Tag: Cancer

Epichlorohydrin – Guide to Hazardous Air Pollutants used by the Irish Air Corps

Epichlorohydrin
(1-Chloro-2,3-Epoxypropane)

CAS  106-89-8

Hazard Summary

Epichlorohydrin is mainly used in the production of epoxy resins.  Acute (short-term) inhalation exposure to epichlorohydrin in the workplace has caused irritation to the eyes, respiratory tract, and skin of workers.

At high levels of exposure, nausea, vomiting, cough, labored breathing, inflammation of the lung, pulmonary edema, and renal lesions may be observed in humans.

Chronic (long-term) occupational exposure of humans to epichlorohydrin in air is associated with high levels of respiratory tract illness and hematological effects.

Damage to the nasal passages, respiratory tract and kidneys have been observed in rodents exposed to epichlorohydrin by inhalation for acute or chronic duration.  An increased incidence of tumors of the nasal cavity has been observed in rats exposed by inhalation. EPA has classified epichlorohydrin as a Group B2, probable human carcinogen.

Please Note: The main sources of information for this fact sheet are EPA's IRIS (2), which contains information on inhalation chronic toxicity and carcinogenic effects of epichlorohydrin and the RfC, and unit cancer risk estimate for inhalation exposure, and the Health and Environmental Effects Profile for Epichlorohydrin. (1)

Uses

  • The primary use of epichlorohydrin is in the production of epoxy resins used in coatings, adhesives, and plastics. (1,5)
  • Epichlorohydrin is also used in the manufacture of synthetic glycerine, textiles, paper, inks and dyes, solvents, surfactants, and pharmaceuticals. (1)
  • Epichlorohydrin is also listed as an inert ingredient in commercial pesticides. (1)

Sources and Potential Exposure

  • Individuals are most likely to be exposed to epichlorohydrin in the workplace. (1)
  • Epichlorohydrin may be released to the ambient air during its production and use. (1)
  • Accidental releases to waterways may expose the general public to epichlorohydrin. (1)

Assessing Personal Exposure

  • No information was located concerning the measurement of personal exposure to epichlorohydrin.

Health Hazard Information

Acute Effects:

  • Acute inhalation exposure to epichlorohydrin in the workplace has caused irritation to the eyes, respiratory tract, and skin of workers.  At high levels of exposure, nausea, vomiting, cough, labored breathing, chemical pneumonitis (inflammation of the lung), pulmonary edema, and renal lesions may be observed in humans. (1,2)
  • Dermal contact with epichlorohydrin may result in irritation and burns of the skin in humans and animals.(1)
  • In rats and mice acutely exposed to epichlorohydrin by inhalation, nasal and lower respiratory tract irritation and lesions, hemorrhage, and severe edema have been observed.  Renal degeneration and CNS depression with paralysis of respiration and cardiac arrest have also resulted from acute inhalation exposure in animals. (1-3)
  • Tests involving acute exposure of rats, mice and rabbits have demonstrated epichlorohydrin to have high acute toxicity from inhalation, oral, and dermal exposure. (4)

Chronic Effects (Noncancer):

  • Chronic occupational exposure of humans to epichlorohydrin in air is associated with high levels of respiratory tract illness and hematological effects (decreased hemoglobin concentration and decreased erythrocyte and leukocyte counts). (1,5)
  • Chronic inhalation exposure has been observed to cause pulmonary effects including inflammation and degenerative changes in the nasal epithelia, severe lung congestion, and pneumonia in rats and mice. Effects to the kidneys were also observed. (1,2)
  • Hepatic damage, hematological effects, myocardial changes, and damage to the CNS have been reported in chronically exposed rats. (1,5)
  • The Reference Concentration (RfC) for epichlorohydrin is 0.001 milligrams per cubic meter (mg/m3) basedon changes in the nasal turbinates in rats and mice. The RfC is an estimate (with uncertainty spanningperhaps an order of magnitude) of a continuous inhalation exposure to the human population (including sensitive subgroups), that is likely to be without appreciable risk of deleterious noncancer effects during a lifetime. It is not a direct estimator of risk but rather a reference point to gauge the potential effects. At exposures increasingly greater than the RfC, the potential for adverse health effects increases. Lifetime exposure above the RfC does not imply that an adverse health effect would necessarily occur. (2)
  • EPA has medium confidence in the study on which the RfC was based because of the inflammation in the respiratory tract of control and exposed animals although it was well conducted and contained detailed histopathological examinations of numerous tissues including the respiratory tract; medium confidence in the database because chronic studies that adequately address the respiratory system and a two-generation reproductive study are lacking and the only chronic inhalation study is confounded by severe nasal inflammation in the controls; and, consequently, medium confidence in the RfC. (2)
  • The provisional Reference Dose (RfD) for epichlorohydrin is 0.002 milligrams per kilogram body weight per day (mg/kg/d) based on kidney effects in rats. The provisional RfD is a value that has had some form of Agency review, but it does not appear on IRIS (6)

Reproductive/Developmental Effects:

  • In humans occupationally exposed to epichlorohydrin, effects on sperm counts, hormone levels, and fertility have been not detected. (1,2)
  • Epichlorohydrin has been demonstrated to reduce fertility in male rats when inhaled or administered orally.(1-3)
  • Teratogenic effects (birth defects) have not been observed in studies of rodents exposed by inhalation or ingestion. (1,2,5)

Cancer Risk:

  • An increased incidence of lung cancer mortality (not statistically significant) was reported in one study of workers exposed to epichlorohydrin. (1,2)
  • An increased incidence of tumors of the nasal cavity has been observed in rats exposed to epichlorohydrin by inhalation. (1,2,5)
  • An increased incidence of forestomach tumors has been reported in rats exposed via gavage (experimentally placing the chemical in the stomach) and in drinking water.  Mice have exhibited local tumors when exposed by subcutaneous injection. (1-3,5)
  • EPA has classified epichlorohydrin as a Group B2, probable human carcinogen. (2)
  • EPA uses mathematical models, based on human and animal studies, to estimate the probability of a EPA uses mathematical models, based on human and animal studies, to estimate the probability of a person developing cancer from breathing air containing a specified concentration of a chemical. EPA calculated an inhalation unit risk estimate of 1.2 × 10-6  (µg/m3)-1. EPA estimates that, if an individual were to continuously breathe air containing epichlorohydrin at an average of 0.8 µg/m3 (0.0008 mg/m3) over hisor her entire lifetime, that person would theoretically have no more than a one-in-a-million increasedchance of developing cancer as a direct result of breathing air containing this chemical. Similarly, EPA estimates that breathing air containing 8.0 µg/m3 (0.008 mg/m3) would result in not greater than a one in-a-hundred thousand increased chance of developing cancer, and air containing 80.0 µg/m3 (0.08mg/m3) would result in not greater than a one-in-ten thousand increased chance of developing cancer. Fora detailed discussion of confidence in the potency estimates, please see IRIS. (2)
  • EPA has calculated an oral cancer slope factor of 9.9 x 10-3 (mg/kg/d)-1. (2)

Physical Properties

  • The chemical formula for epichlorohydrin is C3H5OCl, and its molecular weight is 92.53 g/mol. (1,7)
  • Epichlorohydrin is a volatile and flammable clear liquid at room temperature and is insoluble in water.(1,2,7)
  • The threshold for odor perception of epichlorohydrin is 0.93 parts per million (ppm). Epichlorohydrin has a pungent, garlicky, sweet odor. (2,8) The vapor pressure for epichlorohydrin is 22 mm Hg at 30 °C. (1)

Read the full EPA (USA) PDF on the above Hazardous Air Pollutant with references below.

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Relavance to personnel who served in the Air Corps

  • Epichlorohydrin is a component of PR1829b windshield canopy sealant.

There are possibly more chemicals used by the Air Corps that contain Epichlorohydrin. If you know of some let us know in the comments section. 

Dichloromethane – Guide to Hazardous Air Pollutants used by the Irish Air Corps

Methylene Chloride (Dichloromethane)

Above is a photgraph taken in Irish Air Corps in 2015 of a drum of Dichloromethane. This was in use by the spray paint shop in Baldonnel for stripping paint but was handed out to staff from any other unit that wanted some in containers like soft drinks bottles or milk cartons.

Note : The European Union had banned this chemical 3 years earlier in 2015. The current Health & Safety officer in Baldonnel didn’t know Dichlorometheane had been banned and in fact didn’t even know Dichlorometheane was actually in use as no chemical register was in existance at the time despite being mandatory since 1989.

This was prior to the Irish Air Corps becoming LEADERS in workplace chemical Healh & Safety as “self-declared” recently to the Oireachtas Joint Committee on Foreign Affairs and Trade, and Defence.

CAS  75-09-2

Hazard Summary

Methylene chloride is predominantly used as a solvent. The acute (short-term) effects of methylene chloride inhalation in humans consist mainly of nervous system effects including decreased visual, auditory, and motor functions, but these effects are reversible once exposure ceases.

The effects of chronic (long-term) exposure to methylene chloride suggest that the central nervous system (CNS) is a potential target in humans and animals.

Human data are inconclusive regarding methylene chloride and cancer. Animal studies have shown increases in liver and lung cancer and benign mammary gland tumors following the inhalation of methylene chloride.

Please Note: The main sources of information for this fact sheet are the Agency for Toxic Substances and Disease Registry's (ATSDR's) Toxicological Profile for Methylene Chloride and EPA's Integrated Risk Information System (IRIS), which contains information on oral chronic toxicity and the RfD, and the carcinogenic effects of methylene chloride including the unit cancer risk for inhalation exposure

Uses

  • Methylene chloride is predominantly used as a solvent in paint strippers and removers; as a process solvent in the manufacture of drugs, pharmaceuticals, and film coatings; as a metal cleaning and finishing solvent in electronics manufacturing; and as an agent in urethane foam blowing. (1)
  • Methylene chloride is also used as a propellant in aerosols for products such as paints, automotive products, and insect sprays. (1)
  • It is used as an extraction solvent for spice oleoresins, hops, and for the removal of caffeine from coffee. However, due to concern over residual solvent, most decaffeinators no longer use methylene chloride. (1)
  • Methylene chloride is also approved for use as a postharvest fumigant for grains and strawberries and as a degreening agent for citrus fruit. (1)

Sources and Potential Exposure

  • The principal route of human exposure to methylene chloride is inhalation of ambient air. (1)
  • Occupational and consumer exposure to methylene chloride in indoor air may be much higher, especially from spray painting or other aerosol uses. People who work in these places can breathe in the chemical or it may come in contact with the skin. (1)
  • Methylene chloride has been detected in both surface water and groundwater samples taken at hazardous waste sites and in drinking water at very low concentrations. (1)

Assessing Personal Exposure

  • Several tests exist for determining exposure to methylene chloride. These tests include measurement of methylene chloride in the breath, blood, and urine. It is noted that smoking and exposure to other chemicals may affect the results of these tests. (1)

Health Hazard Information

Acute Effects:

  • Case studies of methylene chloride poisoning during paint stripping operations have demonstrated that inhalation exposure to extremely high levels can be fatal to humans. (1,2)
  • Acute inhalation exposure to high levels of methylene chloride in humans has resulted in effects on the central nervous system (CNS) including decreased visual, auditory, and psychomotor functions, but these effects are reversible once exposure ceases. Methylene chloride also irritates the nose and throat at high concentrations. (1,2)
  • Tests involving acute exposure of animals have shown methylene chloride to have moderate acute toxicity from oral and inhalation exposure. (3)

Chronic Effects (Noncancer):

  • The major effects from chronic inhalation exposure to methylene chloride in humans are effects on the CNS, such as headaches, dizziness, nausea, and memory loss. (1,2)
  • Animal studies indicate that the inhalation of methylene chloride causes effects on the liver, kidney, CNS, and cardiovascular system. (1,2)
  • EPA has calculated a provisional Reference Concentration (RfC) of 3 milligrams per cubic meter (mg/m3) based on liver effects in rats. The RfC is an estimate (with uncertainty spanning perhaps an order of
    magnitude) of a continuous inhalation exposure to the human population (including sensitive subgroups) that is likely to be without appreciable risk of deleterious noncancer effects during a lifetime. It is not a direct estimator of risk but rather a reference point to gauge the potential effects. At exposures increasingly greater than the RfC, the potential for adverse health effects increases. Lifetime exposure above the RfC does not imply that an adverse health effect would necessarily occur. (5)
  • The Reference Dose (RfD) for methylene chloride is 0.06 milligrams per kilogram body weight per day (mg/kg/d) based on liver toxicity in rats. (4)
  • EPA has medium confidence in the RfD based on: high confidence in the study on which the RfD is based because a large number of animals of both sexes were tested in four dose groups, with a large number of controls, many effects were monitored, and a dose-related increase in severity was observed; and medium to low confidence in the database because only a few studies support the no-observed-adverse-effect level (NOAEL). (4)

Reproductive/Developmental Effects:

  • No studies were located regarding developmental or reproductive effects in humans from inhalation or oral exposure. (1,2)
  • Animal studies have demonstrated that methylene chloride crosses the placental barrier, and minor skeletal variations and lowered fetal body weights have been noted. (1,2)

Cancer Risk:

  • Several studies did not report a statistically significant increase in deaths from cancer among workers exposed to methylene chloride. (1,2)
  • Animal studies have shown an increase in liver and lung cancer and benign mammary gland tumors following inhalation exposure to methylene chloride. (1,2,4)
  • EPA considers methylene chloride to be a probable human carcinogen and has ranked it in EPA’s Group B2.(4)
  • EPA uses mathematical models, based on animal studies, to estimate the probability of a person developing cancer from breathing air containing a specified concentration of a chemical. EPA calculated an inhalation unit risk estimate of 4.7 × 10-7 (µg/m3)-1. EPA estimates that, if an individual were to continuously breathe air containing methylene chloride at an average of 2.0 µg/m3 (0.002 mg/m3) over his or her entire lifetime, that person would theoretically have no more than a one-in-a-million increased chance of developing cancer as a direct result of breathing air containing this chemical. Similarly, EPA estimates that breathing air containing 20 µg/m3 (0.02 mg/m3 ) would result in not greater than a one-in-a-hundred
    breathing air containing 20 µg/m3 (0.02 mg/m3) would result in not greater than a one-in-a-hundred thousand increased chance of developing cancer, and air containing 200 µg/m3(0.2 mg/m3) would result in not greater than a one-in-ten thousand increased chance of developing cancer. For a detailed discussionof confidence in the potency estimates, please see IRIS. (4)
  • Note the MAX mathamatical/theoretical EPA level above of 200 µg/m3(0.2 mg/m3) equates to 0.05758ppm (parts per million). Dichloromethane was measured in ERF on Wednesday 12th & Thursday 13th July, 1995 at 175ppm. This equates to 607,880 µg/m3(607.88 mg/m3). So the level the EPA use to calculate a one-in-a hundred thousand increased chance of developing cancer were exceeded by the Irish Air Corps by a factor of 3,039. So statistically if a person inhalled the levels that many Irish Air Corps were exposed to 24/7 for a lifetime they would have a 1 in 33 chance of developing cancer as a result.
  • EPA calculated an oral cancer slope factor of 7.5 x 10-3 (mg/kg/d)-1. (4)

Physical Properties

  • A common synonym for methylene chloride is dichloromethane. (1,4)
    Methylene chloride is a colorless liquid with a sweetish odor. (1,6)
    The chemical formula for methylene chloride is CH2Cl2, and the molecular weight is 84.93 g/mol. (1)
  • The vapor pressure for methylene chloride is 349 mm Hg at 20 °C, and it has an octanol/water coefficient (log Kow) of 1.30. (1)
  • Methylene chloride has an odor threshold of 250 parts per million (ppm). (7)
  • Methylene chloride is slightly soluble in water and is nonflammable. (1,6)

Read the full EPA PDF on the above Hazardous Air Pollutant with references below.

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Relavance to personnel who served in the Air Corps

  1. Dichloromethane was a  component of Ardrox 666 used in ERF.
  2. Dichloromethane was a component of the Paint Remover 82510 used by the Spray Paint Shop but also by technicians in No3 Sp Wing, BFTS & possibly elsewhere.

There are possibly more chemicals used by the Air Corps that contain Dichloromethane. If you know of some let us know in the comments section. We are not statisticians and our interpretation of the cancer statistics are open to correction.

Solvent exposure and Parkinson’s disease

Shaun Wood worked was a painter and finisher  at Royal Air Force (RAF) bases across the world. During the early 1990s he was involved in the very intensive work preparing Tornado aircraft for the first Gulf War, in particular gluing anti-missile patches to the aircraft. This work was often done in confined spaces over long working hours.  He generally wore a respirator but these were not really adequate for the circumstances.

German Tornado Undergoing Maintenance

Shaun has been diagnosed with Multiple System Atrophy (MSA), which is a debilitating Parkinsonian syndrome that affects the nervous system. He is just 53 years of age.

Throughout his work Shaun was exposed to various solvents, but primarily trichloroethylene and dichloromethane. There is not a great deal of information about exposure to these solvents in aircraft maintenance. I have seen results from a survey carried out at an RAF base in Scotland where dichloromethane levels were measured during paint striping in the cockpit area of a Nimrod aircraft. There was only 1.5 m2 of paint removed, but the peak air concentrations were about 700 mg/m3. Results from three monitoring surveys where the British Health and Safety Executive sampled for dichloromethane during paint stripping on aircraft are shown in the following figure. The mean levels measured in each of these surveys were: 330, 790 and 1,960 mg/m3, and the highest individual level measured was 3,590 mg/m3.

Read full article on OH-world.org A blog about exposure science and occupational hygiene

http://johncherrie.blogspot.ie/2011/12/solvent-exposure-and-parkinsons-disease.html

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Below is a photo of one of the locations in the Irish Air Corps that used Dichloromethane, namely the NDT Shop of Engine Repair Flight. Yes that is a stream of the chemicals dripping out of the extractor fan and running down the wall. And yes that is dichloromethane, cresylic acid and the hexavalent sodium chromate all over the floor. The small barrel that is being dissolved by its contents contains Hydrofluoric Acid.

Some extracts from the Ambient Air Monitoring For Health and Safety at Work report dated 2nd August 1995

  1. Dichloromethane levels were measured in the engine shop in Wednesday the 12th and Thursday the 13th of July 1995 at the behest of Captain John Maloney who is still serving in the Irish Air Corps
  2. The level of dichloromethane found in ambient air in the engine
    cleaning area exceeded health and safety limits. 
  3. Levels of Dichloromethane were measured at 175.9ppm (622.5 mg/m3)  while the TWA health & safety limit for this chemical in 1995 was 50ppm.
  4. Significant levels of all parameters monitored were found in nearly all ambient air samples taken in the engine cleaning area.
  5. The ventilation in all areas monitored was deemed to be insufficient. It is thus recommended that mechanical heating and ventilation systems be adapted designed and installed in all areas monitored.

To summarise, the Irish Army Air Corps knew that Dichloromethane levels in the NDT shop in 1995 exceeded health & safety limits by 3.5 times yet officer management…

  1. LEFT personnel of all ranks and none to rot in this exceptionally toxic working environment for a further 12 years.
  2. IGNORED the recommendation to design and install design a proper ventilation system, (they stuck in 2 x Xpelairs).
  3. NEVER re-tested the environment to see if the Xpelair fans worked, we suspect they made things worse by increasing evaporation rate.
  4. NEVER informed personnel of enlisted ranks that their workplace was contaminated to dangerous levels.

DELAY – DENY – DIE

‘Cancer cluster’ fury: The ‘red zone’ residents ‘being left to rot and die’

ALONG one stretch of road, 50 people have been diagnosed with cancer. The people of this Australian town had enough of being told there’s nothing wrong.

THE people of Williamtown know that 50 residents living on one stretch of rural road have been diagnosed with cancer.

They want the Government to admit it. And to fix the problem now.

The fury of those living in the “red zone” of toxic contamination near the RAAF base in the NSW township of Williamtown, near Newcastle, is palpable.

After years of drinking the water, washing in it, cooking in it, they were finally told in 2015 it was contaminated. They are out of patience, and want answers.

And their anger has only been further inflamed by a NSW Health report saying there’s no evidence of a cancer cluster caused by contamination which the Department of Defence allegedly hid from them for three years.

The report dismissing their concerns has left them devastated.

Read more on news.com.au

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This article may be of relevance to Air Corps fire fighting personnel who used AFFF in the past. The Air Corps as usual will not admit whether they used poly-fluoroalkyl substances. In well regulated workplace environments exposure should be minimal but in the Air Corps there was no regulation nor health & safety training for the handling of fire fighting foam.

However as with the Air Corps toxic chemical scandal the Australian DoD is trying to downplay the effects of dangerous chemicals just like Dr. Leo Varadkar did in the Dáil on the 7th of February.

Read information sheet on firefighting foam from the Australian Department of Defence

DELAY – DENY – DIE

Leo Varadkar urged to act on Air Corps chemical exposure ‘legacy’

Taoiseach Leo Varadkar has said he believes the courts should decide whether former Air Corps staff are suffering chronic illnesses due to chemical exposure.

Mr Varadkar made the comments yesterday in the Dáil where Sinn Féin Defence Spokesperson Aengus O’Snodaigh repeated calls for a health study of Air Corps members, similar to an analysis of Australian Air Force staff, which found technicians who worked with carcinogenic chemicals were at greater risk of illness.

Last year, the Irish Examiner revealed the State is facing a number of claims from former staff, and that whistleblowers had raised concerns about the safety of workers using chemicals at Casement Aerodrome, Baldonnel.

“While I have absolutely no doubt that the serious ill-health suffered by some former members of the Air Corps is real, it has not been proven whether this array of illnesses could be caused by chemical exposure,” Mr Varadkar said.

“There is litigation in the courts, which are the best place to assess the evidence and see whether the allegations are supported by that evidence,” he said.

Mr O’Snodaigh said a survey is needed as the implications of widespread staff exposure to the chemicals used goes beyond the seven cases currently against the State. “We do not want to be here in 10 years’ time with a higher death toll, having failed to address this scandal,”he said.

Read full article on Irish Examiner website below…

Delay – Deny – Die

The vast majority of Irish Air Corps Chemical Abuse Survivors are not currently engaged in legal action. For these serving and former personnel the Taoiseach is offering them no respite, not assistance and no hope.

Brendan Howlin: Review Air Corps health claims

Labour leader Brendan Howlin is not satisfied with the Government’s response to the Air Corps chemical exposure scandal, and has called for an external review of the allegations.

In the absence of military or government statistics on untimely deaths in the Irish Air Corps we created our own. We are happy to have these tested or even proven wrong by better statistics gathered by the state in a comprehensive, open and transparent manner. #WeAreNotStatisticians

The State is facing seven High Court claims from former Air Corps technicians, who say they suffer chronic illnesses due to exposure to toxic chemicals while they were cleaning and servicing aircraft.

A number of whistleblowers have made protected disclosures about working conditions in Air Corps headquarters at Casement Aerodrome. The Health and Safety Authority subsequently investigated, and threatened legal action, unless the Defence Forces improved worker safety.

Mr Howlin raised the issue in the Dáil last month, and has since received correspondence from the Government.

“I’ve raised it with the Taoiseach directly and I’ve gotten a two-page response from the minister with responsibility for defence, and I’m not satisfied,” Mr Howlin said. “There needs to be at least an expert-review panel set up to look into this in some detail.”

However, Mr Howlin did not call for a full commission of investigation, but said that the findings of an external review should determine whether such a process is necessary.

“Whether a full tribunal of investigation is required remains to be seen, but the first step to that is to have an external, expert review, and that needs to happen immediately, and I certainly will be pressing for that,” he said.

This review should include a health study of Air Corps members past and present to determine if they have a higher prevalence of chronic conditions compared to the general public, he said.

“That would have to be a critical part of the review, because, once the fears are there, they have to be empirically checked out,” Mr Howlin said.

“They are either fact or not fact. There’s no point in people either dismissing them, or saying it’s a fact. We need to have external, independent, authoritative decisions on these matters.”

Read full article on Irish Examiner website below…

Delay – Deny – Die

 

Hexamethylene Diisocyanate – Just one of the toxic chemicals the Irish Air Corps and State Claims Agency want to hide from former personnel!

  1. Exposure can occur when isocyanates are curing or when cured isocyanates are heated.
  2. An individual’s response to isocyanate exposure can be immediate or may be DELAYED FOR SEVERAL YEARS.
  3. Skin exposure can also cause respiratory sensitisation.
  4. The odour threshold for isocyanates, i.e. the level at which an individual can smell an isocyanate, is typically higher than the allowed exposure limits.
  5. The Air Corps did eventually provide a “supplied air” respirator to spray paint & welding personnel. Unfortunately they sourced the “supplied air” from an old machine compressor located in ERF where the air had previously tested as 3.5 times over the allowed limit for Dichloromethane i.e. allowed limit was 50ppm and sourced air was from a location measured at 175ppm…out of the frying pan and into the fire.

Air Corps Hexamethylene Diisocyanate Usage

Hexamethylene Diisocyanates were a chemical component of polyurethane paint hardener used by the Spray Paint Shop (Dope Shop) at Baldonnel. For most of the existence of this shop personnel were NOT supplied with ANY PPE. The walls between the Spray Paint Shop and Engineering Wing Hangar & Workshops were not sealed and so Hexamethylene Diisocyanate and other chemicals entered these workplaces whilst spraying was in progress exposing all personnel.

Furthermore if a component could not be removed from an aircraft for spray painting it was spray painted in-situ in Engineering Wing Hangar whilst unprotected line & tech personnel worked in adjoining offices & workshops or on other aircraft in the hangar.

Visiting personnel to Engineering Wing hangar such as BFTS personnel doing an IRAN, Heli personnel doing an overhaul & even Military Police on a walkabout were also exposed.

A “waterfall” system with an extractor fan was also present. Personnel spray painted aircraft components toward the waterfall which captured most of the over-spray droplets. Fumes from this waterfall were then extracted by a fan, up a duct and released at approximately 3m height where the prevailing winds then carried the extracted fumes in the doors & windows of : 

  • 5th Maintenance Engineers
  • Air Corps Apprentice School
  • Avionics Squadron
  • BFW Stores
  • Engine Repair Flight
  • Old Tech Stores
  • Training Wing HQ Prefab
  • Parachute Shop

5-20% of people are prone to isocyanate sensitisation. and isocyanate cross sensitisation is a recognised phenomenon. Sensitisation is irreversible and unfortunately once sensitised it is next to impossible to avoid isocyanate allergy triggers in the modern environment as they are used to make all Polyurethane products.

It is also likely that health effects are suffered beyond the respiratory system & skin for example the gastric & nervous systems and it is also probable that sensitisation to isocyanates will lead to allergies to other unrelated chemicals leading to a cascade of triggering chemicals allergies & intolerance for over exposed individuals.

DELAY – DENY – DIE

Navy (New Zealand) veteran’s landmark compensation deal has others with Parkinson’s fearing trichloroethylene

Hundreds of New Zealanders may have been affected by a toxic chemical in a wide range of workplaces, a Weekend Herald investigation has found.

The discovery follows a landmark compensation pay-out to a New Zealand navy veteran who proved links between exposure to the solvent during his military service and his Parkinson’s disease.

The Herald reported last month that Veterans Affairs has provided the ex-serviceman with an entitlement to disability compensation for Parkinson’s, a condition attributed to his exposure to trichloroethylene (TCE) while degreasing and cleaning electronics on a Royal New Zealand Navy ship during the 1948-1960 Malayan Emergency.

The Weekend Herald has since tracked down other men who fear their handling of TCE in the 1960s, 70s, and 80s could have caused their debilitating diseases and who now want to pursue their own compensation cases.

A former New Zealand Post Office telephone exchange technician, a naval dockyards apprentice and an aircraft engineer have all spoken about using TCE in their workplaces for years, without any health and safety precautions.

None of them used gloves or breathing apparatus while being exposed to the potent halocarbon that was popular across an array of sectors and workplaces in New Zealand, including garages, railway and aircraft workshops, and other depots.

“Trichlo was strong enough to bowl you over,” said 65-year-old Steve Walker, an ex-New Zealand Post Office employee at the Balclutha exchange, who now struggles with Parkinson’s. “It seeped into your skin, into your clothes. It took over you completely.”

Dave Schafer, a 58-year-old who used TCE weekly while cleaning instruments on Navy frigates during a five-year apprenticeship at the Devonport naval base, said: “Holy cow, that stuff was powerful. But as apprentices you kept your mouth shut and did your job, you didn’t rock the boat.”

Parkinson’s New Zealand, the Returned and Services’ Association (RSA), and those spoken to by the Weekend Herald, all believe there will be many more New Zealanders – hundreds if not thousands – who have been exposed to TCE over the years.

“Researchers have suggested there could be a significant lag time between exposure to TCE and the onset of Parkinson’s,” said Parkinson’s New Zealand chief executive Deirdre O’Sullivan.

“As such, we have reason to believe there could be many more serving and/or ex-serving NZDF people in a similar situation to this veteran.”

The potentially precedent-setting Navy veteran’s decision was made on appeal to the independent Veterans’ Entitlements Appeal Board, which considered appeals against decisions made under the War Pensions Act 1954.

It was made possible by ground-breaking international research including a major 2011 study on TCE exposure that concluded it was likely to result in a sixfold increase in the chances of developing Parkinson’s.

Read more on the New Zealand Herald’s website

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Interesting that the New Zealand Herald article discusses exposure in the 1960s, 70s, and 80s. No mention of the 1990s onwards obviously because the industries there using the chemical copped on in the 1990’s.

Unfortunately the Irish Air Corps was still exposing personnel to Trike, (without protection) in ERF / Avionics in the 1990s and well into the first decade of this century and likely elsewhere in Baldonnel & Gormanston

DELAY – DENY – DIE

Safe Handling of Cresols, Xylenols & Cresylic Acids

Introduction

Cresols, xylenols and cresylic acids are hazardous substances and dangerous both to people and the environment if handled improperly. Cresols, xylenols and cresylic acid products produced by Sasol Chemicals (USA) LLC are highly versatile materials and are used as intermediates in the manufacture of a wide variety of industrial products such as resins, flame retardants, antioxidants, and coatings. In these and other applications, cresylic acids can be stored, transferred, processed and disposed of safely when proper procedures and safeguards are used. 

“Cresol” refers to any of the three isomers of methylphenol (C7H8O) or combinations thereof. “Cresols” commonly refer to a mixture which is predominantly methylphenol but may also contain lesser amounts of other alkylphenols. “Xylenol” is a common name for any of the six isomers of dimethylphenol (C8H10O) or their various combinations. Material which is predominantly dimethylphenol but which also contains ethylphenols and other alkylphenols may be referred to as “Xylenols”. “Cresylic acid” is a generic term referring to various combinations of cresols, xylenols, phenol or other alkylphenols (ethylphenols, propylphenols, trimethylphenols, etc.). 

Purpose & Scope

The purpose of this document is to provide information gathered through Sasol’s long experience in the safe handling of cresylic acids. It focuses on basic and practical information about working safely with these substances. Additional references are provided and it is strongly recommended that these and others be consulted prior to working with cresylic acids. Please do not hesitate to contact your regional Sasol office if we can be of assistance in the safe storage, handling, processing and disposal of our products.

Hazards

Health Hazards

The primary dangers posed in handling cresylic acids are those resulting from physical exposure. Cresylic acids are highly corrosive and contact with exposed skin or mucous membranes causes severe burns. These burns progress from an initial whitening of the exposed skin to blackishbrown necroses within 24 hours after exposure. Cresylic acids also exhibit anesthetic properties. Therefore, victims frequently misjudge the extent of their exposure when the initial burning sensation rapidly subsides. This can result in prolonged contact, causing toxic effects in addition to the corrosive damage. 

Cresylic acids are readily absorbed through the skin and mucous membranes in liquid or vapor form and act as systemic toxins for which there is no established treatment. Relatively small areas of exposure (e.g. an arm or a hand) can allow sufficient absorption to cause severe poisoning. Progressive symptoms of such poisoning include headache, dizziness, ringing in the ears, nausea, vomiting, muscular twitching, mental confusion, loss of consciousness and, possibly, death from lethal paralysis of the central nervous system. Chronic exposure can lead to loss of appetite, vomiting, nervous disorders, headaches, dizziness, fainting and dermatitis. 

The Occupational Health & Safety Administration (OSHA) has established 5ppm or 22 mg/m3 permissible exposure limits (PEL’s) for cresols on an 8-hour time-weighted average basis. OSHA guidelines also indicate that adequate personal protective equipment (PPE) should be employed to avoid skin contact with cresols. Cresylic acids are not listed as carcinogens by OSHA, the International Agency for Research on Cancer (IARC) or the National Toxicology Program (NTP).

Environmental Hazards

Cresylic acids show high acute toxicity towards both fish and aquatic invertebrates and must be prevented from entering surface or ground waters. Depending upon the specific composition, the material may be classified as a marine pollutant. Please refer to the current label and safety datasheet.

Controls for Working with Cresols

Safe storage, handling, processing and disposal of cresylic acids begin long before they ever arrive on-site. Measures necessary to ensure the health and well-being of employees, customers, the community and the  environment include the development of effective administrative and engineering controls designed to specifically address the hazards associated with cresylic acids. Personal protective equipment (PPE) is integral to safe handling and should be viewed as the last line of defense against an accidental failure of the administrative and/or engineering controls. 

Administrative Controls

Administrative controls are the foundation of any program designed for safely handling cresylic acids. Every company is unique in how they run their business and establish administrative controls. Those specifically developed for working with cresylic acids should address comprehensive process planning, thorough communication of hazards to employees and extensive training of employees on the proper implementation of all safety measures.

Personal Protective Equipment (PPE)

All personnel who work with or near cresylic acids must use adequate personal protective equipment (PPE). The extent of the potential exposure and consideration of established permissible exposure limits (PEL’s) should dictate the level of protection necessary. Personnel working with or near lab-scale quantities should always wear safety glasses with side-shields or

chemical mono-goggles, chemical-resistant or impermeable gloves, long-sleeved shirts and trousers as a minimum.

Circumstances such as elevated temperature and pressure or vacuum conditions should dictate if more substantial protection is necessary, including face shields, chemically impermeable outerwear, and breathing protection. Personnel transferring larger quantities of cresylic acids, or working in areas where a line-break could result in similar exposure, should always wear full protective equipment.

Emergency Procedures

Physical Exposure – External

The primary dangers involved in working with cresylic acids are the corrosive and toxic effects resulting from a physical exposure. Studies suggest that the severity of the exposure depends more on the magnitude of the exposed skin area than the concentration of cresylic acid. Therefore, the critical factor in dealing with an external physical exposure to cresylic acids is to minimize the extent and duration of the contact. To this end, the immediate response must be thorough flushing of the exposed areas with copious amounts of running water to remove all the cresylic acid in contact with the skin or eyes. Any contaminated clothing should be removed as quickly and carefully as possible during this process to avoid any additional skin contact.

Any exposed areas will have readily absorbed the cresylic acids and may be evidenced by a characteristic whitening of the skin. After thorough flushing with water, a solution consisting of 2 parts polyethylene glycol 400 to 1 part ethanol (PEG/EtOH) should be liberally applied to any affected skin (avoid contact with eyes), allowed to remain 15 to 30 seconds and then flushed away with fresh running water. Continue the cycling of PEG/EtOH and water for at least 15 minutes and then finish with thorough washing with soap and water. This decontamination procedure reduces the severity of the exposure, but does not completely eliminate damage to the skin or toxic effects. Medical attention should be sought as soon as possible.

Spill Containment & Clean-Up

Spill containment and cleanup of cresylic acids should only be performed by properly trained personnel employing an appropriate level of protective equipment as dictated by the extent of the spill. Small to medium spills on land should be surrounded by and absorbed onto inert clay absorbent and transferred to a disposal container. Larger land-spills should be diverted away from waterways, contained with booms, dikes or trenches, and collected in a vacuum truck. Any residual cresylic acids remaining after vacuuming should be cleaned up using the clay absorbent. All soils affected by the spill should be removed and placed in approved disposal containers.

Water spills are of particular concern due to the acute toxicity of cresylic acids to marine life. Clean up efforts should focus on containing the spill and quickly removing the cresylic acids that settle in deeper areas of the waterway. This can be aided greatly if the flow of water can be slowed or stopped. Further efforts should focus on removing as much of the dissolved cresylic acids as possible from the water using activated charcoal.

The composition and extent of any spill should be evaluated against local guidelines (ex. SARA Title III and RCRA in the U.S.) and reported to the proper agencies, if necessary. Any non disposable clean-up equipment should be thoroughly decontaminated with soap and water after use.

Source : SASOL / USA

Safe Handling of Cresols, Xylenols & Cresylic Acids

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Some significant points to note about Cresylic Acid

Below is a photo taken 10 years ago in the Irish Army Air Corps NDT shop,  part of the Avionics / ERF building complex. Ardrox 666 can be seen spilled on the ground where it was free to leach through a shore onto the grass verge outside. 

  • 25% of fresh Ardrox 666 used by the Air Corps was Cresylic Acid. This percentage was higher in waste Ardrox 666 as Dichloromethane evaporated.
  • That greenish / yellow stain dripping from the extractor fan is also Ardrox 666 from the air.

DELAY – DENY – DIE

What are Isocyanates?

What are Isocyanates?

An isocyanate is any chemical that contains at least one isocyanate group in its structure. An isocyanate group is a group of atoms containing one nitrogen atom attached by a double covalent bond to one carbon atom, which in turn is attached by a second double bond to an oxygen atom (indicated in structure as -N=C=O). (Do not confuse this with the cyanate functional group which is arranged as –O–C≡N). A chemical containing two such isocyanate groups is called a diisocyanate. Common examples are toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI) and methylene diphenylmethane diisocyanate (MDI).

Isocyanates (a description which includes diisocyanates) are the raw materials that make up all polyurethane products. Isocyanates react with compounds containing alcohols to produce polyurethane polymers – which are used in polyurethane foams, thermoplastic elastomers and “2 pack” type polyurethane paints to improve the performance, durability and finish of painted surfaces. Jobs that may involve exposure to isocyanates include painting with polyurethane products, foam-blowing and the manufacture of polyurethane products like insulation materials, surface coatings, furniture, foam mattresses, under-carpet padding, packaging materials, laminated fabrics, polyurethane rubber, adhesives and also exposure can occur during the thermal degradation of polyurethane products.

Health Effects

Exposure to hazardous materials may be acute or chronic. Acute exposures refer to single high concentration exposures over shorter periods, while chronic exposures are repeated or continuous exposures over longer periods. Exposures to any toxic material may have either acute, immediate effects and/or chronic, long term health effects.

Inhalation:

Isocyanates are known to have a strong effect on the respiratory tract in some people. It is reported that there is a susceptible group in the population (estimated to be 5-20% of workers who are exposed occupationally) who can become sensitised to Isocyanates. Sensitization is the body’s hyper-reactive (allergy-like) response to a substance which has been touched or inhaled by a susceptible individual. Sensitization may develop as a result of a large single overexposure, for example, from a spill or accident, or from repeated overexposure at lower levels.

Once sensitised, these people, when later exposed to even very low concentrations of isocyanates even at levels below the exposure standard, can react by developing asthma-like symptoms, such as chest tightness, cough, wheezing and shortness of breath. Such attacks may occur up to several hours after cessation of exposure (for example, during the night after exposure) but, if a person is particularly sensitive, the attack can occur earlier or immediately. This sensitisation is essentially irreversible and can prevent any further work for the individual in their job using Isocyanates or any position associated with use of Isocyanates – even at very low levels below the regulated exposure level and that may not affect others. Many spray painters working in smash repair shops have had to leave the industry because they are sensitised to isocyanates.

An individual’s response to isocyanate exposure can be immediate or may be delayed for several years. Asthmatic people are more prone to sensitisation and other adverse reactions. Persons with a history of asthma, allergies, hay fever, recurrent acute bronchitis or any occupational chest disease or impaired lung function is advised against risking exposure to isocyanates. In rare cases, death has occurred from a severe asthma attack after significant isocyanate exposure.

Skin

Isocyanates are also skin irritants (causing inflammation and dermatitis) and there is some evidence that skin exposure can also cause respiratory sensitisation.

Eyes

Isocyanates are an irritant to the eyes. Splashes can cause severe chemical conjunctivitis.

Other Health Effects

Other health effects which have been reported include liver and kidney dysfunction. Some Isocyanate materials are considered to be potential human carcinogens (IARC).

Spraying Isocyanate Paints

Spray painters need to understand the health risks involved in spraying polyurethane paints – these are the two-pack mixes of polyurethane paints and possibly also in the one-pack moisture-cured mixes. These products are widely used in the automotive and other industries because of their excellent gloss, hardness, adhesion and chemical resistance.

The major hazard with spraying polyurethane paints is breathing the mist or aerosol droplets of the paint spray and absorbing the isocyanate and other components into your lungs.

The odour threshold for isocyanates, i.e. the level at which an individual can smell an isocyanate, is typically higher than the allowed exposure limits. In other words, if a painter smells the sweet, fruity, pungent odour of an isocyanate, they are probably already overexposed. That is why the recommended respiratory protection for employees spraying isocyanates is a supplied air respirator and not an air purifying respirator (i.e. filter cartridge style). The issue with use of air purifying respirators is that they will reach a point at which the filter becomes saturated and will no longer capture the isocyanate or other solvents. When that filter breakthrough happens, an Isocyanates overexposure can occur, potentially causing an irreversible sensitization. Use of a supplied air system removes this filter change factor – it does not rely on the painter changing his gas/vapour filters at appropriate intervals.

Note: if isocyanate-containing paint is applied by brush, roller or dipping, in a well ventilated area, there is generally no more hazard than with ordinary paints. These application methods usually do not produce the higher concentrations of isocyanate vapour associated with spraying.

After curing, polyurethane paints contain no free isocyanates and are not hazardous under normal use. However, welding or burning of polyurethane coated surfaces can release a range of contaminants. Gases or vapours evolved can include HDI, TDI, MDI as well as many other compounds (metal fumes, organic gases or vapours, particulates), depending on the original polyisocyanate resin used. When welding or cutting metal coated with a polyurethane coating, a worker may be exposed to a range of these decomposition products which will vary depending on type of process being used to weld or cut, the nature of the base metal and type of coating. Respiratory protection that is suitable for welding applications will also provide suitable respiratory protection in these cases

Source 3M Australia / New Zealand

http://multimedia.3m.com/mws/media/777847O/isocyanates-3m-techupdate.pdf

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Some significant points to note from this 3M document.

  1. Exposure can occur when cured isocyanates are heated.
  2. An individual’s response to isocyanate exposure can be immediate or may be DELAYED FOR SEVERAL YEARS.
  3. Skin exposure can also cause respiratory sensitisation.
  4. The odour threshold for isocyanates, i.e. the level at which an individual can smell an isocyanate, is typically higher than the allowed exposure limits.
  5. The Air Corps did eventually provide a “supplied air” respirator to spray paint & welding personnel. Unfortunately they sourced the “supplied air” from an old machine compressor located in ERF where the air had previously tested as 3.5 times over the allowed limit for Dichloromethane i.e. allowed limit was 50ppm and sourced air was from a location measured at 175ppm…out of the frying pan and into the fire.

Air Corps Isocyanate Usage

Isocyanates were used by the Spray Paint Shop (Dope Shop) at Baldonnel. For most of the existence of this shop personnel were NOT supplied with ANY PPE. The walls between the Spray Paint Shop and Engineering Wing Hangar & Workshops were not sealed and so isocyanates and other chemicals entered these workplaces whilst spraying was in progress exposing all personnel.

Furthermore if a component could not be removed from an aircraft for spray painting it was spray painted in-situ in Engineering Wing Hangar whilst unprotected line & tech personnel worked in adjoining offices & workshops or on other aircraft in the hangar.

A “waterfall” system with an extractor fan was also present. Personnel spray painted aircraft components toward the waterfall which captured most of the over-spray droplets. Fumes from this waterfall were then extracted by a fan, up a duct and released at approximately 3m height where the prevailing winds then carried the extracted fumes in the doors & windows of Avionics Squadron & Engine Repair Flight exposing further unprotected personnel.

Sensitisation is irreversible and once sensitised it is next to impossible to avoid isocyanates in the modern environment. It is also likely that health effects are suffered beyond the respiratory system & skin for example the gastric & nervous systems. 

DELAY – DENY – DIE