Short distribution chains for HF Example 1: Cleaner/etchant for preparation of aluminium for powder coating Company 1 - imports 55% HF in bulk for resale. Company 2 - buys 55% HF and uses to formulate a product for resale. Company 3 - (metal processor) purchases and uses product for own use. Example 2: Laboratory reagent. Company 1 - imports 50% HF packed in 500 mL or 2.5 L bottles for resale. Company 2 - buys packed product for resale. Company 3 - (laboratory) purchases and uses product for own use. Long distribution chains for HF Example 1: Rust remover for drycleaning industry: Company 1 - imports 70% HF and dilutes to 10% Company 2 - buys 10% HF in 200 L drums, adds extra ingredients to formulate, then packs into 500mL bottles and labels product, of brand name A. Company 3 - buys bottles of product A and relabels as product B for resale. Company 4 - buys product B for resale. Company 5 - (drycleaner) buys product B for own use Example 2: Mag wheel cleaner for car detailing Company 1 - imports 70% HF for resale. Company 2 - buys 70% HF and formulates 4% HF mag wheel cleaner for resale in 200 L drums Company 3 - purchases, repacks and labels mag wheel cleaner into 5 L and 20 L drums for resale. Company 4 - purchases these packs for resale. Company 5 - (car detailer) purchases for own use. Unusual methods of supply of HF Example 1 Supply for use on ships Company 1- imports 35% HF for resale. Company 2 - formulates a metal treatment product with 10% HF and packs into 25 L drums for resale. Company 3 - purchases product for supply to ships, but does not take delivery of it, directing Company 2 to deliver to Company 4. Company 4 - takes delivery of product and forwards to ships, but is not aware of details of the product, as they are not the purchaser. NICNAS was unable to contact the final user of the product. Example 2: Supply via contract or tender to large institutional users.
Formulated products – Suppliers should advise formulators of the hazards of HF and appropriate recommend alternatives. Formulators of products of > 10% strength should be encouraged to themselves become signatories to the Code. Formulations of > 10% strength should not be sold to the general public. Formulations should not be designed to be atomised, sprayed or heated except under strictly controlled conditions, and the design of the pack should facilitate safe dispensing. Threaded valves are recommended for packs over 5 L. Labels should state the exact percentage of hydrofluoric acid. Education and training – Signatories should provide their staff with comprehensive training on all aspects of hydrofluoric acid, including precautions, legal requirements and the obligations of the Code. Records of training should be kept for 5 years. Reporting of incidents – Signatories and other parties are encouraged to report in writing to PACIA all incidents involving hydrofluoric acid and a sample incident report form is provided. This information is to be circulated to signatories. The organisation representing scientific suppliers, Science Industry Australia, is a signatory to the Code and encourages its members to abide by the principles as detailed in the Code. PACIA were asked to supply information for this assessment on the take-up of the Code of Practice and experience with various aspects. They were not able to provide any information, except that incident reports for HF had not been received. Two respondents to the HF survey reported that they voluntarily restricted the concentration of HF products they were prepared to sell and others would sell only dilute concentrations to purchasers they did not know. It was found to be difficult to do this without the support of regulatory controls, especially when it was known that competitors would supply the higher percentage. Other examples of product stewardship reported by survey respondents include: Inspection of customer premises; verbal and written advice on hazard; supply of first aid products or advice on obtaining them; supply of gloves to customers; laminated aid card provided; product delivered by hand; and consultations with technical staff available.
HF concentration Conditions of exposure Area of body Treatment Effect Reference Dermal: 100% During laboratory synthesis of fluoroborate salt, connecting tube burst, and HF spilt on technician. Estimated exposure was 5 g HF and 2.5% BSA, including the right side of face, neck and forearm. Patient was treated on the spot, and taken to hospital where burns were treated with calcium gluconate Second and third degree burns were eventually treated by plastic surgery. In addition to these, renal abnormalities, severe nausea and stupor in the first days after exposure appeared to be due to systemic effects of fluoride. Burke et al., 1973. 100% 49-year old male exposed to HF in industrial accident. Approx. 5% BSA affected, primarily the lower abdomen and right thigh. Patient to hospital and calcium gluconate injected into subcutaneous tissue beneath the wound. The wound was excised, and later grafted. Burns caused a deep wound. Patient survived and recovered well. Sheridan et al., 1995. 100% 37-year old exposed to HF in workplace accident. 25% BSA exposure, primarily upper arms and torso. Patient was showered in workplace and treated in hospital emergency room with topical calcium gluconate gel. Transferred to another hospital where calcium and magnesium were replaced during cardiac arrest. At first emergency room patient was noted to have conjunctival injection and mild respiratory distress, but was otherwise alert and stable. On arrival at second hospital he was hypotensive and in severe respiratory distress. Then he suffered cardiac arrest and could not be resuscitated. Sheridan et al., 1995.
Health Effects of Dermal/Ocular Exposure To HF Case reports of dermal/ocular exposure to HF (continued) HF concentration Conditions of exposure Area of body Treatment Effect Reference Dermal (cont.): 15% HF 7.5% H2SO4 Cleaned aluminium and stainless steel strips on van without gloves for 1½ h, and for a further ½ h with food grade gloves. Fingers and both hands. Exact details not given. It is likely that hands were washed with water at time injury noticed, and that hospital treatment involved calcium gluconate. Stinging sensation at end of fingers was noticed after 1½ h and progressed to feeling that hands were on fire. Skin discoloured to reddish-brown. Treatment sought at hospital and was required every 2 d for 3 months. Worker had difficulty carrying out normal occupation as bricklayer. Queensland. Department of Employment, Training and Industrial Relations 1999. 15% Technician cleaning oxidation from silver soldering on a copper component was exposed through pinhole in rubber glove. Cotton liners underneath held the solution in contact with skin. Solution used for 1 h. Fingers and hand. Only normal washing carried out at completion of task. Burn not detected until 8 h after task completed. Treatment commenced 24 h after exposure, and calcium gluconate later injected into burned area. Burning sensation and whitening of skin occurred 8 h exposure. Pain increased over the next day. Three months after exposure, hand was still swollen and had reduced use and dexterity of fingers. Seven months after exposure, dexterity had returned but some swelling remained. Minor scarring remained. Stencil & Tobin, 1987. 12% 27-year old male worked with HF for several hours without gloves Fingers and hands. Treatment was sought on 3 occasions, and fingernails were removed on third visit. Magnesium compound soaks and dressings were continued for 3 d. Initial symptom was pain only, in both hands but concentrated in fingertips. Approx 14 h after exposure, the hands were painful, edematous and erythematous. Symptoms resolved by 2 weeks after exposure. Jordan, 1982
Health Effects of Dermal/Ocular Exposure To HF Case reports of dermal/ocular exposure to HF (continued) HF concentration Conditions of exposure Area of body Treatment Effect Reference Dermal (cont.): 10% HF solution used to clean heavy equipment, splashed on gloves and forearm of worker who was filling a garden sprayer with it. Hand and forearm (assumed). Treatment sought on the evening of the exposure because of pain. Hand and forearm started to ache on evening of exposure, and pain intensified. Tissue and bones of hand had been damaged, and part of hand was amputated. Oregon OSHA, 1999. 10% HF spilt on fingers from stopper of bottle, while removing rust stains from sweaters. Fingers. Not known when HF rinsed from skin. Calcium gluconate treatment started after 4 days. 1 h after use, fingers became red and swollen, and later marble-white. The pain became increasingly severe overnight and for several days until treatment. Complete healing occurred after 1 month, with slight scar formation. Klauder et al., 1955. 10% Leaking stain remover spilt on fingers and not washed off. Fingers. Symptoms occurred several hours later and were treated at hospital by subcutaneous injection of calcium gluconate, followed by calcium gluconate gel. Fingers were sore and blistered the next day but there were no ongoing problems with the hand. Orica, 1999. 10% Carpet cleaner used product without gloves for short time, and did not wash off. Fingers. Symptoms occurred several hours later and were treated at hospital with calcium gluconate gel for 24 h. No blisters developed. Orica, 1999.
Health Effects of Dermal/Ocular Exposure To HF Case reports of dermal/ocular exposure to HF (continued) HF concentration Conditions of exposure Area of body Treatment Effect Reference Dermal (cont.): 4.2% HF 7% H2SO4 Employee of used car lot cleaned car wheels for 6 h without PPE. Hands. Calcium gluconate gel not available at workplace. No further details of treatment. Chemical burns to hands. No further details provided. WorkSafe Western Australia, 4% HF 20% H2SO4 Man (26 y) exposed while using cleaning solution. Right hand, primarily fingers. Initially treated with analgesic at clinic and at hospital 5 h with intravenous and topical calcium gluconate, and later Bier block. Fingernails removed. Used solution for 2 h before tingling occurred, progressed to severe pain over 1 h. Treatment did not resolve pain and intramuscular analgesic needed for 72 h. Discharged from hospital after 5 days. Isbister, 2000. 10% ammonium bifluoride and 27.5% phosphoric acid (H3PO4) Exposed when used solution to clean aluminium window frames for 4-5 h without gloves. Fingers. Treatment with diuretics and prednisone tablets commenced 24 h after exposure. Fingers began to tingle 2 h after exposure started. They became painful that evening, with swelling during the night. Gross oedema and reduced sensation of the fingers, which disappeared within 4 d, were noted after 24 h, but no skin lesions. Some nails were lost after 4-6 weeks, but re-grew normally. Pedersen, 1980. 2% 63-year old man used metal cleaner with a cloth, and without gloves. Hands. Treatment probably sought approx. 20 h exposure, and involved application of calcium gluconate gel dressings every 2 h. One hour after exposure, patient developed a burning sensation in his palms, and associated deep bone pain, which intensified over the next 20 h. Treatment resolved symptoms rapidly. Smith, 1992.