Occupational monitoring and regulatory controls

14.3.2Hazard classification

The health hazard assessment of limonene indicates that:

Limonene is a skin irritant in rodents. There are limited data on the potential of limonene to cause eye or respiratory irritation;

The autoxidation products of limonene are skin sensitisers. Limited data are available on the potential for limonene to cause respiratory sensitisation;

Following repeated exposure to limonene in male rats, the target organ is the liver with increased liver weights reported. However this effect is thought to be due to enzyme induction;

Renal tumours found in male rats are sex and species specific. The mechanism is considered to be related to the protein 2-globulin and is not relevant to humans;

Limonene is not mutagenic; and

Limonene has no reprotoxicity or teratogenic potential.

Limonene is currently included in the NOHSC 1999 List of Designated Hazardous Substances with the classification in Table 14.1. The material is identified as CAS number 138-86-3 and the listed names are p-mentha-1,8(9)-diene and dipentene.

The current European Union classification for limonene is also tabulated in Table 14.1. The classification covers d-, l- and dl- limonene (dipentene) as well as trans-isolimonene (not included in this assessment). The hazard assessment for limonene supports this classification, which will be taken up by NOHSC at the next revision of the List of Designated Hazardous Substances.

Liquid substances and preparations presenting an aspiration hazard in humans because of their low viscosity are to be classified as R65 Harmful: May cause lung damage if swallowed. This applies to:

• 
  substances containing aliphatic, alicyclic and aromatic hydrocarbons in a total concentration equal to or greater than 10% and having viscosity and surface tension values as specified (NOHSC, 1999); or
  
• 
  substances and preparations, based on practical experience in humans.
  

Table 14.1 - Current Australian and European Union hazard classification for limonene

	Australian hazard classification (NOHSC, 1999a)	European Union classification (European Commission, 1998)
Classification and Risk phrases#	Irritant Xi R38 R10* - Flammable R38 – Irritating to skin	Irritant Xi R38 R43 R10* - Flammable R38 – Irritating to skin R43 – May cause sensitisation by skin contact Environmental N* R50* – Very toxic to aquatic organisms R53* – May cause long term adverse effects in the aquatic environment
Safety phrases#	S(2)## – Keep out of reach of children S28 – After contact with skin, wash immediately with plenty of soap-suds.	S(2)## - Keep out of reach of children S24 - Avoid contact with skin S37 - Wear suitable gloves S60* – This material and/or its container must be disposed of as hazardous waste S61* - Avoid release to the environment. Refer to special instructions/ safety data sheet
Concentration cut-off levels and classification for mixtures**	At concentrations ≥ 25% Irritant Xi R38 – Irritating to skin	At concentrations ≥ 20% Irritant Xi R38 – Irritating to skin R43 – May cause sensitisation by skin contact At concentrations ≥ 1% & < 20% Irritant Xi R43 – May cause sensitisation by skin contact

# Where the criteria for aspiration hazard are fulfilled, the risk phrase “R65 – Harmful: May cause lung damage if swallowed” and the corresponding safety phrase “S62 –If swallowed, do not induce vomiting; seek medical advice immediately and show this container or label” should also be used.

## The safety phrase S2 can be omitted from the label when the substance or preparation is sold for industrial use only.

Note C: Some organic substances may be marketed either in a specific isomeric form or as a mixture of several isomers.

[Under ‘Name:’ or ‘Synonyms’ in the Full Text field], a general designation of the following type is sometimes used:“xylenol”

In this case the manufacturer or any other person who markets such a substance should state on the label whether the substance is a specific isomer (a) or a mixture of isomers (b).

Example: a) 2,4-dimethylphenol b)xylenol (mixture of isomers)

14.3.3Exposure standard

No national occupational standard has been assigned by NOHSC to limonene. Current overseas occupational exposure standards for limonene are summarised in Table 14.2.

Supporting documentation for the exposure standard adopted by American Industrial Hygiene Association (AIHA) states that the 30 ppm 8-hr TWA was set to protect against liver effects seen in male mice and reduced survival in female rats in a 2-yr NTP study (AIHA, 1993).

Table 14.2 - National occupational exposure standards for limonene

Country	8 h TWA	STEL	Year Adopted	Reference
Norway (OEL)	25 ppm (140 mg/m3)	-	1999	(RTECS, 2001)
Sweden	25 ppm (150 mg/m3)	50 ppm (300 mg/m3)	1990	(Karlberg & Lindell, 1993)
Finland	25 ppm (140 mg/m3)	50 ppm (280 mg/m3)	not known	(Finnish Institute of Occupational Health, 2001)
AIHA	30 ppm (165.6 mg/m3)	-	1993	(AIHA, 1993)

OEL = Occupational exposure limit

STEL = short-term (15-min) exposure limit

TWA = time-weighted average

In Germany no MAK (maximum workplace concentration) has been set for limonene as it was considered that insufficient information was available. However all isomers have been listed as skin sensitisers (Deutsche Forschungsgemeinschaft, 2000).

14.3.4Health surveillance

In accordance with NOHSC National Model Regulations for the Control of Workplace Hazardous Substances (NOHSC, 1994b), employers have to provide health surveillance in those workplaces where the workplace assessment indicates that exposure to a hazardous substance may lead to an identifiable substance-related disease or adverse health effect. Limonene is not listed in Schedule 3 (list of substances requiring health surveillance) and as such there are no formal requirements for health surveillance programs for exposed workers.

No occupational health surveillance was reported for limonene in Australia.

14.3.5Australian Code for the Transport of Dangerous Goods by Road and Rail

Under the ADG Code (FORS, 1998), limonene (dipentene) (UN Number 2052) is classified in Class 3, Packing Group III. Class 3 contains principally flammable liquids. Limonene is assigned Packing Group III (because of its high flash point), indicating that it is of lower hazard than most other flammable liquids. Packing Groups are assigned according to the degree of risk the goods present in transport. Packing Group III indicates minor danger.

The d- and l- isomers are not mentioned specifically under UN Number 2052. As the physico-chemical properties and flammability hazard of the isomers would be similar to the racemic mixture, this number could also be used for d- and l- limonene. An alternative classification used by several companies is the generic category Terpene Hydrocarbons N.O.S., which is identified as UN Number 2319, and has the same class, Packing Group and Hazchem Code as limonene/dipentene.

The ADG Code sets out various requirements relating to the packaging, labelling and transport of limonene by road or rail.

Bulk loads must be placarded with Class label 3 (‘flammable liquid’) and an emergency information panel containing additional information such as the Proper Shipping Name of the dangerous goods (‘dipentene’), its UN Number, Hazchem Code and the name and telephone number for specialised advice. The Hazchem Code for bulk loads of limonene is 3[Y]. The code reflects the initial emergency response recommended in case of fire, leakage or spillage. The number ‘3’ indicates that foam should be used for firefighting. The letter ‘[Y]’ means that there is a risk of violent reaction or explosion; that emergency personnel should wear a breathing apparatus a fire situation; and that any spillage should be contained so as to prevent the chemical from entering drains or water courses.

Additional information used in transport includes Emergency Procedure Guides (EPG) for individual dangerous goods, or the generic Standards Australia “Dangerous Goods – Initial Emergency Response Guide” (SAA/SNZ, 1997), also known as Handbook 76 or HB76. In this document, transporters of UN 2052 and UN 2319 are directed to guides 14 (Liquids – Highly Flammable) and 15 (Liquids – Flammable) respectively.

Under the ADG Code, controls on the transport of smaller quantities of limonene and limonene products within Australia are based primarily on package and labelling requirements.

14.3.6Storage and handling

The NOHSC National Standard for the Storage and Handling of Workplace Dangerous Goods (NOHSC, 2001) and National Code of Practice for the Storage and Handling of Workplace Dangerous Goods (NOHSC, 2001a) form a performance-based foundation for a national framework of control, incorporating the principles of hazard identification, risk assessment and risk control. Implementation of the standard will be via States and Territories.

Existing State and Territory arrangements include requirements in NSW for licensing in that State of premises holding dangerous goods above certain threshold quantities. Information in the Stored Chemicals Information Database (SCID) is used to inform emergency services staff such as fire fighters.

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