practical exercises in physical hazard classification (exercise ......page 1 of 49 practical...

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Practical exercises in physical hazard classification (Exercise set with answers)

General instructions:

Answer each of the following questions as instructed by the moderator for your session. Be prepared to provide your answer during the discussion session as well as to explain how you arrived at this answer. Please note that completing many of the exercises requires reference to the resource materials described at the end of the exercise so please read the exercise in full before attempting to answer the questions. Please also provide the pictogram (if appropriate) signal word and hazard statement for the classifications you have determined.

Exercise 1: What is the hazard? A substance is a mixture made up of the following components

Ammonium Nitrate 71% Water 16% Diesel fuel 8% An emulsifier composed of

Oleic Acid 3% Sodium Hydroxide (50% aq. soln.) 2%

The mixture has a paste like consistency which does not meet the GHS definition of a liquid. Question: Considering the components of this mixture, identify the possible physical hazard classifications for this mixture, providing reasons for your choice. Answer:

Possible classifications are

Explosive – will need to consider if the mixture is intended as an explosive and which

of the complex UN tests it passes or fails

Oxidising substance as a result of the ammonium nitrate component

Flammable solid ‐ consider whether or not the emulsified diesel fuel enable the substance to burn as specified in the UN tests (test are essentially apply a small amount of energy and determine whether a line of the substance would burn faster than 2.2m/s

Exercise 2: An explosive? You are provided with the following information about the mixture described in exercise 1.

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1. The substance as described is intended to provide one component of a substance which,

after other materials are added, will form part of an explosive chain (i.e. including a fuse, detonator material etc), but is itself not manufactured to produce an explosive or pyrotechnic effect.

2. The following results are obtained when the substance is subject to UN test series 8 (see figure 10.4 UNRTDG Manual of Tests and Criteria 4th Edn or Figure 2.1.4 GHS 3rd Edn)

a. Test 8(a) – substance is reported as thermally stable b. Test 8(b) (large scale gap test) – substance is reported as not too sensitive to shock

to be accepted as an oxidising liquid or oxidising solid c. Test 8(c) (Koenen test) – substance is reported as not too sensitive to heat under

confinement d. When tested using the UN standard test methods for oxidising solids the following

results were obtained

3. The mean burn time of the substance when mixed with cellulose and ignited as prescribed in UN Test Series O.1 is as follows

Greater than the mean burn time of a 3:2 mixture of potassium bromate and cellulose

Less than the mean burn time of 2:3 mixture of potassium bromate and cellulose

Question: Determine the physical hazard classification for the substance, explaining how you obtained the classification. Answer:

The mixture is not intended as explosive and test series 8 results show no explosive effect as

defined. The substance is therefore not an explosive

The mixture is not a liquid so it is tested to determine if it is an oxidising solid ‐see data set out

in 3 above and the criteria set out in chapter 2.14 GHS (supplied in resource material)

Conclusion: the mixture is classified as a category 2 oxidising solid

Label elements:

Symbol: flame over circle

Signal word: Danger

Hazard statement: May intensify fire: oxidiser

Discussion points:

Strictly following the test sequences in the UNRTDG Tests and criteria would not require that the test for and oxidising solid be performed. It is included in this exercise for training purposes.

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Resource material To help you complete this exercise please refer to the following resource material

Figure 2.1.4 GHS 4th Edition Chapter 2.14 GHS 4th Edition

Exercise 3: Classify articles A highway patrol officer presents you with a number of small round disks about 30mm in diameter apparently made of a soft metal of some sort. The disks are marked “railway fog signal.” The officer explains that the disks were picked up from the side of a main interprovincial highway and, considering the remnants of a similarly labelled cardboard box found nearby, appear to have fallen from a truck travelling at high speed. When shown a copy of the GHS ‘explosive’ pictogram, the officer agrees that part of the box found may have had a similar symbol on it. (The remnants of the box are not available to you.) Question: Classify these articles, explaining how you derived the classification. Answer:

These items presented are articles so only possible classification is as an explosive, a

classification already suggested by the patrol officer’s report.

1. Check to see if the items are listed articles in the UN Recommendations for the

Transport of Dangerous Goods alphabetical list. (NB: Also include check for similar

names.) Result: there are entries for “signals railway track explosive” with transport

classifications and UN numbers. Several UN numbers are found, 0192, 0492, 0193,

0493 but with different classes

2. Look up the UN number(s) found 0192, 0492, 0193, and 0493 in the dangerous goods list (part 3 volume 1) for further information. Possible classifications are class 1.1 class 1.3, class1.4

3. Consider the intended use of the articles ‐ fog signals are intended to be placed on a railway line to be run over by a train and produce a noise to warn of fog on the line ahead. Conclusion: these articles would exhibit very small blast and little or no projection hazard.

4. Classification is therefore Class: explosive Category: 1.4

Label elements:

Symbol: Exploding bomb (OR 1.4 on orange background (ex‐transport)

Signal word: warning

Hazard statement: Fire or projection hazard

Discussion points

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Classification for explosive articles requires information about the intended

(designed) use

Articles with similar descriptions require more information for effective classification.

(advanced) The GHS applies the classification from the UNRTDDG as packaged. Hazards (and so classification) can be different when these items are not packaged (see note to table 2.1.2 GHS 4th Edn)

Resource material To help you complete this exercise please refer to the following resource material

The alphabetical index of the UN Recommendations for the Transport of Dangerous Goods 16th Edition The UN Recommendations for the Transport of Dangerous Goods 16th Edition dangerous goods list Chapter 2.1 of the GHS

Exercise 4: The flammability of jet fuel Jet A and Jet A‐1 fuel are the commonest forms of jet aircraft fuel in general use. This fuel is virtually identical to kerosene or paraffin. Jet A/A1 fuel (paraffin) has the following flash point and boiling point ranges (these fuels are in practice mixtures with some variance in composition). Flash point 380C – 660C Boiling point 1600C ‐ 3000C In certain parts of the world Jet B fuel is used in aircraft operations. Jet B fuel has the following flash point and boiling point ranges Flash point < ‐310C Boiling point 500C ‐ 2700C Question: Classify Jet A fuel and Jet B for their physical hazards and comment on the consequences of the classifications you make. Answer:

Referring to the table of classes presented in physical hazards session 3

Jet fuel B is Class: flammable liquid Category 2.

Label elements:

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Symbol: flame

Signal word: Danger

Hazard statement: Highly flammable liquid and vapour

Jet fuel A/paraffin is Class: flammable liquid Category 3

Label elements:

Symbol: flame


Hazard statement: Flammable liquid and vapour

Discussion points

As the flashpoint is at a very low temperature, jet fuel B would be easily ignited while being

handled and so requires more precautions.

So why use Jet fuel B at all?

Jet fuel B is used where jet engines are required to be started at very cold temperatures. For

example Jet fuel B is used in Canada – especially in the winter.

Resource material Please refer to the section in the presentation material describing classification for flammable liquids. Reference can also be made to Chapter 2.6 in the GHS 4th Edn

Exercise 5: A flammable gas? You are provided with the following data about the substance TS2. Boiling point: ‐33°C Flammable range: 16% ‐ 25% in air at ambient temperature (20°C) and standard pressure

(101.3 kPa) Question: Classify the substance TS2 and explain your reasoning Answer:

Referring to the decision logic in section 2.2.4.1 GHS 4th Edn

The boiling point quoted means that TS2 is a gas

1. Does TS2 have a flammable range with air at 20 °C and a standard pressure of 101.3 kPa?

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Answer: Yes.

2. At 20 °C and a standard pressure of 101.3 kPa, does it:

(a) ignite when in a mixture of 13% or less by volume in air; or

(b) have a flammable range with air of at least 12 percentage points regardless of

the lower flammable limit?

Answer: No. Neither condition is met by TS2

Classification: TS 2 is classified as Flammable Gas Category 2.

Label elements:

Symbol: No symbol


Hazard statement: Flammable gas

Resource material

Please refer to section 2.2.4.1 GHS 4th Edn

Exercise 6: What sort of gas under pressure? You are provided with the following information about substance HG4.

Vapour pressure at 50 °C is greater than 410 kPa (4.1 bar) Substance when packaged under pressure is entirely gaseous at ‐50 °C HG4 has a critical temperature of ‐240.1 °C HG4 is normally contained in a receptacle which can contain gas at up to 200 bar and is stored at normal room temperature.

Question: To which group in the class gases under pressure does HG4 belong? Answer Following the decision logic of section 2.5.4.1 GHS 4th Edn

1. Is the gas contained in a receptacle at a pressure of 200kPa or more at 20 °C? ANSWER: Yes

2. Is the vapour pressure at 50 °C greater than 300 kPa (3 bar)? ANSWER: Yes.

3. Is the gas dissolved in a liquid solvent under pressure? ANSWER: No.

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4. Is the critical temperature above +65 °C? ANSWER: No.

5. Is the critical temperature between ‐50 °C and +65 °C? ANSWER: No.

6. Is the gas made partially liquid because of its low temperature? ANSWER: No.

7. Is the gas entirely in gaseous state at ‐50 °C? ANSWER: Yes. CLASSIFICATION: The gas is classified in group: compressed gas. Label elements:

Symbol: gas cylinder


Hazard statement: Contains gas under pressure; may explode if heated Resource material

Please refer to section 2.5.4 GHS 4th Edn

Exercise 7: A burning solid A yellow powder was tested using the test method prescribed in the UN Recommendations for the Transport of Dangerous Goods – Manual of Tests and Criteria Part III Sections 33.2.1. The tests showed that the powder burned during the test with the burn time being less than 45 seconds. It is known that the substance is not a powdered metal. Question: Classify the yellow solid using the information supplied, explaining how you arrived at your answer and any uncertainties that remain with the classification. Answer: Referring to the decision logic in section 2.7.4 of the GHS, we find that a burn time with the specified UN test of less than 45 seconds would suggest that the powder is a category 1 flammable solid. However no information is supplied about how the powder behaved with respect to the wetted zone in the test. Classification cannot therefore be completed and the required information should be obtained to complete classification. Resource material To help you complete this exercise please refer to the following resource material Section 2.7.4 GHS 4th Edition

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Exercise 8: A powder seen to give off gas A white powder when tested in accordance with UN test No. 5 as set out in Part III section 33.4.1.4 of the UN Recommendations for the Transport of Dangerous Goods Manual of Test and Criteria is shown to evolve gas at a maximum rate of 11 l/kg of the chemical per hour. The gas does not spontaneously ignite, but is flammable. Question: Identify the type of hazard exhibited and determine the physical hazard classification and the required hazard statement for this substance, including an explanation of how you classified the substance in your answer. Answer: The description of flammable gas evolution suggests this powder may belong to class of substances or mixtures which in contact with water emit flammable gas Comparing the data presented with the criteria in chapter 2.12 GHS shows that the powder is category 3 in this class. The criteria for Category 3 (>= 1l emitted gas/kg chemical/h) are fulfilled, but not the criteria for Category 2 (>20l/kg/h) Classification: Class 2.12, Category 3; Label elements:

Symbol: flame


Hazard statement: In contact with water releases flammable gas

Resource material To help you complete this exercise please refer to the following resource material Section 2.12.2 GHS 4th Edition

Exercise 9: Test results from a yellow powder A yellow powder was exposed to air at elevated temperatures using the test method No.4 of the UN Recommendations for the Transport of Dangerous Goods Manual of Test Criteria Part III Section 33.3.1.6 (“Burn test”). The following results were observed (results as defined by the test)

1. A positive result using a 100 mm sample cube at 140 °C. 2. A negative result using a 100 mm sample cube at 100 °C. 3. A negative result using a 25 mm sample cube at 140 °C.

Additional information: the powder is to be packed in containers with a volume: < 450 l Question: Identify the type of hazard shown by these results and determine the physical hazard classification, explaining how you arrived at the result.

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Answer:

The results presented suggest that the powder may be self‐heating substance or mixture.

Comparing the test results provided with the decision logic of chapter 2.11 of the GHS we find that

the powder should be considered for this class given test result 1

the powder is not Category 1, since test result 3 is negative

the powder is not category 2 since test result 2 is negative and it is to be packed at less than 450 l volume

The powder therefore cannot be classified as self‐heating and is not within the scope of the GHS based on this property.

Discussion point: remember that the powder may still have other hazardous properties (e.g. toxicity)

Resource material

To help you complete this exercise please refer to the following resource material (attached)

Section 2.11.4 GHS 4th Edition

Exercise 10: Organic peroxides – the effect of diluents

Benzoyl peroxide (IUPAC name dibenzoyl peroxide) is used widely in various formulations to

Initiate polymerisation reactions

Treat certain skin conditions As a bleach

The molecular structure of dibenzoyl peroxide is as shown Question1: Calculate the lowest concentration of this substance in an inert diluent which would be classified as an organic peroxide, explaining how you arrived at you answer. Answer: To perform this calculation, the formula in section 2.15.2 GHS 4th Edn is solved for the mass % concentration of organic peroxide using 1 (the threshold percentage of available oxygen as specified in this section) That is, solve 1 = 16 X C / (Molecular Weight benzoyl peroxide) for C

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C = mass concentration of organic peroxide Using the following atomic weights C = 12 O = 16 H = 1 The molecular weight of benzoyl peroxide is 242 Solution: the lowest concentration = 15.13% Question 2: Benzoyl peroxide is to be shipped as a 38% dispersion in water for use as a polymeriser in the fibre reinforced composite boat building industry. Determine its physical hazard classification, and explain how you arrived at this classification. Answer: Look up benzoyl peroxide in table of section 2.5.3.2.4 UNRTDG. (supplied in resource materials) On referring to this table we find that the 38% benzoyl peroxide described is referred to as < 42% stable dispersion in water. This gives this dispersion a UN number of 3109. Looking up this UN number in the table in the part 3 dangerous goods list of the UNRTDG we find that classification is organic peroxide type F. Label elements:

Symbol: flame


Hazard statement: Heating may cause fire

Resource material To help you complete this exercise please refer to the following resource material Section 2.15.2 GHS 3rd Edition The UN Recommendations for transport of Dangerous Goods 16th Edition Listing of Organic Peroxides The UN Recommendations for transport of Dangerous Goods 16th Edition Listing of UN Numbers

Exercise 11: Mass loss from a metal A chemical when brought in contact with aluminum sheets causes a mass loss from the aluminum of 21 % after 11 days at 55 +/‐ 1°C (conditions as specified in Part III Section 37.4 of the UN Recommendations for the Transport of Dangerous Goods ‐ Manual of Test and Criteria) Question: Using the above information, determine the physical hazard classification including the required Hazard statement for this substance. Your answer should explain your reasoning.

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Answer: The mass loss is due to corrosion by the chemical so the potential Hazard classis 2.16 Corrosive to Metals Using the table of equivalencies in the physical hazards presentation, (corrosion of metals section) we see after using an interpolation step, that the mass loss given is equivalent to a corrosion rate of more than 6.25mm /year. From the hazard classification of section 2.16 of the GHS the chemical is therefore Class: Corrosive to Metals Category 1 Label elements: Symbol: Corrosion symbol Signal wo d Warning Hazard statement May be corrosive to metals Resource material The material describing classification of substances corrosive to metals is given in the physical hazards presentation, section on the hazard class corrosive to metals.

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Health Hazards Classification of Substances/ Mixtures Exercises/Examples: Questions

General instructions:

Answer each of the following questions as instructed by the moderator for your session. You will be given a group of exercises to complete and then the moderator for your session will ask the whole group to discuss the answers to these exercises. Be prepared to provide your answer during the discussion session as well as to explain how you arrived at this answer. Please note that completing many of the exercises requires reference to the resource materials given at the end of the exercise so please read the exercise in full before attempting to answer the questions. If you have any time after answering the questions please also provide the GHS label element for the classifications you have determined.

A. Substances (45 minutes)

Acute Toxicity:

Resource material : GHS Purple book (PB), 4rd rev. ed, Table 3.1.1, Annex 1

Substance 1

Acute Oral Toxicity

Test Data GHS Classification Rationale

Oral LD50 : 300 mg/kg bw (observed in a GLP‐compliant study in rats)

Category 3

LD50=300mg/kg bw is considered an Acute Toxicity Estimate (ATE) for classification purpose; according to the classification criteria for acute oral toxicity, 300mg/kg bw is the upper value for Category 3. Therefore, it is assigned Category 3 Acute Oral Toxicity classification

Danger

Toxic if swallowed

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Substance 2

Acute Oral Toxicity

Use of adequate and reliable human data allowing classification according to table 3.1.1. Animal data not appropriate.


Toxicity Data:

Animal test data: oral LD50 (rat) > 5,000mg/kg bw (several values)

Human experience: lethal in relatively low dose range (ca. 300‐1,000mg/kg)

Category 3

.

Valid human data from a large data base (case studies) have precedence over animal data; the rat is in this case not the appropriate test species

Danger

Toxic if swallowed

Substance 3

Acute Dermal Toxicity

(Note use of non‐standard‐guideline test data)


Animal data:

A study to evaluate the acute dermal toxicity was performed in rabbits. The following test data results were reported:

‐ At the dose level of 50 mg/kg bw: no mortality was observed

‐ At 200 mg/kg bw: 100% mortality

Therefore, LD50 was estimated to be between 50mg/kg bw and 200mg/kg

Category 2 Since the dermal LD50 is above 50 mg/kg bw and less than 200 mg/kg bw, Category 2 classification is warranted

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bw

Danger

Fatal in contact with skin

Substance 4

Acute Inhalation Toxicity: experimentally obtained LC50 value


A gas

Animal data:

A GLP‐compliant test for acute inhalation toxicity (gaseous form) was performed in accordance with test guideline 403 in rats. The following LC50 was calculated: LC50: 4500ppm/4h

Category 4 LC50 = 4500 ppm is considered an Acute Toxicity Estimate (ATE) for classification purposes; according to the classification criteria for acute inhalation toxicity for gases, this value corresponds to Category 4. Therefore Category 4 Acute Inhalation Toxicity classification is warranted.

Warning

Harmful if inhaled

Substance 5

Acute Inhalation Toxicity (solid): Time extrapolation


Solid substance Category 3 The classification criteria for acute inhalation toxicity refer to a 4h exposure

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Animal data:

The acute inhalation toxicity was studied in rats in a GLP compliant study performed in principle according to OECD Test Guideline 403, but with respect for transport only with 1‐h exposure. The LC50 (1‐h) of 3 mg/l was calculated.

time; therefore to classify a substance, existing inhalation toxicity data generated from 1‐hour exposure should be converted accordingly: 1hour LC50 values have to be converted by dividing by 4 (Haber’s rule/law, dusts and mists)

LC50 (4‐h) = (LC50 (1‐h) / 4) = (3 mg/l / 4) = 0.75 mg/l, thus Category 3 classification is warranted

Danger

Toxic if inhaled

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Skin Corrosion/Irritation

Resource material : GHS Purple book (PB), 4rd rev. ed, Tables 3.2.1, 3.3.2, Annex 1

Substance 6

Skin Corrosion/Irritation


Toxicity data:

‐ No in vivo data available

‐ In vitro skin corrosion: Human skin model test (OECD 431): Positive

Other relevant information: determination of pH and acid/alkali reserve (buffering capacity) pH < 2 with low buffering capacity

Category 1

According to the criteria the valid positive in‐vitro test warrants classification in Cat 1 though buffering capacity is low.

Danger

Causes severe skin burns and eye damage

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Substance 7

Skin Corrosion


In OECD Test 404 full necroses/irreversible skin damage after 4 h exposure within 14 d were observed in one animal

Cat 1/(1C) According to the classification criteria for Skin Corrosion/Irritation the production of irreversible damage to the skin after 4h exposure in at least one animal warrants classification in Category 1/1C.

Danger


Substance 8

Skin Irritation


According to OECD Test Guideline 404 test substance was applied for 1 hour and three minutes. No scars or other irreversible effects were found. The scoring results obtained after 4

hours application time are

Erythema/Eschar: 2.7, 3, 0.66

Oedema: 1.7, 2, 1

Skin Irritant Category 2

The classification is made on basis of 2 of 3 animals exceeding 2.3 mean score for erythema.

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Warning

Causes skin irritation

Eye Damage/Irritation


Substance 9

Serious Eye Damage


Toxicity data: neither in vivo data nor in vitro data available

Other relevant information: pH 1.9; no info on buffering capacity

Category 1

Based on a pH <2, the substance is a skin corrosive Cat 1 according to the evaluation strategy for skin corrosion and irritation potential and deemed to cause irreversible eye effects; according to the evaluation strategy for serious eye damage and eye irritation the substance is then also causes eye damage (irreversible effects on the eye) Cat 1.

.

Danger

Causes serious eye damage

Substance 10

Eye Irritation


In an OECD Test Guideline 405 study the test substance was applied on the eyes

Eye irritant Category 2 The test results show:

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of three rabbits. The scoring results obtained are

Corneal opacity: 2, 2, 1.3

Iritis: 1, 1, 1

Conjunctival redness: 2, 1, 1

Conjunctival edema (chemosis): 3, 1.7, 2.3

Reversibility: The effects were reversible.

Cornea ≥ 1 (in all animals)

Iritis ≥ 1 (in all animals) Conjunctival redness ≥ 2 (in 1 animal)

Conjunctival edema ≥2 (in 2 of 3 animals)

The Category 2 criteria are fulfilled by the Cornea, Conjunctiva and Iris scores.

Warning

Causes serious eye irritation

Substance 11

Eye Irritation


OECD Test Guideline 405: Acute Eye Irritation/Corrosion test results:

Corneal opacity: mean score 0.6

Iritis: mean score 1.3

Conjunctival redness: mean score 2.4 (from 2 of 3 animals)

Conjunctival edema (chemosis): mean score 1.4

Reversibility: The effects were fully reversible after 7 days

Category 2B Since the mean score for redness over 24, 48, and 72 hours in 2of 3 animals is 2.4 and therefore > 2.3, and the effects are fully reversible, the criteria for classification in Category 2B are fulfilled.

No pictogram Warning

Causes eye irritation

Substance 12

Serious Eye Damage SAR


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The material is a new aliphatic secondary amine. No data is available. The test substance has Structure Activity Relationships (SAR) to substances with similar structure known to be corrosive to the skin.

Category 1 Based on expert judgment using SAR information the classifier concluded that Category 1 is justified, since there is a much data on aliphatic amines which are skin corrosives Category 1 and thus deemed to cause irreversible eye effects resulting in Serious Eye Damage Category 1 according to the evaluation strategy.

Danger

Causes serious eye damage

Sensitization


Substance 13

Respiratory Sensitizer Enzymes


The material is an enzyme with many well‐documented human case studies for respiratory sensitization occurring in workers exposed during the manufacturing process.

Respiratory Sensitizer

Category 1

Because of the clear evidence from valid human studies, classification for respiratory sensitization was warranted.

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Danger

May cause allergy or asthma symptoms or breathing difficulties if inhaled

Substance 14

Skin Sensitization


Toxicity data: There are many well documented human case reports on contact sensitization at very low concentrations and in addition positive animal study results showing a high potency

Skin Sensitizer, Category 1A

The classification criteria are clearly fulfilled based both on human and animal evidence.

.

Warning

May cause an allergic skin reaction

Germ Cell Mutagenicity:

Resource material : GHS Purple book (PB), 4rd rev. ed, Figure 3.5.1, Annex 1

Substance 15

Germ Cell Mutagenicity


Positive result in vivo in the Mammalian Bone Marrow Chromosome Aberration Test (OECD Test Guideline 475) and also positive in several in vitro tests for mutagenicity

Category 2 The test result fulfills the Germ Cell Mutagenicity Category 2 classification criteria of positive evidence obtained from a somatic cell mutagenicity tests in vivo in mammals

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Warning

Suspected of causing genetic defects (state route of exposure if it is conclusively

proven that no other routes of exposure cause the hazard)

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Carcinogenicity:


Substance 16

Carcinogenicity


Occupational exposure has been strongly associated with bladder cancer in numerous case reports from many countries. The association has also been observed in several epidemiological studies. In one extreme instance, all five of a group of workers continuously employed in manufacture of the substance for 15 years or more developed bladder cancer.

The substance was tested in mice, rats and hamsters by oral administration, in mice and rats by subcutaneous administration and in rats by inhalation and intraperitoneally. Following its oral administration to mice of different strains, both sexes, newborn and adult, and following its subcutaneous administration, it significantly increased the incidence of liver‐cell tumors (benign and malignant). In female rats, it markedly increased the incidence of mammary tumors; and in male and female hamsters, it increased the incidence of liver tumors following its oral administration. It also induced bladder carcinomas in dogs.

The substance gave positive results in several in vitro and one in vivo genotoxicity studies, no data were available on the genetic and related effects in humans.

Category 1A There is sufficient evidence that the substance is carcinogenic to mice, rats, hamsters and dogs and there is sufficient evidence that S32 is carcinogenic to humans.

Sufficient human evidence demonstrates causality between human exposure and the development of cancer, and sufficient evidence in animals shows a causal relationship between the substance and an increased incidence of tumors.

Danger

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May cause cancer (state route of exposure if it is conclusively proven that no other

routes of exposure cause the hazard)

Substance 17

Carcinogenicity (Derivation of classification from lists)


Classified as Group 3: Not Classifiable as to Carcinogenicity to Humans by IARC (1999)

Classified as Category A4: Not Classifiable as a Human Carcinogen by ACGIH (2001)

Classified as Category D: Not Classifiable as to Human Carcinogenicity by EPA (1995)

Not classified Due to the fact that the substance is classified as Group 3 by IARC (1999), Category A4 by ACGIH (2001) and Category D by EPA (1995).

No hazard communication

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Reproductive Toxicity:


Substance 18

Reproductive Toxicity


Human epidemiological studies in IRIS Toxicological review (2005) and ATSDR (2000), describe increased incidence of natural abortion after exposure, abnormal development and malformation of newborns caused by prenatal abuse and decreased plasma concentrations of luteinizing hormone and testosterone after exposure.

Increased risk of late spontaneous abortions associated with exposure at levels around 88 ppm (range 50‐150 ppm).

Evidence of increased incidences of fetal death and delayed ossification, a decrease and unossification of sternebrae, a shift in rib profile, excess ribs, retarded skeletal development, delayed reflex response, learning disability and early vaginal opening and testes descent at dosing levels not toxic to dams from rat and mouse teratogenicity tests.

Category 1A Evidence of adverse effects on development in humans and in animal studies

Danger

May damage fertility of the unborn child (state specific effect if known)(state route of exposure if it is conclusively proven that no other routes of exposure cause the hazard)

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Specific Target Organ Toxicity – Single and Repeated Exposure:

Resource material : GHS Purple book (PB), 4rd rev. ed, Figures 3.8.1, 3.9.1, Annex 1

Substance 19

STOT‐SE Human Experience


There is broad human experience from many case reports of blindness following oral ingestion of a single dose.

Acute oral toxicity in rats is low (LD50 values > 7,000 mg/kg body weight with no evidence of specific target organ toxicity observed in rats).

STOT‐SE

Category 1

The classification criteria for STOT‐SE Category 1 are fulfilled, as there is clear human evidence of a specific target organ toxicity effect. The rat is the standard animal species for single exposure tests and is not sensitive as it did not predict the specific target organ toxicity potential seen in humans.

Danger

Causes damage to organs (or state all organs affected if known)(state route of exposure if it is conclusively proven that no other routes of exposure cause the hazard)

Substance 20

STOT‐RE


Human evidence including "hemolytic anemia, a decrease in white blood cell count" (ACGIH (7th, 2001)), and evidence from animal studies including "a decrease in mean corpuscular hemoglobin, hemoglobin concentrations, red blood cell count and hematocrit levels," and "adrenal degeneration" (MOE Risk Assessment Vol.3 (2004)).

Category 1 (adrenal, blood system)

The effects on experimental animals were observed at dosing levels within the guidance value ranges for Category 1

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Danger

Causes damage to organs (state all organs affected, if known) through prolonged or repeated exposure (state route of exposure if it is conclusively proven that no other routes of exposure cause the hazard)

Substance 21

STOT


In valid animal experiments narcotic effects (transient effect on the nervous system including lethargy, lack of coordination and narcosis) were observed following a single inhalation exposure at ≥ 8 mg/l.

STOT Category 3

Narcotic effects

The classification criteria for narcotic effects STOT Category 3 are fulfilled based on results in an animal experiment.

Warning

May cause drowsiness or dizziness

Aspiration Hazard:

Substance 22

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Aspiration Hazard


The material is a hydrocarbon and has a kinematic viscosity of 0.74mm3/s at

25 .

Case reports of human symptoms "May cause pulmonary edema if inhaled and chemical pneumonia if swallowed." (ATSDR (2001)).

Category 1 Fulfills criteria

it is a hydrocarbon and has a kinematic viscosity ≤ 20.5 mm2/s, measured at 40° C.

Also based on the description in reports of human symptoms, the Category 1 critera are fulfilled:

Danger

May be fatal if swallowed and enters airways

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B. Mixtures (1 hour)

Exercise 1 (=PCI Example 1)

Acute oral toxicity of a mixture

The following example demonstrates the application of data when the available range data spans

more than one acute toxicity range estimate in Table 3.1.2.

Ingredient information:

Ingredient Wt% Test Data

Ingredient 1 16 Oral LD50: 1,600 mg/kg

Ingredient 2 4 Acute oral toxicity range estimate: 200 < LD50 < 2,000

Ingredient 3 80 Oral LD50: 3,450 mg/kg

Answer:

Apply the equation in paragraph 3.1.3.6.1:

nmixture ATEi

Ci

ATE

100

450,3

80

200

4

600,1

16100

mixtureATE

Therefore: ATEmixture = 1,880 mg/kg, Category 4

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Warning

Harmful if swallowed

Rationale:

(a) Classification via application of substance criteria is not possible since acute toxicity test data

was not provided for the mixture (paragraph 3.1.3.4);

(b) Classification via the application of bridging principles is not possible since data on a similar

mixture was not provided (paragraph 3.1.3.5.1);

(c) Classification of the mixture based on ingredient data can be considered (paragraph 3.1.3.6);

(d) Applying the “relevant ingredients” concept from paragraph 3.1.3.3(a) means that all

ingredients will be considered when applying criteria in paragraph 3.1.3.6;

(e) Data is available for all ingredients so criteria in paragraph 3.1.3.6.1 apply;

(f) Ingredients 1, 2 and 3 are all included in the ATEmixture calculation because they have data that

fall within a GHS acute toxicity category [paragraph 3.1.3.6.1 (a)].

(g) Applying the guidance in Note (a) to Table 3.1.1:

(i) The LD50 data for ingredients 1 and 3 are used in the ATEmixture calculation since data are

available;

(ii) The use of expert judgment is needed to determine what value to use in the ATEmixture

calculation for ingredient 2. Since the experimentally obtained acute toxicity range

estimate of 200 < LD50 < 2,000 for ingredient 2 is existing data developed prior to

development of the GHS criteria it does not match up with the ranges provided in Table

3.1.2. The lower end of the range falls within the Category 3 range of 50 – 300 mg/kg and

the converted acute toxicity point estimate for an Oral Category 3 ingredient is 100. Given

that the converted point estimate is lower than the experimentally determined value of >

200 mg/kg it does not make sense to use the converted point estimate. In this case, one

should apply the known information, and 200 mg/kg should be used in the ATEmixture

calculation.


Acute oral toxicity of a mixture

The following example demonstrates the application of the “relevant ingredients” criteria in

paragraph 3.1.3.3.

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Ingredient Wt% Classification Test Data

Ingredient 1 4 Oral Category 3 LD50: 125 mg/kg

Ingredient 2 92 ‐ No data available

Ingredient 3 3 Oral Category 4 LD50: 1500 mg/kg

Ingredient 4 0.9 ‐ No data available

Ingredient 5 0.1 Oral Category 2 LD50: 10 mg/kg

Answer:

Apply the equation in paragraph 3.1.3.6.2.3:

n i

i

mixture

unknown

ATE

C

ATE

ifC %10100

1500

3

125

4)92(100

mixtureATE

Therefore: ATEmixture = 235 mg/kg, Category 3, and

“92% of the mixture consists of an ingredient of unknown toxicity.”

Danger

Toxic if swallowed

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Rationale:

(a) Classification via application of substance criteria is not possible since acute toxicity test

data was not provided for the mixture (paragraph 3.1.3.4);

(b) Classification via the application of bridging principles is not possible since data on a

similar mixture was not provided (paragraph 3.1.3.5.1);

(c) Classification of the mixture based on ingredient data can be considered (paragraph

3.1.3.6);

(d) Applying the “relevant ingredients” concept from paragraph 3.1.3.3 (a) means that

ingredient 4 could be excluded from both the ATEmixture calculations. This is true for the

calculation in either paragraph 3.1.3.6.1 or 3.1.3.6.2.3. This same reasoning could also

apply to ingredient 5, as it is below the “relevant ingredients” threshold; however, the use

of expert judgment is necessary to make this decision for ingredient 5 as it is classified in

Category 2. For this example, it was decided that since the percentage of this ingredient is

well below the threshold (i.e. 0.1%) and the ingredient is classified in Category 2, it would

be excluded from the ATE calculation;

(e) The total concentration of ingredients with unknown acute toxicity (i.e. ingredient 2) is

92%, therefore, the ATEmixture equation in paragraph 3.1.3.6.2.3 must be used. This

calculation corrects for ingredients with unknown acute toxicity above 10% of the mixture;

(f) Ingredients 1 and 3 are included in the ATEmixture calculation because they have data that

fall within a GHS acute toxicity category [Paragraph 3.1.3.6.1 (a)];

(g) Applying the guidance in Note (a) to Table 3.1.1 results in using the LD50 data for

Ingredients 1 and 3 in the ATEmixture calculation since data are available;

(h) Ingredient 2 does not have any useable information for the oral route ATEmixture calculation

and is in the mixture at a concentration 1% so an additional statement is included

(paragraph 3.1.3.6.2.2.);

Exercise 3 (= PCI example 5)

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The following example demonstrates application of data for skin corrosion/irritation for mixtures

when additivity may not apply (paragraphs 3.2.3.3.4 and 3.3.3.3.4). A similar approach would be

used for serious eye damage/irritation.


Ingredient Wt% Classification Ingredient information

Ingredient 1 4 Skin Category 1 pH = 1.8

Ingredient 2 5 Skin Category 2 ‐

Ingredient 3 5 Skin Category 3 ‐

Ingredient 4 86 ‐ No data available

Mixture information: Mixture pH = 4.0

Answer:

For this mixture, the classification was assigned as a Category 1 because ingredient 1 (Category 1) is

in the mixture at 1%

Danger


Rationale:

(a) Classification via application of substance criteria is not possible since test data (other

than a pH) was not provided for the mixture (paragraph 3.2.3.1.1);

(b) The overall mixture pH of 4.0 does not result in classification in Category 1 since this

does not fall within the criteria of pH 2 or pH 11.5 ( paragraph 3.2.3.1.2);

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(c) Classification via the application of bridging principles is not possible since data on a

similar mixture was not provided (paragraph 3.2.3.2.1);

(d) Classification of the mixture based on ingredient data can be considered (paragraph

3.2.3.3);

(e) Ingredient 1 with a pH = 1.8 is an ingredient for which additivity might not apply as

described in paragraph 3.2.3.3.4 and summarized in Table 3.2.4. Expert judgment would

be needed to determine whether or not additivity applies. Knowledge of the

components is important. Given the limited information in this example, the classifier of

this mixture chose to apply non‐additivity for a conservative approach. Without

information on the mode of action of Ingredient 1, the mixture could be corrosive

regardless of the overall pH. Therefore, the criteria described in paragraph 3.2.3.3.4

were applied (i.e. “A mixture containing corrosive or irritant ingredients that cannot be

classified based on the additivity approach shown in Table 3.2.3, due to chemical

characteristics that make this approach unworkable, should be classified as skin

Category 1 if it contains ≥ 1% of a corrosive ingredient and as skin Category 2/3 when it

contains ≥ 3% of an irritant ingredient”).

Exercise 4 Classification of “AllRound”: a pesticide mixture used for crop protection The Table below provides compositional information on “Allround”, which is a mixture of three different

commercial pesticide formulations, an unknown ingredient and two different solvents, plus water. The

toxicological data/classifications for the different ingredients of the mixture are provided in the Table. The

data in the table are generally based on Safety Data Sheets and other information in the Internet. There are

no test data on the mixture as a whole. There are no test data on similar tested mixtures.

Ingredients % AT oraL

LD50 ...mg/kg/ Classification

AT dermal LD50.mg/kg /Clas‐ sification

AT Inhal‐ ation LC50 Mg/l/4h

Skin Corr./Irr

Eye damage/ Irritation (EI)

Sensitization Carc Mut Repro‐ ductive toxicity

1. Pesticide formulation A Fungicide

7.2 NC >5,000

NC >5,000

NC Tested at max. conc

NC Cat 2 Respiratory: NC Skin: Cat 1

NC NC Cat 2

2. Pesticide formulation B Insecticide

35 Cat 4 LD>2000 1.62 mg/l/4h

NC „May cause slight EI NC

NC Negative

NC NC

3. Pesticide formulation C Herbicide

12 NC >5,000

NC >5,000

NC Tested at max.conc.

Cat 2 Cat 2 Negative

Neg. Neg Neg.

4. Ingredient (Unknown)

0.8 No data No data No data No data No data No data No data

No data

No data

5.Ingredient (a solvent)

11 NC NC Unknown NC NC NC NC NC NC

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6. Solvent : 1,2 Propyleneglycol

16 NC NC NC NC NC NC NC NC NC

7. Water 18 NC NC NC NC NC NC NC NC NC

Question 1: Which procedure for mixture classification has to be used?

Question 2: Which Hazard classes/differentiations have to be taken into consideration?

Question 3: Are there any ingredients which can be totally neglected in the mixture classification

procedure? If any, why?

Question 4: Determine for each respective Hazard class/differentiation which ingredients have to

be taken into account (“Cut‐off values)”.

Question 5: What is the classification of the mixture? Rationale?

Question 6: The manufacturer of the pesticide wants a formulation classified in Acute oral toxicity

Cat 5. What is the maximum concentration of the relevant ingredient?

Resource material Excerpts from Chapter 3.1, 3.2, 3.3, 3.4 and 3.7 GHS 3rd Edition

Category 5 Acute Oral Toxicity

No pictogram Warning

May be harmful if swallowed

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Hazardous to the aquatic environment

Exercise/Examples: Answers with Questions General instructions:

Answer each of the following questions as instructed by the moderator for your session. You will be given a group of exercises to complete and then the moderator for your session will ask the whole group to discuss the answers to these exercises. Be prepared to provide your answer during the discussion session as well as to explain how you arrived at this answer. Please note that completing many of the exercises requires reference to the resource materials given at the end of the exercise so please read the exercise in full before attempting to answer the questions. Please also provide the GHS label elements (pictogram, signal word, and hazard statement) for the classifications you have determined.

A. Substances

Exercise 1: Potential Acute (short‐term) aquatic hazard?

A substance has been tested with respect to acute aquatic toxicity with the following results:

‐ Daphnia EC50 5.6mg/l/48h

‐ Algae ErC50 99mg/l/72h

Question: Determine the classification including the pictogram, signal word, and hazard statement (as appropriate)

Answer:

Classification: Acute aquatic toxicity Category 2 (see Table 4.1.1.) No pictogram No signal word Hazard statement: H401=Toxic to aquatic life Rationale for classification: The L(E)C50 for the most sensitive species (daphnia) in a valid study is > 1mg/l but =< 10 mg/l, and thus the criteria for Category 2 are clearly fulfilled. The algae data are not taken anymore into consideration. Resource material

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GHS Purple book, 3rd rev. ed, Tables 4.1.1 and 4.1.6 Exercise 2:

A substance has been tested in all representative aquatic species with respect to acute toxicity with

the following results:

‐ Fish LC50 0.002mg/l/96 h

‐ Daphnia EC50 4.6mg/l/48h


Question: Determine the classification including the harmonized label elements and, if applicable, the Multiplying factor (M factor) Answer:

Classification: Acute aquatic toxicity Category 1 (see Table 4.1.1.) M‐factor: 100 (s. Table 4.1.5) Environmental pictogram Warning Hazard statement: H400=Very toxic to aquatic life Rationale for classification: The L(E)C50 for the most sensitive species (fish) in a valid study is below the cut‐off level of <= 1 mg/l for Category 1, and thus the criteria are clearly fulfilled Resource material GHS Purple book, 3rd rev.ed, Tables 4.1.1 and 4.1.5 Exercise 3: Potential acute aquatic hazard A mixture has been tested in all representative aquatic species with respect to acute toxicity with

the following results:

‐ Fish LC50 0.8 mg/l/96 h (study with flaws)

‐ Daphnia EC50 10 mg/l/48h


Question: Which classification is appropriate? Discuss the crucial point and show options for solutions. Answer:

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Classification: Acute Cat 2 No pictogram or signal word; Toxic to aquatic life NB: Application of a very conservative approach would lead to Cat 1 Rationale: Based on the lowest valid value of 10 mg/l for daphnia the criteria for Cat 2 are fulfilled. Based on expert judgement on the total weight of evidence the invalid study has not been used for classification. Other options: ‐ Request the full fish study report and have it evaluated in order to decide if it is really in total invalid and not usable even in part (expert judgement) ‐ Perform a new fish study in order to clarify the toxicity in this species (Not required by GHS) Resource material GHS Table 4.1.1 and chapter 1.3.2.4.2, 1.3.2.4.8 and 1.3.2.4.9.2 (excerpts) Exercise 4: Potential aquatic hazard of an organic substance? A substance has been tested with the following results. ‐ Fish early life stage: NOEC 0.75 mg/l

‐ Daphnia reproduction: NOEC 1.6 mg/l

‐ Degradation: OECD test No. 301 > 70% biodegradability in 28days Question 1: Which kind(s) of aquatic hazards can be assessed on the basis of the available data? Question 2: Determine the classification including the label elements and if applicable the Multiplying factor (M factor) Answers:

1: Since no data with respect to acute toxicity are available, only chronic aquatic hazards can be determined 2. Classification: Chronic Cat 3; there is no specific M factor , since the NOEC is < 0.001 mg/l No pictogram No signal word Harmful to aquatic life with long lasting effects Rationale: The substance is rapidly degradable. Since there are adequate chronic data available, Table s. 4.1.1 b. ii applies for classification. The lowest valid chronic NOEC is > 0.1 mg/l and <= 1 mg/l, therefore Cat Chronic 3; H 412=Harmful to aquatic life with long lasting effects According to Table 4.1.5 there is no specific M factor

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Resource material GHS Table 4.1.1, 4.1.5 and 4.1.6 Exercise 5: Potential aquatic hazard? A substance has been tested with the following results. ‐ Fish early life stage: NOEC 0.045 mg/l

‐ Daphnia reproduction: NOEC 1.6 mg/l

‐ Rapid biodegradation: no useful data available Question 1: What is the classification including the label elements? Question 2: Discuss the consequence of the lack of data on degradation Answer: Classification: Cat 1 Environmental pictogram Warning H 410=Very toxic to aquatic life with long lasting effects Rationale: Assumption not readily biodegradable; see Note 4 to Table 4.1.1. Therefore Table 4.1.1(b) i has to be applied. Consequence: It’s one of the cases, where data gaps can lead to a more stringent classification (Cat 1 rather than Cat 2) Resource material: GHS Tables 4.1.1 and 4.1.6 Exercise 6: Potential aquatic hazard? A substance has been tested with the following test results:

Data:

‐ Fish LC50 8.2 mg/l

‐ Daphnia EC50 56 mg/l

‐ Algae ErC50 122 mg/l

‐ Biodegradability <5%

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‐ log Kow 2.1

Question: Identify the type of hazard exhibited and determine the environmental hazard classification and the required label elements for this substance, include an explanation of how you classified the substance. Answer: There is relevant acute and chronic aquatic toxicity

Classification: Acute and chronic aquatic toxicity Cat 2

Environmental pictogram

No signal word

Toxic to aquatic life with long lasting effects

Rationale:

Acute toxicity Cat 2, since EC50 >1 and <=10 mg/l (Table 4.1.1 a)

No adequate chronic toxicity data available, therefore Table 4.1.1b (iii)

Not readily biodegradable, Log Kow not taken into account

Resource material: GHS Table 4.1.1 Exercise 7: Potential aquatic hazard of a green powder? A substance has been tested with the following test results: ‐ Fish LC50 8.2 mg/l

‐ Daphnia EC50 56 mg/l

‐ Algae ErC50 122 mg/l

‐ Daphnia reproduction NOEC > 1mg/l


‐ log Kow 2.1

Question: What is the classification including the label elements? Answer: Classification: Acute and chronic Cat 2

Environmental pictogram

No signal word

Toxic to aquatic life with long lasting effects

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Rationale:

Acute Cat 2 from Fish data according to Table 4.1.1a

Not readily degradable; this information combined with acute data for fish gives chronic 2 ( s. Table

4.1.1 b (iii)

No BCF; log Kow not taken into account

Chronic data NOEC > 1mg/l (daphnia) cannot be used for non‐classification since not from the same

species for which acute classification is based on (fish)

Resource material: GHS Table 4.1.1 Exercise 8: Potential aquatic hazard? A substance has been tested with the following test results ‐ Fish LC50, Daphnia EC50, Algae ErC50 all > water solubility

‐ Water solubility 35 mg/l


‐ log Kow 2.1

Question1: Determine the classification for acute and chronic aquatic toxicity and label elements Answer:

Acute and chronic no classification No hazard communication Rationale: ‐ Acute toxicity values > water solubility ‐ Not readily degradable, but log Kow< 4; no BCF ‐ No chronic data Therefore no classification according to criteria in Table 4.1.1 (c) Resource material: GHS Table 4.1.1

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B. Mixtures


The following example demonstrates application of the summation methods when classification information is available for some or all of the ingredients of a mixture.


Ingredient Wt% Acute classification

(M‐factor)

Chronic classification

(M‐factor)

Ingredient 1 0.01 Acute 1

(M‐factor: 10)

Chronic 1

(M‐factor: 10)

Ingredient 2 1.0 Acute 2 Chronic 2

Ingredient 3 25.0 Not classified Chronic 4

Ingredient 4 68.76 Not classified Not classified

Answer:

Acute Classification - Not classified because:

Acute 1: (Acute 1) x M 25%

using data from ingredients of the mixture:

(0.01% x 10) = 0.1% (Not classified)

Acute 2: (M x 10 x Acute 1) + Acute 2 25%


(10 x 10 x 0.01%) + 1.0% = 2.0% (Not classified)

Acute 3: (M x 100 x Acute 1) + (10 x Acute 2) + Acute 3 ≥ 25%


(10 x 100 x 0.01%) + (10 x 1.0) = 20% (Not classified)

Chronic Classification - Category 4 because:

Chronic 1: (Chronic 1) x M 25%


0.01% x 10 = 0.1% (Not classified)

Chronic 2: (M x 10 x Chronic 1) + Chronic 2 25%


(10 x 10 x 0.01%) + 1.0% = 2% (Not classified)

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Chronic 3: (M x 100 x Chronic 1) + (10 x Chronic 2) + Chronic 3 ≥ 25%


(10 x 100 x 0.01%) + (10 x 1.0%) = 20% (Not classified)

Chronic 4: Chronic 1 + Chronic 2 + Chronic 3 + Chronic 4 ≥ 25%


0.01% + 1.0% + 25.0% = 26.01% (Classified)

Rationale:

(a) Classification via application of substance criteria is not possible since aquatic toxicity test data was not provided for the mixture (paragraph 4.1.3.3);

(b) Classification via the application of bridging principles is not possible since data on a similar mixture was not provided (paragraph 4.1.3.4);

(c) Classification based on ingredient data for the mixture can be considered (paragraph 4.1.3.5);

(d) Acute and chronic classification data is available for some of the ingredients of the mixture and the percentage of these ingredients classified as “Acute” or “Chronic” will feed straight into the summation method (paragraph 4.1.3.5.51);

(e) Adequate toxicity data is not available so the additivity formula cannot be considered (paragraph 4.1.3.5.2)

Acute classification:

(f) Applying the “relevant ingredients” concept from paragraph 4.1.3.1 means that:

(i) The use of expert judgment is necessary to make the “relevant ingredient” decision for ingredient 1 since it is a highly toxic ingredient with an M-factor of 10. In this case it was decided to include the ingredient because its concentration in the mixture (i.e., 0.01%) is still significant given the M factor and the constants used in the Acute 2 and 3 calculations for Acute 1 ingredients;

(ii) Ingredient 2 will be included in the calculation because it is in the mixture at a concentration 1%;

(g) The summation method approach described in paragraph 4.1.3.5.5.3 applies and the cut-off value/concentration limits provided in Table 4.1.3 are used for classification.

Chronic classification:

(h) Applying the “relevant ingredients” concept from paragraph 4.1.3.1 means that:

(i) The use of expert judgment is necessary to make the “relevant ingredient” decision for ingredient 1 since it is a highly toxic ingredient with an M-factor of 10. In this case it was decided to include the ingredient because its concentration in the mixture (i.e., 0.01%) is still significant given the M factor and the constants used in the Chronic 2 and 3 calculations for Chronic 1 ingredients.

(ii) Ingredients 2 and 3 will be included in the calculation because they are in the mixture at a concentration 1%.

(i) The summation method approach described in paragraph 4.1.3.5.5.4 applies and the cut-off value/concentration limits provided in Table 4.1.4 are used for classification.

(End of example 1)

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Exercise 10 (=PCI 2)

The following example demonstrates application of a stepped approach where the additivity formula is used for the part of the mixture that has chronic toxicity data and passing that result into the summation method.


Ingredient Wt% Chronic toxicity data NOEC

or ECx

Rapidly

degradabl

e

Classification

NOEC (28 day for fish) 4.1

Ingredient 1 15 NOEC (21 day for

crustacea)

0.13 Yes ‐

Ingredient 2 5 NOEC (for algae) 0.8 No ‐

Ingredient 3 80 ‐ Chronic 3

Answer:

Mixture is Chronic Category 3

Step 1:

Applying the additivity formula based on chronic toxicity from 4.1.3.5.2 (b):

nnm NOECj1.0

Cj

NOECi

Ci

EqNOEC

CjCi

where:

Ci = concentration of ingredient i (weight percentage) covering the rapidly

degradable ingredients;

Cj = concentration of ingredient j (weight percentage) covering the non‐

rapidly degradable ingredients;

NOECi = NOEC (or other recognized measures for chronic toxicity) for

ingredient i covering the rapidly degradable ingredients, in mg/l;

NOECj = NOEC (or other recognized measures for chronic toxicity) for

ingredient j covering the non‐rapidly degradable ingredients, in mg/l;

N = number of ingredients, and i and j are running from 1 to n;

EqNOECm = Equivalent NOEC of the part of the mixture with test data;

EqNOECm = 20/((15/0.13) + 5/(0.1x 0.8)) = 0.11 mg/l

The part of the mixture (i.e., 20%) with Chronic toxicity data (i.e., ingredients 1 and 2) has an EqNOECm of 0.11 mg/l. As the NOEC of the ingredients that are considered not-rapidly degradable have already been multiplied with the factor 0.1

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the EqNOECm can now be applied to table 4.1 b (ii) resulting in a classification of Chronic 3.

Step 2:

Ingredient information going into the summation method calculations:

Ingredient Wt % Classification

Additivity result – part of mixture with only

toxicity data

20 Chronic 3

Ingredient 3 80 Chronic 3


0% (Not classified)


using data from the additivity result & ingredients of the mixture:

(10 x 0%) + 0% = 0% (Not classified)

Chronic 3: (M x 100 x Chronic 1) + (10 x Chronic 2) + Chronic 3 ≥ 25%

using data from the additivity result & ingredients of the mixture:

(100 x 0%) + (10 x 0%) + 20% + 80% = 100% (Classified)

Alternatively apply summation method straight away.

Rationale:

(a) Classification via application of substance criteria is not possible since acute aquatic toxicity test data was not provided for the mixture (paragraph 4.1.3.3);

(b) Classification via the application of bridging principles is not possible since data on a similar mixture was not provided (paragraph 4.1.3.4);

(c) Classification based on ingredient data for the mixture can be considered (paragraph 4.1.3.5);

(d) The percentage of the ingredient classified as Chronic 3 will feed straight into the summation method (paragraph 4.1.3.5.1);

(e) Adequate toxicity data for the other ingredients are available so the additivity formula in combination with the summation method can be considered (paragraphs 4.1.3.5.2 & 4.1.3.5.5.4);

(f) Applying the “relevant ingredients” concept from paragraph 4.1.3.1 means that ingredients 1, 2, and 3 will be considered in the calculations (paragraph 4.1.3.5.2 (b));

(g) When applying the additivity formula the preferred method is to calculate the toxicity of this part of the mixture for each ingredient toxicity values that relate to the same taxonomic group (i.e. fish, crustacean or algae) and then to use the highest toxicity obtained (i.e., use the most sensitive of the three groups). However, when toxicity data for each ingredient are not available in the same taxonomic group the data from the most sensitive test organism should be used (paragraph 4.1.3.5.3). In this case ingredient 1’s toxicity data for Crustacea is used because it is has the lowest value (i.e. highest toxicity) and ingredient 2’s Algae data is used;

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(h) Application of the chronic additivity formula results in 20% of the mixture being classified at Chronic Category 3, which is used in the summation method with the classification information provided for ingredient 3;

(i) If the mixture is classified in more than one way, the method yielding the more conservative result is valid (GHS 4.1.3.5.4);

Exercise 11 (PCI 3)

The following example demonstrates application of the tiered approach to determining the mixture’s classification where acute toxicity data is available on the mixture as a wholeas well as on the ingredients, and chronic classification information is only available on the ingredients.


Ingredient Wt% Acute toxicity data L(E)C50 mg/l Chronic classification

LC50 (for fish) 12

EC50 (for crustacea) 18

Ingredient 1

5

ErC50 (algae) 0.9

Chronic 1

(M Factor: 1)

LC50 (for fish) 40


Ingredient 2 1.5

ErC50 (algae) 9.5

Chronic 2

LC50 (for fish) > 100

EC50 (for crustacea) > 100

Ingredient 3 93.5

ErC50 (algae) > 100

Chronic 4

Information on tested mixture:

Acute toxicity data L(E)C50 mg/l

LC50 (for fish) 68


ErC50 (algae) 12.5

Answer:

Acute classification - Category 3

Chronic classification - Category 2 because:


5% x 1 = 5% (Not classified)


using data from the ingredients of the mixture:

(1 x 10 x 5%) + 1.5% = 51.5% (Classified)

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Rationale:

Acute classification:

(a) Classification via application of substance criteria is possible for acute toxicity since acute aquatic toxicity test data was provided for the mixture as a whole (paragraph 4.1.3.3);

(b) The higher toxicity value (from the most sensitive test organism) which in this case is Algae or other aquatic plants is used to classify the tested mixture (paragraph 4.1.3.3.3 (a));

Chronic classification:

(c) Classification via application of substance criteria is not possible since chronic aquatic toxicity test data was not provided for the mixture as a whole(paragraph 4.1.3.3.4 (a));

(d) Classification via the application of bridging principles is not possible since data on a similar mixture was not provided (paragraph 4.1.3.4);

(e) Chronic classification data is available for some or in this case all of the ingredients of the mixture and the percentage of these ingredients will feed straight into the summation method (paragraph 4.1.3.5.1);

(f) Adequate chronic toxicity data is not available so the additivity formula cannot be considered (paragraph 4.1.3.5.2);

(g) Applying the “relevant ingredients” concept from paragraph 4.1.3.1 means that ingredients 1, 2, and 3 will be considered when applying criteria in paragraph 4.1.3.5.5;

(h) The chronic summation method approach described in paragraph 4.1.3.5.5.4 applies and the cut-off value/concentration limits provided in Table 4.1.4 are used for classification.

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Exercise 12 Mixture classification: acute and chronic hazards based on classification of ingredients Available information:

Ingredient % GHS‐Classification of ingredient

Relevant ingredient/ Ingredient to be taken into account

M‐Factor (M) On basis of avail‐able information

Ingredient 1 0.2 Aqu.chron. Cat 3; H 412 No; < 1% NA*

Ingredient 2 0.15 Aqu. akut Cat 1; H 400 Aqu. chron. Cat 1; H 410

Yes; > 0.1 % Yes; < 0.1 %

1 1

Ingredient 3 0.4 Aqu. chron. Cat 2; H 411 No; < 1% NA*

Ingredient 4 5.5 Aqu. chron. Cat 3; H 412 Yes; > 1% NA*

Ingredient 5 24.9 Aqu. acute Cat 1; H 400 Yes; > 0.1 % 1

Ingredient 6 21 Aqu. chron. Cat 4; H 413 Yes; > 1% NA*

Ingredient 7 47.85

*NA= Not applicable since not classified in Cat 1

Question 1: Which method is applicable? Why? Question 2: Apply the chosen method and classify the mixture Answer: Answer 1:

‐ No test data for the mixture as a whole, thus direct classification not possible

‐ No test data for similar mixtures, therefore Bridging principles not applicable

‐ No complete data sets for the ingredients, therefore Additivity formula not applicable

Summation method (§ 4.1.3.5.5) on basis of classified ingredients

Answer 2:

1. Acute aquatic toxicity (Table 4.1.3 ):

Cat 1; Criteria: Sum relevant Cat 1‐ ingredients x M) >= 25%:

0. x1 + 24,9%x1 = 25,05%

Cat 1

Remark: other Cats can be disregarded

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2. Chronic aquatic toxicity (Table 4.1.4):

Cat 1; Criteria: Sum (relevant chronic Cat 1‐ ingredients x M )>= 25%:

0.15x1 < 25%

No Classification (NC)

Cat 2; Criteria: Sum (M x 10x rel. chron. Cat 1‐ingredients) + rel. chron. Cat2‐ingredients >= 25%:

1x10x0.15 + 0= 1.5 < 25%

NC

Cat 3; Criteria: Sum ( M x 100 x rel. Chron. Cat 1‐ingredients)+ (10x rel. chron. Cat2‐ingredients)

+ rel. chron. Cat 3‐ingredients):

1 x 100 x 0.15 +0+5.5 = 20,5 < 25%

NC

Cat 4; Criteria: Rel. chron. Cat 1‐ingredients+ rel. chron. Cat 2‐ingrdients + rel. chron. Cat 3‐

ingredients

rel. chron. Cat 4‐ingredients:

0.15 + 0 + 5.5 + 21 = 26.65 >25%

Cat 4

Resource material

PB Tables 4.1.3 and 4.1.4

practical exercises in physical hazard classification (exercise ......page 1 of 49 practical...

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