environmental hazard

Review Articles Environmental Hazard, Part I

Chemicals Regulation Assessment

Environmental Hazard

- Assessment of Chemicals and Products

Part I: General Assessment Principles* Part II: Persistence and Degradability of Organic Chemicals Part III: The Limits to Single Compound Assessment Part IV: Life Cycle Assessment (LCA)

*) Parts II - IV will be published in the following issues of ESPR.

Walter Kl6pffer

C. A. U. GmbH, Daimlerstrat~e 23, D-63303 Dreieich/Frankfurt, Germany

Survey on the Series

- Abstracts of Parts I - IV

Part I: General Assessment Principles

Hazard assessment is based both on estimates of environmental exposure and ecotoxic, toxic, and other noxious effects. Environmental criteria are given to enable a preliminary categorization of the hazard posed by a chemical. Depending on the amount and quality of data, the hazard estimates may be very rough (so that large safety margins are required), or more or less satisfactory. Risk assessment (not considered in detail) requires sufficient quantitative information, not available for most chemicals. Scoring systems give first approximations ff many chemicals are to be assessed with a minimum amount of data. More elaborate hazard assessment systems are shortly discussed. A main problem of all assessment procedures are the extremely toxic chemicals with no or very small production and the persistent chemicals without known adverse effects. Suggestions are made how to deal with these difficult cases.

Part II: Persistence and Degradability of Organic Chemicals

The criteria "Persistence" and "Degradability" are defined and ex- plained, starting from the "functional" definition of the environment. In this definition, the environment is the counterpart of the technosphere, which consists of all processes controlled by man. A substance is persistent if there are no sinks (degradation processes). It is shown that persistence is the central and most important crite- rium of environmental hazard assessment of organic chemicals. It follows that all substances released into the environment should be degradable, preferentially into small inorganic molecules (mineral- ization). As examples for persistent substances, the polychlorinated biphenyls (PCB), the chlorofluorohydrocarbons (CFC), bis(2- ethylhexyl) phthalate (DEHP), and 2,3,7,8-tetrachloro-dibenzo- dioxin (TCDD) are discussed. Finally, an attempt to quantify persistence is made.

Part II1: The Limits to Single Compound Assessment

The principles and basic assumptions of single compound assessment are briefly reviewed. Limitations to this approach are shown, especially with regard to complex mixtures of similar substances, substitution products, and complicated (final) products containing chemicals and materials produced by the chemical industry. A new thinking in product lines and life cycles is emerging, leading to new assessment methods. In some cases, substitution has not improved the environmental performance of products, since very similar chemicals were used as substitutes.

Part W: Life Cycle Assessment (LCA)

The first LCAs (or eco-balances) were carried out in about 1970 when energy saving became a topic of general concern. Further pio- neering work was performed in the 80's, but public interest has been induced only in the last few years. A modern LCA, as defined by SETAC, consists of four main com- ponents: Goal Definition, Inventory, Impact Assessment (including Valuation), and Improvement Analysis. The backbone of each LCA is the Inventory, a quantitative cradle- to-grave analysis of all relevant mass and energy fluxes related the product(s) or systems studied, including the toxic or ecotoxic emissions. Impact Assessment is the environmental assessment of the emissions according to a set of criteria. In the broader approach (much discussed in Germany) of "Produkdinienanalyse', social and economic impacts are also considered in the Impact Assessment component. Impact Assessment also contains the "Valuation"-step which goes beyond (exact) science due the to normative and subjective factors invariably involved. Therefore, LCAs cannot replace political and economic decisions, but rather provide more rational (as opposed to emotional) and scientific foundations. The best use of LCA is the comparative assessment of products and systems serving the same purpose to improve manufacturing, waste management etc. over the whole life cycle. In order to compare different products or systems, a "functional unit" has to be defined, allowing a fair comparison between the alternatives. All data (e.g. total energy consumption, emissions, wastes, impacts) are related to this functional unit, so that a quantitative and differentiated comparison of different options becomes possible.

ESPR-Environ. Sci. & Pollut. Res. 1 (1) 47-53 (1994) 47 �9 ecomed publishers, D-86899 Landsberg, Germany

Environmental Hazard, Part I Review Articles

Environmental Hazard

- Assessment of Chemicals and Products

Part h General Assessment Principles

Wal te r Kl6pffer

C. A. U. GmbH, Daimlerstrage 23, D-63303 Dreieich/Frankfurt, Germany

Part h General Assessment Principles

Hazard assessment is based both on estimates of environmental exposure and ecotoxic, toxic, and other noxious effects. Environmental criteria are given to enable a preliminary categorization of the hazard posed by a chemical. Depending on the amount and quality of data, the hazard estimates may be very rough (so that large safety margins are requiredl, or more or less satisfactory. Risk assessment (not considered in detail) requires sufficient quantitative information, not available for most chemicals. Scoring systems give first approximations if many chemicals are to be assessed with a minimum amount of data. More elaborate hazard assessment systems are shortly discussed. A main problem of all assessment procedures are the extremely toxic chemicals with no or very small production and the persistent chemicals without known adverse effects. Suggestions are made how to deal with these difficult cases.

1 I n t r o d u c t i o n

1.1 Rat ionale for Assessment W o r k

The environmental assessment of chemical substances and products is pe r formed to recognize and to unders tand the hazard posed by them, preferent ia l ly before an actual damage occurs. Assessment is also a p repara t ion for decisions and actions, including further testing and evaluat ion work , restrict ions of the use, and total ban in case of very dangerous substances, mixtures and other products .

The main reasons for the necessity of assessment work are in the author ' s view:

- The responsibility we have for future generations. - The insight that the existence of mankind depends on the biosphere

(-~ Fig. 1). The "cultural sphere" [1, 2] or "technosphere" [3] is of very recent origin, compared with the biosphere and the energy/matter basis below, and strongly depends on the state of its substrate. Drastic changes of the biosphere may therefore destroy the basis of our existence [4, 5, 6], whereas changes in the technosphere may (perhaps severely) alter but never completely destroy the biosphere [21.

- Responsible politicians have developed an international action plan [7], with a central demand for "sustainable development", i.e. a development of all peoples which does not destroy the natural basis. First steps on this basis were taken at the World Conference in Rio de Janeiro (1992).

- More specifically, chemical legislation as an important part of environmental protection is the immediate incentive for assessing the potential contribution of chemicals to damage the biosphere (or the "environment" as the counterpart of the technosphere [3]).

Cultural Sphere

~ J J f f J J f J f f J f f f J J J J J ~ , ( =

B,osphere

l=,=,=,=,=,=,=,q

-'= Energy/ i - t # f j j j j J J / , . �9 FffJJJfJf,~lP

�9 Matter i .~

_ - K . . . . .

; ~ i m i l l m l n l i m l l l i , i l i l l

~ l J J J f . f J J J f f J J J , f J f J j f j j j j ~ j p j j ~

|

limiting altering < 1

@ U N I T OF TIME (YEARS)

Fig. 1: Schematic presentation of technosphere (cultural sphere) and environment (biosphere + energy/matter) after BRETSCHKO [2]; reproduced by permission of the Austrian Academy of Sciences

The chemical legislation in several industr ia l ized countries considers:

1. The assessment of "Existing Chemicals", i.e. to identify the dangerous substances from roughly 100 000 chemicals which were manu- factured before the new chemicals laws were issued [8 - 13].

2. The assessment of"New Chemicals" [14 - 19] which have to be no- tiffed according to the laws.

Recently, the German Par l iament (Bundestag) has instal led a commiss ion to inquire abou t potent ia l dangers of chemicals to human health and the environment [20]. The mis- sion of this "Enqu~te Kommission" is not restricted to chemicals in the na r row sense (as substances p roduced by chemical industry) but also includes substance flows resulting from other activities of the technical civil ization, e.g. traffic.

In 1992, the European Counci l adop ted the 7th Ammend- ment of Directive 6 7 / 5 4 8 / E E C [65] requiring a "risk assessment" of notified substances according to rules to be defined in a separate Directive.

1.2 Envi ronmenta l Haza rd Cri ter ia of Chemicals

In assessing the environmenta l hazard of chemicals , some general cri teria should be defined [3, 21]:

- Persistence means the longevity of a compound in the environment and is caused by the absence, inefficiency or inaccessibility of chemical or biological sinks for the substance,

- Accumulation causes high local concentrations, e.g. in sediments and fat tissues of animals. Accumulation is most frequendy observed in strongly lipophilic chemicals.

- Mobility is the dispersion tendency of a substance in the environment. Mobile substances can be distributed worldwide, if they =live" long enough; they enter preferentially into the mobile media, espe-

48 ESPR-Environ. Sci. & Pollut. Res. 1 (1) 1994


dally the lower atmosphere (troposphere). Therefore, most mobile chemicals have a high vapour pressure and/or a high gas/water distribution (Henry-) coefficient.

- Amount (of a chemical reaching the environment) is usually defined as the annual input into the environmental compartments and may range from about 0.1% to 100 % of the annual production of a chemical.

- Noxious Effects of a chemical may be directed versus man (toxicity), versus animals, plants or biotopes/ecosystems (ecotoxicity), or versus non-biological targets.

These criteria may be too broad to be used directly for a de- tailed hazard assessment; however, they are useful for qualitative categorizations, for the general understanding of the environmental behavior (fate) of chemicals, and for charac- terizing the hazard they constitute for the environment.

2 Environmental Hazard and Risk

2.3 Hazard and Risk

There is still some debate whether risk assessment can be quantitative and objective in cases less obvious than, e.g., car accidents [30, 31]. There is no doubt, however, that risk assessment, imperfect as is may be, is basically a (more) quantitative exercise compared to hazard assessment (see also [32]). RICHARDSON [25- 27] is therefore right to say that risk assessment goes one step beyond the hazard estimation (---, Fig. 2).

CHEMICAL I

I i TOXICITY EXPOSURE

ASSESSM ENT ASSESSM ENT

QUANTITATIVE I HAZARD ESTIMATION

2.1 Hazard

There is considerable confusion about the meaning of the term "Hazard" [22-27] . A useful, albeit not very precise definition has been given by an expert group of the OECD Hazard Assessmen t Project ("Step System Group" [22]):

The hazard o f a chemical is a function of two broad considerations, the potential of the chemical to harm biological systems (or damage other systems) and its potential for exposure such that the harm or damage can occur.

According to this definition, hazard is determined by exposure and noxious effects, both biological (toxic/ecotoxic) and non-biological (abiotic).

A somewhat different definition of "Hazard" has been given by RICHARDSON [25, 27]:

Hazard (is defined as) the set of inherent properties o f a chemical substance or mixture which makes it capable of causing adverse effects in man or the environment when a particular degree o f exposure occurs.

This "particular degree of exposure" is also dependent on "inherent properties": the physical-chemical properties which determine distribution, degradation, and ultimate fate of a chemical [29].

2.2 Risk

The term "Hazard" is often confused with "Risk". Risk assessment, however, contains a quantitative probability esti- mate, which is very difficult to obtain for the case of general environmental (as opposed to direct human) exposure. The term "Risk" is well defined as the product of the probability (of occurence), and the magnitude of the damage [64] and originates from the insurance business and the assessment of technologies with regard to accidents.

Again, a somewhat different definition was proposed for environmental and human health risk assessment of chemicals [25,27]:

Risk (is defined as) the predicted or actual frequency o f occurence o f an adverse effect o f a chemical substance or mixture from a given exposure to humans or the environment.

RISK ASSESSMENT J

Fig. 2: Scheme of Hazard- and Risk Assessment of Chemicals according to PdCHagDSON [26]

A discussion of the different meanings and proposed defini- tions of the terms "hazard" and "risk" and their German equi- valents has recently been published by SCHON [66]. It also seems that the EC Directive [65] is using the terms synony- mously.

As a formalization of the hazard definition given by OECD [22], the following equation was proposed by the author [28, 41]:

HAZARD = EXPOSURE x EFFECTS (1)

The multiplication signe (X) indicates that there should be no hazard if there is either no exposure or no adverse effect. This seems to be logical but, in a strict sense, contradicts the basic postulate of environmental hazard assessment that "it is scientifically impossible to prove that a substance will not pose a threat" [33, 34].

As shown in Fig. 2, most assessment systems involve separate exposure and effect assessments. Of course, the accu- racy of the results depend strongly on the amount and quality of data available. Chemical legislation provides for tiered (mostly three level) testing systems, which depend on the annual production volume of the chemical [19, 33, 35]. For exposure analysis, at least some useful data are available at the Zero-Level (or minimum pre-market ing/MPD/ level) of the testing system for new chemicals [29, 33, 36, 37]. However, the situation is very poor, in the case of effect data [28, 38, 39].

According to RUDOLVH & BOJE [40], the toxic and ecotoxic effects should be known at the different levels of organiza- tion: from the cells, organs, organisms etc. up to ecosystems and the biosphere as a whole. This information cannot be provided by any testing system, however. Only a few single species tests are available at the Zero-Level according to

ESPR-Environ. Sci. & Pollut. Res. 1 (1) 1994 49


European chemical laws. For Level 1 and 2 the situation is somewhat better, but still far from being satisfactory.

For s o m e existing chemicals which for a long time have been suspected to be hazardous, many data are available, although only few at the ecosystem level. In most cases data on non- biological systems are only available if adverse effects have been either detected by chance or scientifically predicted. Nearly nothing is known about the effects of transforma- tion products.

3 Principles of Scoring S y s t e m s

Scoring may be considered as the "zeroth approximation" to solve equation (1) [41]. As in physics, precise results cannot be expected in this case. Scoring systems may be useful in the early stages of assessment in chemical notification ("New Substances") and in sreening large inventories of "Existing Chemicals", e.g. the European inventory EINECS [11, 12, 17, 37, 42 -49 ] .

The principle of scoring consists in reducing test results or calculated properties to dimensionless numbers (the scores), e.g. in three steps: high ( + 3) - medium ( + 2) - low ( + 1). The scores are added up to a total score which approximates the relative hazard. In more elaborate scoring systems this may be done separately for the compartments water, air, soil and sediment [3, 11, 16, 43, 50].

Another feature of many scoring systems are the weighting factors for individual scores, which may [3, 21], or may not [47] be introduced in order to fit the results to a ranking obtained by expert judgement. Fig. 3 shows the results obtained with weighted scores for several chemicals, ranging from relatively harmless to hazardous.

Rl1112 HCB/~ 20- D /

t- .9 1 5 -

_~ / 2,4,5 -T / >

�9 T r i / M y -o L

N 1 0 - / O M e P

t - / . - Ha o

t_ IBu ,,o 5: / OMe

I I I I 0 1 2 3 4

C a t e g o r i e s of s u b j e c t i v e hazard eva lua t i on

Fig. 3: Results of formalized ranking (scoring) of Hazard vs. the results of expert judgement after FRlSCrtE et al. [3, 21]

Abbrev ia t ions --~ Fig, 3

Ha: Urea

Me: Methanol

P: Propane

Bu: Butane

Tri: Trichloroethene

MC: Dichloromethane (Methylenechloride)

MeP: Methyl Parathion

DOP: DEHP Di(2-ethylhexyl)phthalate

R 11/12: CFC 11/12 (R = refrigerant)

HCB: Hexachlorobenzene

2,4,5-T: 2,4,5,-Trichloro-phenoxyacetic acid and salts

In this case, the sum of weighted scores in a formalized scoring scheme was compared with the results obtained in expert sessions after intense discussion and using all information available at that time. For the scoring exercise, much less information has been used in order to simulate the situation of initial assessment of "New Chemicals" [21].

There are too many scoring systems to allow the discussion of all detail. Mrs. Judy HUSHON, already in 1982, summa- rized 33 systems at the Copenhagen Symposium [18, 44]. To be useful, a few general requirements should be met by any scoring and other simple hazard ranking systems [41]: - First of all, the scoring system has to be in accordance with expe-

rience gained from well known environmental chemicals. However the calibration process is not unproblematic since hazard assessment is not performed in the same way by different expert groups, agencies or individuals.

- Secondly, the system should be compatible with the assessment at higher levels of the testing and evaluation procedure. This demand cannot mean that the results must be identical (otherwise the higher levels would not be necessary!), but it means that the assessment procedures at all levels must be conceived in the same spirit.

- Due to the limited data base at the zero-level, the results obtained should be more conservative ("at the safe side") at this level than at the higher tiers.

- Last, but not least, the system should be transparent for all users, including the notifier; he should know which results the agency will obtain out of the data submitted. This last item favours, in the author's view, a formalized ranking (at least as a first step of hazard ranking of"New Substances"). How- ever all subjective elements (e.g. weighting factors) have to be discussed and agreed upon with all parties responsible for chemical assessment so that the results are widely accepted.

4 Advanced Hazard A s s e s s m e n t

If only a few substances with a good data base have to be assessed, there is less need for a formal (scoring) treatment, and a "case-by-case" procedure can be applied. Such a system has been developed by RIPPEN et al. [19] to make opti- mal use of the data provided by Level 1 + 2 according to Annex VIII of the Sixth Amendment (EC, 1979). Further advanced approaches have been presented by WEBER and BARBEN [51] and by LANDNER [52].

The exposure analysis has not been formalized by RIPPEN et al. [19] and can be done, starting from the use - and esti- mated release pattern, using appropriate multimedia models

5 0 ESPR-Environ. Sci. & Pollut. Res. 1 (1) 1994


[50, 53, 54]. If one compartment or medium, e.g. water, is strongly preferred by a specific chemical, a more sophisti- cated model for this compartment can be used. In the fre- quent case of surface water, the well known program by US- EPA ("EXAMS") may be used, or the PC model ABIWAS, developed for Umweltbundesamt, Berlin [55, 68]. Though this model is primarily developed for the assessment of abiotic degradation, it can easily be adjusted to biodegrada- tion, if appropriate rate constants are avaiblable [55].

The hazard assessment system by RIPPEN et al. [19] consists essentially of series of comprehensive and coherent check- lists for each compartment and for the essential pathways by which man can be exposed to the chemical (indirect human exposure). Depending on the data on amount, distribution, degradation, and adverse effects, different options and recommendations for actions are obtained.

Similar schemes are used by the notification agencies (e.g. [56]). The EC is preparing a uniform "Risk Assessment" system to be included into a new Directive on chemical assessment [57, 65]. The comparison between calculated concentrations and No Observed Effect Levels (NOEL) will be restricted to the medium water, for the time being.

Recently, the European Chemical Industry Ecology & Toxi- cology Centre (ECETOC) has published a compilation of existing and proposed hazard assessment schemes and sug- gested a scheme for hazard assessment of chemicals released to water [67]. This scheme is based on the estimation of exposure (Predicted Environmental Concentration - PEC) and effects (Predicted No-Effect Concentration - PNEC).

5 E x t r e m e l y T o x i c a n d P e r s i s t e n t C h e m i c a l s

In general, the hazard assessment based on equation (1) un- derrates two limiting cases:

- very high toxicity at small or not recognizable exposure (e.g. con- finement in closed systems)

- exposure without evident or known noxious effects.

The first case has been taken into account by WEISS et al. [11] in a scoring system for Existing Chemicals by intro- ducing an "extra black box" for highly toxic chemicals with low production volume. This should give a warning sign of a special danger as for the fact that these compounds are not overlooked in the selection procedure.

The second weak point is due to persistent chemicals, which, in general, have low acute toxicity [3, 21, 58, 59]. The first recognition of persistent chemicals in waters goes back to the 50's. The "Report of the Committee on Synthetic Deter- gents" by the British Ministry of Housing and Local Govern- ment from 1 9 5 6 [60] contains an impressive documentation of foam due to persistent or "refractory" tensides contained in the detergents of that time. These so-called hard tensides have meanwhile been banned and replaced by more degradable molecules, e.g. the anionic tenside (Sodium-) Linear Alkylbenzenesulfonate (LAS).

The first recognition of the general importance of persistence is due to STEPHENSON (1977) [58]. The main point made by

STEPHENSON is the fact that persistent chemicals cannot be removed from the environment, should a noxious effect be detected.

A further big step in understanding environmental chemicals is the recognition that apparent toxicity and environmental hazard may often be not related as stated by GE- BAUER (1986) [61]:

It's a dilemma - the more toxic chemicals generally are those which are more tolerable to the environment, while the low toxicity materials may often have more environmental problems.

This is certainly true with regard to the acute toxicity. In general, acute toxicity is not the greatest problem in the environment, due to the typically very low concentrations; however, it is a problem for the safe handling of the chemicals in the technosphere. Acute toxicity is a problem, of course, in the case of accidents and inproper handling of highly toxic chemicals (e.g. pesticides).

Important examples of persistent chemicals are [59]:

- Tetrapropylene benzenesulfonate (TPBS) - Perchloro-, Perfluoro - and Chlorofluorohydrocarbons (CFC) - 1,1,1-Trichloroethane ("Methylchloroform") - Polychlorinated Biphenyls (PCB) - D D T / D D D / D D E and Hexachlorobenzene (HCB) - Di(2-ethylhexyl) phthalate (DEHP) - Silicones (oligomeric Dialkylpolysiloxanes) - Polychlorinated Dibenzodioxins (PCDD) and Polychlorinated Di-

benzofurans (PCDF)

These well known persistent chemicals or "Xenobiotica" (KORTE et al. 1987 [62]) have been detected in many environmental samples; they will be discussed in Part II of this series in more detail. The polychlorinated Dibenzodioxins (PCDD) and Dibenzofurans (PCDF) are mentioned here as they present the very rare case of e x t r e m e l y t o x i c s u b s t a n -

c e s t h a t are a l s o p e r s i s t e n t . This is the worst possible com- bination of properties we can think of. PCDD and PCDF are produced only in very small quantities for research purposes. They are inadvertendly formed in several processes as impurities within the technosphere and partly emitted to the environment. The environmental exposure, therefore, is relatively small due to the small quantities involved. In order not to underestimate the hazard of such chemicals, the "hazard equation" should better be expressed in the following form (2):

HAZARD = EXPOSURE + EFFECTS (2)

The sign + in (2) indicates that the hazard posed by a chemical is n o t necessarily zero, if either Exposure or Effects are not measurable or unknown. Equation (2) expresses that chemicals with either

- very high exposure potential without known effects (especially persistent chemicals), or

- extreme toxicity coupled with very low or not recognizable exposure potential

should be considered as an environmental hazard.

Two further problems related to hazard assessment of persistent and toxic chemicals are [63 , 64]:

- substitution products for banned chemicals - beneficial effects in relation to human health v e r s u s environment.

ESPR-Environ. Sci. & PoUut. Res. 1 (1) 1994 5 1


The first addresses the question of substitution products. It is not sufficient to ban a known hazardous substance, without thinking about substitution products or methods, which may also pose environmental problems of a similar or different nature compared with the substance to be replaced.

The second problem is mosdy discussed with regard to DDT [63, 64], which had great beneficial effects in combating the malaria and other infectuous diseases (its discovery was hon- oured with the nobel price in medicine, 1948, to Paul MOLLER). Environmentally more acceptable substitution products are more expensive, so that third world countries cannot afford them. One solution of this problem could be that the more expensive insecticides are provided as development aid. This would also have a beneficial effect for the industrialized countries by reducing the "import" of DDT via the atmosphere and products from these countries.

6 References

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