lost one of the authors,Professor Lucas Herna´ndez, from the Universidad Auto´noma de Madrid, anexcellent scientist and a good friend He became ill while writing his chapterand died before seeing the final version of this book On the other hand,

Professor Lourdes Ramos, from the CSIC, became pregnant and we celebratethe arrival of her baby Lucas So, in fact this book is also a piece of life, ahuman project, written by a number of analytical chemists who believe there

is a better way to do their work than just thinking about the traditionalfigures of merit of their methods We hope that readers will enjoy the results

Chapter 1 Past, Present and Future of Green Analytical Chemistry 1

Miguel de la Guardia and Salvador Garrigues

1.5 The Future: A Democratic Analytical Chemistry

Chapter 2 Direct Analysis by Green Spectroscopy and Spectrometry 19

Salvador Garrigues and Miguel de la Guardia

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2.5 Direct Analysis of Solid and Liquid Samples Without

2.5.1 Mineral Analysis by X-ray Techniques 362.5.2 Molecular Analysis by NMR Spectroscopy 362.5.3 Molecular Analysis by Vibrational

2.7 Remote Sensing and Teledetection Systems 44

Manel del Valle

3.1 Chemical Analysis Performed with Sensors 55

3.2.1 Use of Metal and Metal Oxide

3.3 Colorimetric Sensing with a Smartphone Camera 653.4 Electrochemical Biosensors Using a Portable

3.6 Smart Systems: Electronic Noses and Electronic

Chapter 5 Greening Sample Preparation: New Solvents,

5.2.3 Dispersive Liquid–Liquid Microextraction 125

5.3.1 Miniaturized Solid-phase Extraction 1295.3.2 Microextraction by Packed Sorbent 1335.3.3 Miniaturized Dispersive Solid-phase

6.2.5 Multicommutation and Multipumping

6.4.4 Minimization of Reagent Consumption and

Paloma Ya´n˜ez-Seden˜o, Susana Campuzano and

Jose´ Manuel Pingarro´n

7.2 Electrodes and Electrochemical Sensors 1827.2.1 Alternatives to Mercury Electrodes 1827.2.2 Novel Eco-inspired Electrode Materials 185

Chapter 8 Green Solvents for Analytical Chemistry 221

Anne-Sylvie Fabiano-Tixier, Harish Karthikeyan Ravi,

Boutheina Khadhraoui, Sandrine Perino, Maryline Abert-Vian,Cyrille Santerre, Nadine Vallet and Farid Chemat

8.2 Decision Support Tools for the Choice of Alternative

8.2.1 Solubility Prediction Methods According to

8.7 NADESs as Green Solvents for Analytical Chemistry 2408.7.1 Green Solvents from Ionic Liquids (ILs) andDeep Eutectic Solvents (DESs) to Natural

Chapter 9 Green Chromatography: State-of-the-art, Opportunities

Justyna P!otka-Wasylka, Magdalena Fabjanowicz,

Kaja Kalinowska and Jacek Namies´nik

9.3 Portable Chromatographs and On-line and At-line

Chapter 10 Chemometrics as a Green Analytical Tool 277

Kanet Wongravee, Mika Ishigaki and Yukihiro Ozaki

10.5 Applications of Chemometrics in Optical Chemical

10.6 Some Examples of Applications of

10.6.1 Moving Window Partial Least-squares

Regression (MWPLSR) and Its Application

to In Vivo Non-invasive Monitoring ofBlood Glucose by Near-infrared Diffuse

10.6.2 Near-infrared (NIR) Electronic Spectroscopy

Study of a Calcination Reaction of HighlyReflective Green–Black (HRGB) Pigments 32410.6.3 Raman Imaging Study of the Lycopene

Chapter 11 Evaluation of the Greenness of Analytical Procedures 337

Marta Bystrzanowska, Jacek Namies´nik and Marek Tobiszewski

11.3 Assessment of Procedures by Scoring 343

11.4 Comparative Assessment of Procedures 346

CHAPTER 1

Past, Present and Future of

Green Analytical Chemistry

MIGUEL DE LA GUARDIA* AND SALVADOR GARRIGUES

Department of Analytical Chemistry, University of Valencia, ‘‘Jeroni

Mun˜oz’’ Research Building, c/Dr Moliner 50, 46100 Burjassot, Valencia,Spain

*Email: miguel.delaguardia@uv.es

Nobody could imagine at the end of the last century the wonderful successthat green analytical chemistry (GAC) would achieve In fact, preliminaryproposals in this field spoke about environmentally friendly conscientiousanalytical chemistry1or an integrated approach of analytical methods,2theformer being referred to in the title of the editorial in the first special issuedevoted to clean analytical methods, published in the Royal Society ofChemistry journal The Analyst in 1995

It could be considered that as analytical chemistry involves relatively smallvolumes of chemicals compared with synthetic and industrial chemical ac-tivities, the deleterious side effects of analytical methods would not be ofgreat concern However, the importance of analytical measurements, rec-ognized by Paul Anastas in his books on green chemistry (GC),3,4and the factthat analytical chemistry methods are used extensively in both academic andapplication laboratories, made this subject of special relevance in everydayactivities.5 As a result, GAC has experienced tremendous growth since theend of the twentieth century In fact, from 1995 to 2000 only 27 papers werepublished on this topic and the main part of those concerned only clean or

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sustainable methods, not using the term ‘‘green’’ directly In 2001, JacekNamies´nik published the paper ‘‘Green analytical chemistry – some re-marks,’’ including for the first time the term green analytical chemistry inthe title.6This contribution was followed in 2002 by ‘‘Some remarks on gaschromatographic challenges in the context of green analytical chemistry’’(Wardencki and Namies´nik)7

and a paper by Joseph Wang entitled time electrochemical monitoring: Toward green analytical chemistry’’8 inthe electroanalytical field Despite this, it is important to note that up to

‘‘Real-2019 fewer than 60 papers have been published that included the completeterm green analytical chemistry in the title However, some efforts have beenmade in studies of the theoretical aspects of GAC and this will improve thedevelopment of green methods in the present century

Figure 1.1 shows the evolution of the literature on green analyticalmethods from data obtained from the Web of Science Core Collectiondatabase considering the presence of the terms ‘‘green analytical chem-istry’’, ‘‘green analytical method’’, ‘‘clean analytical method’’ or ‘‘environ-mentally friendly method’’ From the comparison of these data with thoseincluded in the book Green Analytical Chemistry: Theory & Practice,9 pub-lished in 2011, it can be concluded that the impact of this subject on theanalytical literature of this century has been substantial, especially after thepublication in 2010 of the first book on GAC by Mihkel Koel and MihkelKaljurand entitled Green Analytical Chemistry.10

Up to 2007, only 29 review papers were published on general GAC orspecial topics closely related to it, such as miniaturization, sensors, lessaggressive sample preparation techniques to the environment, flow analysis

Figure 1.1 Evolution of the literature on green analytical chemistry from 1994 to

2018

or green aspects of special application fields such as gas chromatography,electrochemical methods, spectroscopy, plasma-based techniques and ionicliquids.9In fact, in only 12 of the published reviews was the term ‘‘greenanalytical’’ included in the title Along with this progress in publicationsconcerning GAC, the evolution of the number of times these papers havebeen cited is also evident, as can be seen in Figure 1.2, indicating an ex-ponential increase in the citations of the papers considered in Figure 1.1.The most cited papers relating to GAC are listed in Table 1.1.5,8,11–26As can

be seen, most of them correspond to reviews published in the journal Trends

in Analytical Chemistry (TrAC), including studies related to GAC mentals and greener metrics or applied techniques evaluated from the point

funda-of view funda-of GAC The importance funda-of papers relating to sample preparationconcerning the use of microextraction techniques and the large number ofcitations received per year (taking into consideration that the absolutenumber of citations per year and not the cumulated number is presented)are noticeable

Concerning authors publishing papers on GAC, Spain, Brazil, Poland, theUSA and China are the countries that have contributed the most from 1994until now, with Talanta, Trends in Analytical Chemistry, Journal of Chroma-tography, Analytica Chimica Acta, Analytical and Bioanalytical Chemistry,Analytical Methods and Microchemical Journal being the most commonjournals for publication, with more than 35% of the total contributions Thisclearly supports what Professor Kaljurand said about GAC: ‘‘Authors try to beenvironmentally friendly, editors and journals love the term and green iseasily understood by the whole of society, thus we can expect a great futurefor GAC’’ (M Kaljurand, personal communication)

Year

Figure 1.2 Number of times the papers relating to green analytical chemistry

considered in Figure 1.1 have been cited

Past, Present and Future of Green Analytical Chemistry 3

In fact, one of the reasons for the success of GAC in applications tories, but also at the academic level, is that green methods are, in general,less expensive than classical methods This is an added value that is wel-comed by the scientific community It explains the fact that many journalshave devoted special issues to GAC that reveal the growth in this field andthe permanent interest of editors and authors In the same context, it is notastonishing that the first book devoted to GAC, as indicated previously, waspublished in 201010and that, as can be seen in Table 1.2, nowadays there aremany books available9,10,29–33 and some of these are undergoing new edi-tions, whereas from 1996 to 2007 books and journals devoted to green topicsconcerned just green chemistry.

labora-In short, the data reported on GAC evidence today’s interest in the fieldand the growth of the literature that has dramatically changed the mentalityabout the consumption of energy and reagents, modified many of the habits

in laboratories and provided new activities devoted to minimizing ordetoxifying analytical waste, providing a change of the paradigm fromchemurgy to ecological chemistry, as was expounded by Professor HannsMalissa in 1987.34

The attitude of the general population towards the environment, with theexception of a small number of politicians, has been modified in the last

20 years owing to the problems created by the environmental impact ofhuman activities on climate change The evidence for the limits of the

Table 1.2 Books relating to green analytical chemistry

Year Authors/Editors Title Publisher Ref

Green Analytical Chemistry:

Theory & Practice

Elsevier 9

2011 M de la Guardia and

S Garrigues (eds)

Challenges in GreenAnalytical Chemistry

John Wiley &

Springer 31

2017 E Iban˜ez and

A Cifuentes (eds)

Green ExtractionTechniques: Principles,Advances and Applications

Green Analytical Chemistry:

Past, Present andPerspectives

Springer NatureSingapore PteLtd

73

human and social development of our societies, the reduction of fossil fuelreserves and the new challenges created by plastic and solid residues ingeneral, gas emissions into the atmosphere and pollution of sweet waterreservoirs, including the effect of human activities on polar ice, havemoved many people to have serious concerns regarding environmentalprotection In such a frame, it is clear that any activity related to environ-mentally friendly laboratories should be welcomed, and GAC is noexception.

The concern about the deleterious side effects of many reagents, sively used in the past in our laboratories, has moved authors, refereesand editors to think seriously about the replacement of toxic compoundswith innocuous materials or, at least, with less harmful products, and thisalso involves worries about the safety of method operators and environ-mental damage Therefore, nowadays many efforts are being devoted tosearching for new renewable feedstocks to be used as reagents and solv-ents, such as agrosolvents,35and to incorporate smart materials that areable to improve the sensitivity and selectivity of sample preparationmethods.36In short, it can be concluded that GAC has provided new ideasand objectives for basic research and hence it does not concern ecologicalopposition to the use of chemicals On the contrary, GAC involves the deepevaluation of new alternatives and, because of that, the new mentality hasevidenced clever solutions in the face of chemical problems and put thespotlight on the resolution of problems and new challenges and not at all

exten-on a fundamental ecologism that cannot provide correct answers at thelevel of consumer needs

The mixture of a pragmatic point of view and an ethical compromise withenvironmental sustainability has given prestige to the so-called green ana-lytical methods which, ultimately, provides correct solutions at the requiredaccuracy, sensitivity, selectivity and precision levels without side effects foroperators and the environment

On the other hand, the efforts made to move from off-line batch terminations in the laboratory to point-of-care and in situ analysis or remotesensing of target analytes provide strong reductions in the consumption ofreagents and waste generation and also energy demands, and all of thisreduces the method costs, thus offering cheaper alternatives that are greatlyappreciated by companies and applications laboratories Thus, as ProfessorFarid Chemat said: ‘‘green analytical chemistry could also be called pooranalytical chemistry’’ (F Chemat, personal communication), and this point

de-of view is close to the common use de-of vanguard methodologies37in greenanalytical methods rather than costly conventional rearguard analyticalsystems and the extended use of screening methods suitable to provide anappropriate level of information in a short time, once again contributing todecreasing methodology costs

Summarizing, it is not at all astonishing that GAC was developed after thepopularization in the 1970s of flow methodologies, because they contributed

to the adoption of method automation, taking advantage of flow injection

Past, Present and Future of Green Analytical Chemistry 7

analysis (FIA),38 sequential injection analysis (SIA),39lab-on-a-valve (LoV)40and lab-on-a-chip41 and multicommutation42 developments to reduce theconsumption of samples and reagents and minimize operator manipulationand waste generation.

Automation is, basically, a very useful tool to integrate, in a single fold, all the steps required in analytical methods and to minimize operatorand environmental risks Further, the addition of a waste treatment stepafter analyte determination has evidenced that chemical problems could besolved with an extra bit of chemistry43and, once again, this opens up newperspectives for basic and applied research

mani-An additional reason for the importance of GAC methods comes from theefforts to make available the advantages of analytical chemistry to isolated andless developed societies, making extra efforts to move from sophisticatedmethods, based on the use of high-cost instrumentation, to the modelling ofsignals obtained with relatively low-cost and readily available instruments.Based on the use of chemometrics and direct measurements, it is possible todevelop fast and cheap methods, using a series of samples well characterized

by reference methodologies as calibration standards.44Thus, extensive datamodelling and the use of lower cost instruments and free-of-charge softwareavailable in the cloud have extended the analytical tools and the availability ofthese methodologies to a large number of beneficiaries and users

All the aforementioned reasons are summarized in the scheme inFigure 1.3, which shows that reasons for moving to GAC concern knowledgeadvancement together with ethical and economic reasons

CHARACTERISTICS OF GREEN METHODS

1.3 Theoretical Developments in GAC

At the end of the twentieth century, the ‘‘Twelve Principles of GreenChemistry’’, defined by Anastas and Warner,4oriented alternative research

on sustainable chemistry Of these principles, the 11th was devoted to theneed for real-time analysis to prevent pollution, but many of these analysescould be directly translated to the requirements of GAC methods, henceavoiding derivatizations, if possible, is a common point between the GC andGAC principles established by Ga"uszka, Migaszewski and Namies´nik in

201312and also the use of renewable feedstocks and the reduction of risks,waste and energy consumption (see Table 1.3)

In fact, the so-called SIGNIFICANCE mnemonic can be considered anexcellent translation to the everyday work in analytical chemistry of the mainprinciples of Anastas, independently of the fact that GC put the stress oncatalytic methods and GAC must try to be adapted to the user’s needs, andwell crystallized the four priorities of GAC established by Namies´nik in

2001,6 regarding (1) elimination or reduction of reagents and solvents,(2) reduction of emissions, (3) elimination of toxic reagents and (4) reduction

of labour and energy, and our own six basic strategies for greening analyticalchemistry, established at that time, concerning (1) direct analysis of un-treated samples, (2) alternative sample treatments, (3) miniaturization andautomation, (4) on-line decontamination, (5) search for alternative reagentsand (6) evaluation of energy consumption.9

The aforementioned theoretical approaches, together with efforts toevaluate method greenness (see Chapter 11 for additional details), have

Table 1.3 Principles of green chemistry versus principles of green analytical

chemistry

Green chemistry Green analytical chemistry

1 Prevent waste S Select direct analytical techniques

2 Design safer chemicals and

4 Use renewable feedstocks N Never waste energy

5 Use catalyst not stoichiometric

7 Maximize atom economy I Increase safety of operator

8 Use safer solvents and reaction

conditions

C Carry out in situ measurements

9 Increase energy efficiency A Avoid derivatizations

10 Design chemicals and products to

degrade after use

N Note that sample number and sizeshould be minimal

11 Analyse in real time to prevent

contributed to the regularization and systematization of GAC in universitycourses and laboratory practice, thus creating a new generation of analyticalchemists for the future.

One of our objectives when in 2011 we started the production of books lated to GAC was to extend the ideas from our laboratory to as many researchteams as possible involved all around the world on these kinds of problemsand, for example, the number of authors varied from two in the 2011 Elsevierbook9to 24 in the Royal Society of Chemistry book also published in 201129and to 50 in the 2012 Wiley book.30In the last book mentioned there werecontributors from India, Poland, Estonia, Taiwan, Argentina, Italy, Japan,Iran and Brazil, thus clearly showing that, in addition to Spanish labora-tories, there was general worldwide interest in the subject

re-Figure 1.4 shows the general distribution of papers published from 2007

in different fields of GAC, including spectroscopy (atomic and molecular),electroanalytical methods and separation methods, covering chroma-tography and electrophoresis techniques Methods based on imaging treat-ment are also included

From the reported published papers, it can be concluded that the mostnumerous is the group concerning fundamentals, which include papersrelating to the principles of GAC, green metrics and those, mainly reviews,regarding sample preparation and the use of extraction techniques

A detailed study of the evolution of the contributions on GAC indicatedthat prior to this century electroanalysis, electrophoresis and especially

Atomic spectroscopy 8%

Molecular spectroscopy 14%

Vibrational spectroscopy 6%

Electroanalytical 5%

Electrophoresis 2%

Liquid Chromatography 20%

Figure 1.4 Distribution of green analytical chemistry publications as a function of

the instrumental field involved in the period from 2007 to 2019

molecular spectroscopy were the main techniques considered Molecularspectroscopy continues to be the most common greener alternative techni-que From 2010 there has been an increase in papers relating to othertechniques, such as atomic spectroscopy and chromatography, particularlyliquid chromatography, and also a proliferation of studies relating to samplepreparation, especially focused on extraction techniques This trend con-tinued to grow in the following years so that currently most of the studiesrelating to GAC concern sample preparation and the use of chromato-graphic, molecular spectroscopic and electroanalytical techniques, with theprogressive incorporation of applications based on image processingthrough the direct use of cameras and smartphones or devices coupled tothem.45

From recently published papers, it can be also concluded that there is ageneral trend of authors to use remote sensing or direct methods, withoutinvolving any chemical modification of samples or analyte extraction.However, greening the analytical methods also involves reducing the con-sumption of reagents and energy in traditional methods, reducing and/ordegrading the generated wastes and, in short, enhancing the so-called en-vironmentally friendly characteristics of methods in addition to preservingthe main features of the methods Achieving the appropriate levels of ac-curacy, sensitivity and selectivity required for making decisions continues to

be a basic requirement of being green.46

Paradigm?

In recent years, the conceptual advancement on GAC has moved in parallelwith efforts to incorporate new screening tools and low-cost tools to solveanalytical problems

In 1975, the pioneering work on FIA47and the use of microwave ovens forsample digestion48 paved the way for methodological improvements ofavailable methods for both analyte detection and sample preparation andalso evidenced the possibility of finding appropriate low-cost solutions.Thus, the use of readily available inexpensive apparatus favours the devel-opment of methods suitable for use all around the world and in spite of thelevel of laboratory budgets.49

Regarding sample preparation, the use of closed reactors showed thatpressure, temperature and reagents were the main variables for assuring thecomplete extraction of target analytes and correct matrix removal or partialmatrix decomposition In recent years, it has been demonstrated that inaddition to classical hard digestion methodologies, such as dry ashing andwet ashing, the use of microwave-assisted methods50and soft energy tech-nologies such as ultrasound-assisted procedures51provided efficient heatingsystems that permitted the quantitative recovery of target analytes, with astrong reduction of matrix effects during the measurement step together

Past, Present and Future of Green Analytical Chemistry 11

with reductions in analyte losses and contamination, also increasing thepossibilities for metal speciation.52Additionally, these alternative digestionmethods provided relatively low-cost tools in terms of both equipment andenergy consumption On the other hand, modern sample treatment alter-natives were also highly compatible with the automation of systems, thusoffering well-integrated methodologies.53

In recent years, the search for the design of point-of-care tools has takenadvantage of the reduction of the power supply requirements of microwaveovens to make possible the in-field extraction of essential oils from plants,54and these treatments could be also adapted for in-field mineral analysis ofsolid samples based on closed reactor digestion and the use of colorimetricassays

Another recent advance in sample preparation concerns the use of hardcup espresso machines to improve fast analyte extraction (of the order of lessthan 100 s), based on the use of relatively high temperature and pressureconditions,55and this is an important contribution that permits analyticalproblems to be solved with inexpensive and worldwide readily availableinstrumentation

Hence it can be concluded that new tools for sample preparation providelow-cost and sustainable methodologies that have also reduced drasticallythe time, labour and costs of sample preparation Additionally, the advan-tages concerning the main analytical features of selectivity and, in somecases, sensitivity that were improved by the new approaches must also betaken into consideration

In the list of new tools to make analytical determinations easier, the use ofportable devices for air quality control,56lateral flow analysis sensors57and,

in general, bio(chemical) sensors58 provides point-of-care low-cost natives to rearguard methods

alter-A good example of the changes introduced into analytical chemistry by thedevelopment of the aforementioned green tools concerns the extended use

of image processing methods Both general sample parameters59and cific sample characteristics60 could be determined for natural sampleswithout any chemical or physical damage, just based on the treatment ofimages obtained by using digital and smartphone cameras.45Additionally,image treatment methods together with simple colorimetric assays and/orpaper chromatography61,62 or gel electrophoresis63 improve the sensitivityand selectivity of these in situ determinations

spe-The advances in chemometrics (see Chapter 10) together with the use ofthe available software permits a move from costly and expensive instru-mentation to the use of low-cost, readily available and point-of-care meth-odologies, which could change the perspective of analytical chemistry64–68even though the use of powerful rearguard methodologies is required inmost cases for a complete characterization of samples to be used for cali-bration purposes

On the other hand, the Internet and the tremendous development of cial networks will provide new data distribution approaches without any

time delay between data acquisition and data distribution, leading, at thesame time, to great possibilities for fast decision-making but also creatingproblems to confirm true information.49Thus, as indicated in Figure 1.5, thedemocratic analytical chemistry (DAC) concept has moved from the exten-sion of benefits to the main aspects of data production.

In fact, analytical chemistry throughout the world at the human scalelooks very promising as an added-value side effect of GAC that will movefrom a main objective of being safe and sustainable to a new perspective inorder to be beneficial for the whole population and all practitioners.69The adoption of the term ‘‘democratic analytical chemistry’’ (DAC) todescribe the new perspective49,70was made taking into account not only theadvantages but also the risks involved in the new situation Figure 1.6compares some of the deleterious aspects of classical methods of analysis,described as old concepts that provided pretentious ideas about analyticalscience and analytical chemists, and the fact that in the new scenario created

by DAC the availability of low-cost instrumentation and easy and fastmeasurements, free access of software in the cloud, the tremendous devel-opment of on-site and point-of-care data acquisition with speed-of-light datasharing through the Internet will create a new frame of solidarity andglobalization that will provide open diffusion of data and opinions In thisrespect we are absolutely convinced that it has tremendous advantages butalso involves many risks

Figure 1.7 summarizes the main risks associated with the misuse ofreadily available instrumentation, inexperienced data acquisition and theirresponsible generation and distribution of false analytical information.From the lack of representative or inexperienced data to the misuse of truedata and distribution of false data, all these mistakes or bad attitudes can

● REMOTE SENSING

● POINT of CARE methodology

● Improved ACCESS to low-cost

INSTRUMENTATION

● FREE ACCESS SOFTWARE in the CLOUD

● READILY AVAILABLE INSTRUMENTATION

● DATA DISTRIBUTION through SOCIAL NETWORKS

A SINGLE WORLD at HUMAN SCALE

from BENEFITS to DATA PRODUCTION

CONCEPT of

DEMOCRATIC ANALYTICAL CHEMISTRY

Figure 1.5 Concept of democratic analytical chemistry (DAC)

Past, Present and Future of Green Analytical Chemistry 13

dramatically affect both the trueness of analytical results and the prestige ofour discipline In view of the aforementioned risks, education and analyticalchemistry education, together with self-control and social responsibility ofoperators71,72 and the critical attitude of data receptors, could be the mainpotential solutions to the risks of democratic analytical chemistry.Additionally, the development of a simple and clear analytical chemistrylanguage is necessary so as to be able to transmit technical analytical in-formation to the general population, without a requirement for an adequatelevel of technical knowledge, in order to avoid misunderstandings that cancreate unjustified alarm situations.

RISKS of DEMOCRATIC ANALYTICAL CHEMISTRY

● Lack of representative data IMPORTANCE of ANALYTICAL

CHEMISTRY EDUCATION

● Irresponsible distribution of

non-rigorous data SOCIAL RESPONSIBILITY

● Misuse of true data CRITICAL ATTITUDE of data

receptors

● False data distribution SELF CONTROL & POLICY

● Inexperienced data acquisition IMPROVED EDUCATION

Figure 1.7 Risks and potential solutions of problems related to the advancement of

democratic analytical chemistry

● LABORATORY as space for science production

● COMPLEX & EXPENSIVE methodology

● Protected software

● Academic obscurantism

● Slow data transmission

● Low cost instrumentation

● Easy measurement

● Free access software in the cloud

● On-site & Point-of-care data acquisition

● Speed of light data sharing

● Solidarity & Globalization

● OPEN DIFFUSION of data & opinion

● Closed & Protective

Figure 1.6 The change of scenario provided by democratic analytical chemistry

compared with classical analytical chemistry

From a social point of view, it is important to highlight the contributionthat the developments based on the principles of GAC can provide for society

in important matters such as clinical analysis and diagnosis or environmentalcontrol with clear implications for improving the quality of people’s lives andthe environment The development and widespread use of fast, cheap andportable techniques in less developed countries, but also in those who callthemselves first world but lack social and universal models of healthcare andbase their policies on services provided in the health sector by private com-panies, may help governments to offer adequate health programmes to theentire population in a social and responsible way, avoiding the commercialinterests of private companies Portable systems for the control of parameterssuch as blood glucose, or smart watches that control other clinical and vitalparameters, can support democratic access to the improvement of the quality

of life of the population and improving their health In the same sense, havingadequate methods that allow in situ environmental control in a generalizedand sustainable manner will allow rapid and efficient decision-making, such

as establishing limitations in the traffic of cities and controlling domesticemissions and urban spills, among others

In short, we are absolutely convinced that GAC has provided the principlesfor a new DAC frame in which (1) screening methodologies and fast meth-odologies will provide elements for preliminary decision-making, (2) the use

of readily available and low-cost apparatus and instrumentation will increasethe number of data acquisition personnel and multiply the eyes that look at

an analytical problem and (3) the expanding social networks will improve thespeed of communication of data and results However, it seems clear thatadditional efforts will be required to educate well the new analytical chem-istry operators and to put real data at the service of communities This is thechallenge and we must strive to provide correct answers to the multipleproblems and risks in the future

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CHAPTER 2

Direct Analysis by Green

Spectroscopy and Spectrometry

SALVADOR GARRIGUES* AND MIGUEL DE LA GUARDIA

Department of Analytical Chemistry, University of Valencia, ‘‘Jeroni

Mun˜oz’’ Research Building, c/Dr Moliner 50, 46100 Burjassot, Valencia,Spain

*Email: salvador.garrigues@uv.es

Direct analysis methods have the tremendous advantage of obviating theneed for sample treatment, thus reducing both of the main drawbacks ofanalyte contamination and loss and environmental side effects They alsoenhance the decision-making process and reduce the cost and time requiredfor carrying out determinations Hence one of the main objectives of greenanalytical chemistry (GAC) is to obtain on-site as much information aspossible about the samples without any chemical pretreatment and with no

or minimal sample manipulation for a representative sampling and analysis

It also favours remote sensing and point-of-care analysis and shortensthe time required to make decisions, based on the advantages offered bychemometrics and modern information technologies Figure 2.1 summar-izes the hierarchical classification of the different alternative green directapproaches that can be employed

The physical state of samples is a starting point that limits the acquisitionand use of direct spectroscopic measurements It is evident that most ana-lytical techniques work well in the analysis of liquids or previously dissolved

Green Chemistry Series No 66

Challenges in Green Analytical Chemistry: 2nd Edition

Edited by Salvador Garrigues and Miguel de la Guardia

r The Royal Society of Chemistry 2020

Published by the Royal Society of Chemistry, www.rsc.org

19