ISSN 19907931, Russian Journal of Physical Chemistry B, 2015, Vol. 9, No. 3, pp. 406–411. © Pleiades Publishing, Ltd., 2015. Original Russian Text © N.P. Tarasova, F.I. Ingel’, A.S. Makarova, 2015, published in Khimicheskaya Fizika, 2015, Vol. 34, No. 6, pp. 5–11.
CHEMICAL PHYSICS OF ECOLOGICAL PROCESSES
Green Chemistry as a Tool for Reduction of Environmental Risks from Exposure to Chemically Hazardous Facilities N. P. Tarasovaa, F. I. Ingel’b, and A. S. Makarovaa a
Mendeleev University of Chemical Technology of Russia, Moscow, 125047 Russia b Sysin Research Institute of Human Ecology and Environmental Higiene, Ministry of Health of Russian Federation, Moscow, Russia email:
[email protected] Received October 31, 2014
Abstract—The lack of the quantitative characteristics of planetary boundaries for biosphere’s chemical pol lution is a source of increased risk for humanity. This complicates the control of the stability limits of the glo bal system. Note that chemical pollution leads to negative consequences for not only biota but also the health of the human population. It also affects the social health of a society because the state of psychological com fort is replaced by emotional maladjustment. The result is depression, increasing anxiety, decreasing labor productivity, and an increasing likelihood of accidents and emergencies caused by the human factor. These factors lead to economic losses. Green chemistry is a tool to break out of a vicious cycle (cycle with a positive feedback). However, the successful implementation of this direction requires joint efforts made by the busi ness community and the state. The state should provide administrative and legal grounds and set criteria for the evaluation of chemical hazards. The business community, in turn, should develop specific strategies for implementing the principles of green chemistry in Russian factories. Keywords: green chemistry, environmental analysis, social and economic analysis, governmental regulation, voluntary bodies DOI: 10.1134/S1990793115030227
In 1972, the group of young scientists from the Massachusetts Institute of Technology under the supervision of Meadows published The Limits to Growth ordered by the Club of Rome, where they analyzed the global consequences of anthropogenic action on the biosphere [1]. The WORLD2 computer model was developed for evaluating the limits, which showed that the main biospheric resources necessary for maintaining the vital activity of humanity at a cur rent level will be exhausted by the middle of the 21st century. In 2009, Rockström et al. [2] introduced the term planetary boundaries for the more detailed evalu ation of the limits of technogenic action on the planet and computed the main anthropogenic loads. The planetary boundaries were determined through the following nine key parameters: climate fluctuation, ocean acidulation, ozone layer depletion, the state of nitrogen and phosphorus (key biogenic elements) glo bal cycles, the utilization level of the world reserves of freshwater, changes in terrestrial ecosystems, biodiver sity loss level, atmospheric emissions of aerosols, and chemical pollution level [2]. Boundary values were determined for seven of the nine selected parameters, which can lead to irreversible changes in the biosphere under outofcontrol conditions. However, such boundaries were not established for aerosols released into the atmosphere and chemical pollution. The rea
son for this was a multidimensional problem. For example, the humankind currently uses a wide variety of chemicals in large amounts, which enter into com plex interactions with each other and exert a complex combined effect on different environmental objects; the health, activity, and behavior of humans; and the health of the future generations. The exact number of chemicals that circulate on the world market is unknown; however, according to the Regulation on Registration, Evaluation, Authorisation and Restric tion of Chemicals (REACH) requirements of the European Union, about 144000 chemical substances were subjected to preliminary registration. Thus, it is possible to determine an approximate number of chemicals in the commercial circulation throughout the world [3]. The absence of established boundaries for the chemical pollution indicates the absence of knowledge on the global degree of risk for humanity from this form of action and, correspondingly, the absence of a possibility for risk control. In this case, it is necessary to note that the current chemical pollution causes seri ous apprehensions in the world. In 2006, the Dubai Declaration on International Chemicals Management was prepared in the context of the Rio de Janeiro dec laration and the Johannesburg Plan of Implementa tion. It was declared that the sound management of
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chemicals is essential if we are to achieve sustainable development, including the eradication of poverty and disease, the improvement of human health and the environment, and the elevation and maintenance of the standard of living in countries at all levels of devel opment [4]. This is consistent with the statement of Dr. Maria Neira, World Health Organization (WHO) Director, Department of Public Health, Environmen tal and Social Determinants of Health (PHE), on the fact that the welfare of business depends on the health of workers [5]. It is important to understand that the health of workers at chemicalindustry plants depends not only on contacts with chemicals, among which mutagens and carcinogens can widely occur, and operations under severe conditions (temperature, pressure, noise, vibration, and the action of other physical factors) but also on the response of the body to these actions (stress). In accordance with the determination of WHO, health is the state of physical, spiritual, and social prosperity rather than only the absence of dis eases or physical defects [6]. Thus, the health is the state of adaptative stress, when the response to all experienced actions does not exceed the limits of an individual norm of reaction. However, as a result of longterm action of chemi cal production factors, the worker’s state of adaptative stress changes to nonadaptive stress (state of psycho logical comfort is changed to emotional deadapta tion), which leads to a decrease in the resistance of the body, all its systems, and even genetic structures to any actions [6]. Thus, for instance, the examinations of workers from several chemical plants in Russia showed that the sensitivity of blood lymphocytes from perons in state of emotional deadaptation to in vitro irradia tion was higher and the frequency of programmed cell death (apoptosis) was lower (Fig. 1). Because in vitro irradiation is a recognized model for evaluating the sensitivity of human and animal genomes to the action of environmental factors, the experimental data make it possible to conclude that the state of emotional deadaptation is related to an increase in the sensitivity of genetic structures to the entire set of factors. The data shown in Fig. 1 reflect the general regularity reported earlier by Ingel’ et al. [7]: in healthy organism (psychological comfort taken as a standard), cells with genetic damages are by differ ent ways, including programmed cell death (apopto sis); in organism in state of emotional deadaptation, apoptosis is blocked what retains the viability of dam aged cells and allow them to give defective posterity thus fixing genetic damages in generations of dividing cells. Note that, all other factors being the same, the state of nonadaptive stress (emotional deadaptation) is characterized by the perception of pressure of social load by a human being as heavier or intolerable. This inadequate perception only increases the degree of deadaptation of the organism to increase its sensitivity RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B
Binuclear cells with micronuclei and the frequency of apoptosis, %
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6 *
5 4 3 2
*
1 0 Binuclear cells with micronuclei
Apoptosis
Fig. 1. Radiosensitivity of blood lymphocytes of chemical enterprise workers to in vitro irradiation with 60Co γ quanta (1.0 Gy; apparatus, Cirus; dose rate, 0.2 Gy/min; irradiation after 24h cultivation; cytochalasin B, after 44 h cultivation) based on the data of laboratory study per formed at Sysin Federal State Research Institute of Human Ecology and Environmental Higiene, Ministry of Health of Russian Federation in 2003–2005: (䊐) norm, (䊏) emotional adaptation, and * significant in comparison with a level (P ≤ 0.05).
to environmental and industrial factors; this creates a vicious circle (cycle with positive feedback): in partic ular, emotional stress leads to the aggravation of the perception of social load pressure, which only strengthens emotional stress and increases the sensi tivity of the organism; therefore, the risk of getting a disease due to any weak action increases. Thus, a pre disposition to the following diseases as the first targets of nonadaptive stress is created: cardiovascular dis eases, neuroimmune diseases, endocrine disturbances and chronic diseases of gastrointestinal tract. Further more, the state of prolonged nonadaptive stress creates conditions for the early aging of the organism and the development of tumors. The inclusion of nonadaptive stress in the list of the leading negative factors of chemical production based on the results of our studies [7] found confirmation in studies carried out at BASF. Yong et al. [8] noted that the high level of anxiety and depressions in BASF workers is an important problem. The reproduction of the above basic paradigm under other conditions (in a country with radically different social conditions, at factories of another type, and in the course of studies carried out with the aid of other psychological tests) is primarily indicative of not only the reality but also the universality of regularities related to the appearance of the vicious circle of stress. Their detection requires, first, the development of universal strategy for the determination of the basic reasons of changes in the health status of workers at chemical enterprises. Because the appearance of a vicious circle is a sys tem problem, which has several mutually amplifying outlines, the solution should be systemic with consid eration for many factors. For the solution of this prob Vol. 9
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47% 50%
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0 High risk
Medium risk
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Fig. 2. Comparison between the perceptions of commer cial risks related to green chemistry by (䊏) Russian enter prises and (䊐) enterprises in the OECD member countries.
lem, we developed an integrated approach that includes the cytome analysis of genetic damages and genome sensitivity, woker’s sociopsychological exami nation, and the chemical analysis of his workplace conditions; the set of these data makes it possible to reveal factors decreasing the adaptive potential of a particular worker. Green chemistry will play an important role in the practical implementation of the concept present in this publication. On the one hand, green chemistry (green manufacture, green production) causes a posi tive reaction in the majority of people. On the other hand, in accordance with the definition of the Inter national Union of Pure and Applied Chemistry (IUPAC) [9], the main goal of green chemistry is the discovery, development, and application of chemical products and processes, which decrease or exclude the use and formation of dangerous substances [10], to decrease the environmental pollution. The positive perception of a chemical enterprise and/or work on it will make it possible to decrease the pressure level of social load on the personnel of the enterprise and on the neighboring population. Green chemistry is also a tool for improving the quality of life and the welfare of people. According to the WHO definition, the quality of life (QOL) is the perception of their positions in life by individuals in the context of culture and the systems of values, in which they live, in accordance with their purposes, expectations, standards, and concerns [11, 12]. The good status of human health in many respects depends on an impression of to what extent the personal needs of a human being and the needs of her/his family are satisfied; according to WHO data, the contribution of the complex of social factors to the health status of a human is no lower than 50% [6]. In order to estimate the need for green chemistry in the Russian Federation, a sociological study was car ried out at the UNESCO Department Green Chemis try for Sustainable Development of the Mendeleev University of Chemical Technology of Russia; this study covered Russian enterprises in the chemical industry and related industries [13]. The results of the
inquiry showed that, in 20 years since the first publica tion in this subject area, the principles of green chem istry found propagation almost in a half of the enter prises of the Russian chemical industry. Because green chemistry is considered a line in the development of enterprises the main purpose of which is to make a profit, the perception of the commercial effectiveness of the introduction of green chemistry principles in the Russian Federation was evaluated (Fig. 2). Note that the results of evaluating the com mercial risk by Russian enterprises were found compa rable with the results obtained in the course of an inquiry at enterprises in the member countries of the Organization for Economic Cooperation and Devel opment (OECD) [14]. Such a consideration of industry for risks related to the introduction of green chemistry suggests that the state support is necessary for the successful use of its innovation potential in the Russian Federation. The main actions of the state to facilitate the practical implementation of the principles of green chemistry can be the following: —the determination of criteria for the evaluation of hazardous chemicals; —the prioritization of chemicals in circulation; —the development of a state regulation system for the circulation of hazardous chemicals; —the development and implementation of infor mation and educational programs; —the development of economic and noneco nomic mechanisms for the support of green initiatives. The importance and effectiveness of the state in the solution of problems related to the stimulation of the discovery, development, and application of chemical substances and processes to decrease or exclude the use and formation of harmful chemicals can be illus trated based on the following examples. A notable increase in the anthropogenic mobiliza tion of mercury is a universal acute problem caused by an increase in the chemical load. This increase is caused by the presence of mercury in raw materials and fossil fuels, which is released into the environment in the course of processing and combustion, by the use of mercury catalysts in a number of chemical pro cesses, and by the presence of mercury in finished pro duction [15]. Although the majority of the countries acknowl edged the danger of mercury pollution, the world community ambiguously considers the degree and nature of mercury danger. In the course of the study carried out at the UNESCO Chair Green Chemistry for Sustainable Development of the Mendeleev Uni versity of Chemical Technology of Russia, a compara tive analysis of data on the estimation of the danger and classification of mercury in different countries (European Union, Japan, and New Zealand) was per formed. Databases [16–20] served as information sources for the analysis. In the course of the analysis of
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Results of the comparative analysis of the evaluation and classification of the dangers of metal mercury exposure in different countries Information source Hazard class
Acute toxicity
Corrosive to metals inhalation oral
European Chemical Substances Information System (ESIS) [17]
The GHSJ database of GHS classification results by the Japanese government [18]
Hazardous Substances and New Organisms Chemical Classification Information Database, New Zealand [19, 20]
–
–
Category 1 (national 8.1A). May be corrisive to metals
Category 2. Fatal if inhaled
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Category 2 (national 6.1B). Fatal if inhaled
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–
Category 2 (national 6.1B). Fatal if swallowed
Skin sensitization
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Category 1. May cause an allergic Category 1 (national 6.5B). May skin reaction cause an allergic skin reaction
Germ cell mutagenicity
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Category 2. Suspected of causing genetic defects
Reproductive toxity
Specific target organ toxicity
single exposure
repeated/pro longed exposure
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Category 1B. May damage Category 1A. May damage fertility Category 1* (national 6.8A). May fertility or the unborn child or the unborn child damage fertility or the unborn child Category 1. Cause damage to res piratory organs, kidneys, central – nervous system, gum, gastrointes tinal tract, cardiovascular system, and liver upon inhalation Category 1** (national 6.9A (inh)). Cause damage to organs and systems Category 1. Cause damage to Category 1. Cause damage kidneys, central and peripheral upon inhalation to organs and systems nervous systems, gum, cardiovas through prolonged cular and circulatory systems, or repeated exposure and liver through prolonged or repeated exposure
Hazardous to the aquatic Category 1. Very toxic environment, shortterm to aquatic life (Acute)
Category 1*** (national 9.1A). Very toxic to aquatic life
–
Hazardous to the aquatic Category 1. Very toxic to Category 4. Very toxic to aquatic environment, longterm aquatic life with longlasting life with longlasting effects (chronic) effects * The division of category 1 mutagens into subcategorie 1A and 1B is absent from the classification system of New Zealand. ** The division of chemicals possessing selective toxicity into chemicals with selective toxicity upon single exposure and chemicals with selective tox icity upon repeated/prolonged exposures is absent from the classification system of New Zealand. *** The division of chemicals into those possessing acute toxicity for the aquatic environment and those possessing chronic toxicity for the aquatic envi ronment is absent from the classification system of New Zealand.
information (see the table), it was noted that different countries differently evaluated the danger of metal mercury. The revealed disagreement in the estimations of danger is very important for Russia, where the state system for the regulation of chemicals is under forma tion. The attribution of a substance to the category of substances that is extremely dangerous to the environ ment can be of crucial importance for its practical application. RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B
One additional example is the control of risks related to chemical exposures when inadequately studied chemicals whose effects on human beings and the environment are not clearly understood are in cir culation. In particular, these chemicals include perflu orinated compounds. The states that ratified the Stockholm [21], Rotterdam [22] and/or Helsinki con ventions [23] faced with a problem to minimize the circulation of perfluorochemicals. Perfluorochemicals do not occur in nature, and they are xenobiotics. We Vol. 9
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Environmental impact Carcinogenicity, mutagenicity, and reprotoxicity Irritating action Acute toxicity on inhalation, swallowing, etc. 0
20
40
60
80
100%
Fig. 3. Results of the analysis of the availability of information on perfluorochemicals in circulation according to different types of action on human beings and/or the environment: (1) information available and (2) no data.
have compiled a list of perfluorochemicals (270 com pounds) circulated in the Russian Federation and ana lyzed the availability of information necessary for eval uating their danger (Fig. 3). Special attention should be focused on the reliabil ity of available data. As shown above based on the example of elemental mercury, there are significant differences in the estimations of the danger of chemi cal substances. The basic reason for these differences is the fact that particular scientific information on the characteristics of substances may be acknowledged or unacknowledged by state inspectorate bodies as reli able and important. In conclusion, it is necessary to note that only an effort of the state to successfully apply green chemistry principles in practice and use its innovation potential is insufficient because this regulation is characterized by rigidity and carelessness. It is difficult to perform a mild stepbystep transition to green technologies by the tools of government control, and violent regula tory measures are an additional source of stress, which can level economic and social benefits from the intro duction of green technologies. In our opinion, for the solutions of problems related to the complex and simultaneous action on the economic, ecological, and social factors, the government control should occur exclusively as a framework mechanism. The practical implementation of the intended targets must be achieved due to enterprises taking the initiative. This initiative should be supported and approved by the government. These recommendations directly follow from the Millennium Development Goals declared in 2000 at the Millennium Summit [24] as a program ori ented to reduce extreme poverty and to increase the general standard of living. In the Russian Federation, there are great opportu nities for the promotion and use of green chemistry principles within the framework of the Responsible Care program [25]. This program was declared by the Russian Union of Chemists as the program of the sus tainable development of the branch [26]. It was recog nized and supported by an authoritative international structure such as the United Nations Environment
Programme (UNEP). The Responsible Care helps to introduce the concept of green chemistry into the branch and to use currently available mechanisms for the stimulation of the voluntary initiatives of enter prises. The principles of green chemistry and the base positions of the Responsible Care program become the elements of an integrated enterprise management technology. At present, 34 companies signed an agree ment on cooperation according to the Responsible Care program; among them are three international companies—OAO Nizhnekamskneftekhim, SIBUR, and EvroKhim. Thus, as a result of the sociological study carried out by the UNESCO Chair in Green Chemistry for Sustainable Development of the Mendeleev Univer sity of Chemical Technology of Russia, interest of Russian chemical enterprises in green chemistry and the potential need for this line were revealed. Russian enterprises consider the tool of green chemistry as a way of increasing the competitive ability of Russian production. However, the blind adoption of western technologies together with the proposed estimations of ecological risks is not applicable under the condi tions of our country because it is not supported by the systems analysis of social, ecological, and economic consequences. We developed an integrated approach to the evaluation of the chemical pollution of the envi ronment, including the cytome analysis of genetic damages and genome sensitivity, the sociopsychologi cal examination of a person, and the chemical analysis of her/his workplace conditions; the set of these data makes it possible to reveal factors decreasing the adap tive potential of a particular worker. Green chemistry possesses a high innovation potential; however, it needs a set of instruments for practical implementation, which can be proposed by a management system (the estimation of exposure and risk aspects, audit, information exchange, etc.). Pri vate and government partnership can be a key element of the introduction. The application of the principles and tools of green chemistry will make it possible to increase the indus trial and technological potential of an enterprise,
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which will lead to the renewal of plant, technological advancement, and modernization of working condi tions. The above factors will contribute to the effective control of environmental, economic, and social risks faced by the enterprise in the course of basic produc tion activity. ACKNOWLEDGMENTS This work was supported in part by the Ministry of Education and Science of the Russian Federation (state contract no. 5.2598.2014/K). REFERENCES 1. D. H. Meadows, J. Randers, and D. L. Meadows, The Limits to Growth the 30Year Update (Chelsea Green Publ., White River Junctiont, Vermont, 2004). 2. J. Rockström, W. Steffen, K. Noone, et al., Nature, No. 461, 472 (2009). 3. www.unep.org/pdf/GCO_Synthesis%20Report_CBDTIE_ UNEP_September5_2012.pdf 4. www.saicm.org/images/saicm_documents/saicm%20texts/ SAICM_publication_RU.pdf 5. http://apps.who.int/iris/bitstream/10665/44307/11/ 9789244599310_rus.pdf?ua=1 6. http://apps.who.int/gb/bd/PDF/bd47/RU/constitution ru.pdf?ua=1 7. F. I. Ingel’, E. K. Krivtsova, V. V. Yurchenko, et al., Gig. Sanit., No. 5, 44 (2011). 8. M. Yong, M. Nasterlack, R. P. Pluto, et al., Work: J. Prevent., Assessm. Rehabil. 46, 347 (2013). 9. P. Tundo, P. Anastas, D. St. C. Black, et al., Pure Appl. Chem. 72, 1207 (2000). 10. N. P. Tarasova, O. M. Nefedov, and V. V. Lunin, Russ. Chem. Rev. 79, 439 (2010). 11. The WHOQOL Group, Soc. Sci. Med., No. 41, 1403 (1995). 12. F. I. Ingel’, Ekol. Genet. 3 (3), 38 (2005). 13. N. P. Tarasova, A. S. Makarova, S. Yu. Vavilov, S. N. Varla mova, and M. Yu. Shchukina, Herald Russ. Acad. Sci. 83, 499 (2013).
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14. The Role of Government Policy in Supporting the Adoption of Green/Sustainable Chemistry Innovations, ENV/JM/ MONO(2012)3, OECD Environment, Health and Safety Publ. Ser. on Risk Management (OECD, Paris, 2012), No. 26. 15. “On signing Minamata convention on mercury,” Order of the Government of the Russian Federation No. 1242r from 07.07.2014, with the application— Minamata Convention Project. http://www.pravo.gov.ru, 10.07.2014 16. eChemportal OESR. http://www.echemportal.org/ 17. ESIS: European Chemical Substances Information System. http://esis.jrc.ec.europa.eu/ 18. GHSJ DataBase of Classified Substances in Japan (Natl. Inst. Technol. and Estimation in Japan). http:// www.safe.nite.go.jp/english/files/ghs_xls/classification_ result_e(ID001100).xls 19. Hazardous Substances and New Organisms Chemical Classification Information Database. http://www.epa.govt. nz/searchdatabases/Pages/cciddetails.aspx?SubstanceID =2654 20. www.epa.govt.nz/Publications/hsnogenghsnzhazard. pdf 21. “Stockholm Convention on Persistent Organic Pollut ants,” Collection of the Legislation in the Russian Fed eration, No. 7, 785 (2012); Byull. Mezhdunar. Dogo vorov., No. 12, 11 (2012). 22. “Rotterdam Convention on the Prior Informed Con sent Procedure for Certain Hazardous Chemicals and Pesticides in International Trade,” Collection of the Legislation in the Russian Federation, No. 36, 5125 (2011); Byull. Mezhdunar. Dogovorov., No. 9, 45 (2012). http://www.conventions.ru/view_base.php?id=66 23. “On Approval of the Protection Convention of the Marine Environment of the Baltic Sea in 1992,” Order of the Government of the Russian Federation from 15.10.1998. http://docs.cntd.ru/document/901719069 24. United Nations Millennium Declaration, adopted by Resolution No. A/RES/52/2 on the 8th plenary meet ing of the 55th session of the UN General Assembly ot 08.09.2000 (New York, 2000). 25. I. G. Kukushkin, Ros. Khim. Zh., No. 9, 30 (2014). 26. www.ruschemunion.ru/initiatives/responsible_care/
Translated by V. Makhlyarchuk
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