Mixtures of liquids

Mixtures of liquids which are toxic on inhalation shall be assigned to packing groups according to the following criteria:

If LC50 is known for each of the toxic substances constituting the mixture, the packing group may be determined as follows:

(a)calculation of the LC50 of the mixture:

where fi = molar fraction of constituent i of the mixture;

LC50i = average lethal concentration of constituent i in ml/m3.

(b)calculation of volatility of each mixture constituent:

where Pi = partial pressure of constituent i in kPa at 20 °C and at standard atmospheric pressure.

(c)calculation of the ratio of volatility to LC50:

(d)the values calculated for LC50(mixture) and R are then used to determine the packing group ofthe mixture:

Packing group I R≥10 and LC50(mixture) ≤1 000 ml/m3;

Packing group II R ≥ 1 and LC50(mixture) ≤3 000 ml/m3, if the mixture does not meet the criteria for packing group I;

Packing group III R≥1/5 and LC50(mixture) ≤5 000 ml/m3, if the mixture does not meet the criteria of packing groups I or II.

In the absence of LC50data on the toxic constituent substances, the mixture may be assigned to a group based on the following simplified threshold toxicity tests. When these threshold tests are used, the most restrictive group shall be determined and used for carrying the mixture.

A mixture is assigned to packing group I only if it meets both of the following criteria:

(a)A sample of the liquid mixture is vaporized and diluted with air to create a test atmosphereof 1 000 ml/m3vaporized mixture in air. Ten albino rats (5 male and 5 female) are exposed tothe test atmosphere for 1 hour and observed for 14days. If five or more of the animals diewithin the14-day observation period, the mixture is presumed to have an LC50equal to or lessthan 1 000ml/m3;

(b)A sample of vapour in equilibrium with the liquid mixture is diluted with 9 equal volumes ofair to form a test atmosphere. Ten albino rats (5 male and 5 female) are exposed to the testatmosphere for 1 hour and observed for 14days. If five or more of the animals die withinthe14-day observation period, the mixture is presumed to have a volatility equal to or greaterthan10 times the mixture LC50.

A mixture is assigned to packing group II only if it meets both of the following criteria, and does not meet the criteria for packing groupI:

(a)A sample of the liquid mixture is vaporized and diluted with air to create a test atmosphere of3 000 ml/m3vaporized mixture in air. Ten albino rats (5 male and 5female) are exposed to thetest atmosphere for 1 hour and observed for 14days. If five or more of the animals die withinthe 14-day observation period, the mixture is presumed to have an LC50equal to or lessthan 3 000ml/m3;

(b)A sample of the vapour in equilibrium with the liquid mixture is used to form a testatmosphere. Ten albino rats (5male and 5female) are exposed to the test atmosphere for1 hour and observed for 14 days. If five or more of the animals die within the 14-dayobservation period, the mixture is presumed to have a volatility equal to or greater than themixture LC50.

A mixture is assigned to packing group III only if it meets both of the following criteria, and does not meet the criteria for packing groups I or II:

(a)A sample of the liquid mixture is vaporized and diluted with air to create a test atmosphere of5 000 ml/m3vaporized mixture in air. Ten albino rats (5 male and 5 female) are exposed to thetest atmosphere for 1hour and observed for14days. If five or more of the animals die withinthe14-day observation period, the mixture is presumed to have an LC50equal to or lessthan 5 000ml/m3;

(b)The vapour concentration (volatility) of the liquid mixture is measured and if the vapourconcentration is equal to or greater than 1000ml/m3, the mixture is presumed to have avolatility equal to or greater than 1/5 the mixture LC50.

Methods for determining oral and dermal toxicity of mixtures

When classifying and assigning the appropriate packing group tomixtures in Class 6.1 in accordance with the oral and dermal toxicity criteria (see 2.2.61.1.3), it is necessary to determine the acute LD50of the mixture.

If a mixture contains only one active substance, and the LD50 of that constituent is known, in the absence of reliable acute oral and dermal toxicity data on the actual mixture to be carried, the oral or dermal LD50 may be obtained by the following method:

    LD50 value of preparation= LD50 value of active substance x 100
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percentage of active substance by mass

If a mixture contains more than one active constituent, there are three possible approaches that may be used to determine the oral or dermal LD50 of the mixture. The preferred method is to obtain reliable acute oral and dermal toxicity data on the actual mixture to be carried. Ifreliable, accuratedata are not available, then either of the following methods may be performed:

(a) Classify the formulation according to the most hazardous constituent of the mixture as if thatconstituent were present in the same concentration as the total concentration of all activeconstituents; or

b) Apply the formula:

where:

C = the percentage concentration of constituent A, B, ..., Z in the mixture;

T = the oral LD50values of constituent A, B, ...Z;

TM = the oral LD50value of the mixture.

NOTE: This formula can also be used for dermal toxicities provided that this information is available on the same species for all constituents. The use of this formula does not take into account any potentiation or protective phenomena.

Classification of pesticides

All active pesticide substances and their preparations for which the LC50and/or LD50values are known and which are classified in Class 6.1 shall be classified under appropriate packing groups in accordance with the criteria given in 2.2.61.1.6 to 2.2.61.1.9. Substances and preparations which are characterized by subsidiary hazardsshall be classified according to the precedence of hazard Table in 2.1.3.10 with the assignment of appropriate packing groups.

If the oral or dermal LD50value for a pesticide preparation is not known, but the LD50value of its active substance(s) is known, the LD50value for the preparation may be obtained by applying the procedures in 2.2.61.1.10.

NOTE : LD50 toxicity data for a number of common pesticides may be obtained from the most current edition of the document "The WHO Recommended Classification of Pesticides by Hazard and Guidelines to Classification" available from the International Programme on Chemical Safety, World Health Organisation (WHO), 1211Geneva 27, Switzerland. While that document may be used as a source of LD50 data for pesticides, its classification system shall not be used for purposes of transport classification of, or assignment of packing groups to, pesticides, which shall be in accordance with the requirements of ADR.

The proper shipping name used in the carriage of the pesticide shall be selected on the basis of the active ingredient, of the physical state of the pesticide and any subsidiary hazardsit may exhibit (see 3.1.2).

If substances of Class 6.1, as a result of admixtures, come into categories of hazarddifferent from those to which the substances mentioned by name in Table A of Chapter 3.2 belong, these mixtures or solutions shall be assigned to the entries to which they belong on the basis of their actual degree of danger.

NOTE: For the classification of solutions and mixtures (such as preparations and wastes), see also2.1.3.

On the basis of the criteria of 2.2.61.1.6 to 2.2.61.1.11, it may also be determined whether the nature of a solution or mixture mentioned by name or containing a substance mentioned by name is such that the solution or mixture is not subject to the requirements for this Class.

Substances, solutions and mixtures, with the exception of substances and preparations used as pesticides, which are not classified as acute toxic category 1, 2 or 3 according to Regulation (EC) No 1272/20083, may be considered as substances not belonging to class 6.1.

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