CHEMICAL HAZARD

acute toxicology - A quantity of substance that produces a harmful effect very quickly. - registered within seconds, minutes or hours.
chronic toxicity - quantity of the substance will take a long time to cause a harmful effect say a month or years Information required for toxicity evaluation: 1. 2. 3. 4. Reaction or body changes produced by the substance Complete chemistry of the substance Dosage level required to cause body reaction or changes Secondary information such as how, in conjunction with other substance or compounds, the body changes are affected considering age, sex, and general health of the possible victim

for

Classification of Relative Toxicity for a Fatal Single Oral Dose (1 mg = 0.001 g)

Toxicity Rating Commonly Used Terms Probable Human Lethal Dose for 70 kg (150 lb) man 5 mg/kg 5-50 mg/kg 50-500 mg/kg 5-5g/kg 5-15 g/kg 15 g/kg Range of common Quantities Example of Toxic Substance

6 5 4 3 2 1

Spatoxic Extremely Very toxic Moderately Slightly toxic Practically

A taste: 7 drops 7 drops 1 teaspoon 1 tsp. 1 oz. 1 ounce 1 pt. or 1 lb. 1 pt. qt. or 1 lb. 1 pint 1 lb.

Nicotine Leas Arsenate Hydroquinone Propan-2-02 Sorbic acid Propylene Glycol

There are three routes wherein deleterious substance can enter the body. 1. By absorption through the gastro-intestinal tract, known as ingestion 2. By absorption through the skin, known as absorption 3. By absorption through the lungs, known as inhalation

Controlling Toxic Substances

The most important aspect of toxicological studies is determination of the conditions and concentrations in which a substance can be used safely. Knowledge in this area can serve as criteria in the sage occupational exposure of workers to toxic substances or environment. One of the most important organizations which examines toxicological data and which sets safe working limits is the American Conference of Government Industrial Hygienists (ACGIH). These limits are known as Threshold Limit Values (TLV), which are published by the United Kingdoms Health and Safety (HSE). The categories of the Threshold Limit Values (TLV) TLV Time Weighted Average (TWA) this gives exposures based upon an 8-hour day, 40-hour week, which will not produce harmful effects. Threshold Limit Value-Short Term Exposure Limit (TLV-STEL) this controls for some substances higher levels of exposure above the TLV-TWA, for periods up to 15 minutes provided no more than four short-term exposures are allowed in the day, with a minimum spacing of 1 hour between the exposure periods. TLV-Ceiling this is a level that must never be exceeded for any time period.

1. 2.

3.

The TLV system is intended to be used as guide to the higher limits of exposure to toxic substances. In practice the lower limits must always be used only under the guidance of an experienced industrial hygienist. More often than not technicians lack the expertise in applying the system and therefore need the guidance from them.

TLVs do not show the following: 1. Index of relative toxicity of substances 2. Indicated the relative hazardous nature of the substance. This can be illustrated by studying the TLVs for hydrogen cyanide and hydrogen chloride.
TLV-TWA 10 ppm 5 ppm TLV-STEL 15 ppm 5 ppm

Hydrogen cyanide (SKIN) Hydrogen chloride

1.

2.

The TWA value for hydrogen cyanide can be increased by 50% to give the STEL value for hydrogen cyanide in a ceiling value (C) and should never be surpassed. Without doubt hydrogen cyanide is potentially an extremely toxic substance. If the STEL value is increased by a factor of three to a concentration of 45 ppm, most people would die within 5 to 10 minutes results in unpleasant experience but unlikely lethal. The skin notation against hydrogen cyanide shows that it has the ability to enter the body by skin absorption as well as by inhalation and ingestion. Hydrogen chloride would only be inhaled. This shows that hydrogen cyanide is more hazardous than hydrogen chloride

There are many chemical and elements in industry and the household that are poisonous to which people are exposed. If any of these substances come in contact with the body by accident through improper storage, by entering sprayed areas or by eating sprayed foods from which sprayed residues have not been removed, lethal effects may result. Another method of exposure is by exposure of those who work with aricultural poisons during manufacture, preparation for use, storage and application. Some of these poisons are as follows:

Cleaning Equipment Carbon tetrachloride Solvent distillate Lye (sodium hydroxide) Ammonia Bleach sodium hypochloride, oxalic acid Dry cleaner lye, sodium acid sulfate Rug cleaner chlorinated hydrocarbons Wallpaper cleaner kerosene Laundry ink Aniline Medicines Salicylates aspirin, methyl salicylate Sedatives barbiturates, bromides Anti-epileptic agents bariturates, hydantoins Antihistamines (cold tablets) and seasickness pills Cathartic pills strychnine, drastic cathartics Cough mixtures codeine, methadone Nose drops ephedrine, privine Reducing or sliming tablets amphetamines Cardiac drugs digitales, quinidine, veratrum preparations Antiseptics - boric acid, mercuric chloride, iodine, phenol Liniment camphorated oil, aconite, methyl salicylate Cosmetics Hair silver salts, anilines, potassium bromate, selenium sulfide Hobby Toluene (cement), methanol (stencils), photography chemicals

Storeroom
Paint and Painting Supplies Paints thinner, lead, arsenic,, chlorinated hydrocarbons Paint remover chlorinated hydrocarbons, acids, alkalies Lacquer ethyl acetate, amyl acetate, methyl alcohol Shellac methyl alcohol Wood bleach oxalic acid Pesticides moth balls (naphthalene) Yard or storage (garage) Insecticides Benzene hexachloride Chlordane and lindane DDT and taxaphene Arsenic and lead Rodenticides Sodium flouracetate Phosphorus Methyl bromide Plants

tetrathylpryophosphate parathion and malathion dichloroethyl ether fumigants nicotine cyanide strychnine thallium and barium

Cherry cyanide Foxglove digitalis Thorn apple atropine

mushrooms oleander poison ivy

Safe Storage and Use 1. 2. 3. All medicines, insecticides and rodenticides should be stored in locked cabinets properly labeled. Dust-forming operations must be in closed system with exhaust ventilation. Lye, polishes, kerosene, and other poisonous chemical should never be left in low shelf or on the floor but should be in locked storage. 4. Dangerous solutions should never be left in drinking glasses or beverage bottles. 5. Inhalation of spray or fumes must be prevented during painting or application of insecticides by spraying downwind. 6. Unnecessary toxic substances such as boric acid and others should be discarded by flushing down the drain and dust vacuum cleaned. 7. Combustion devices should be adequately vented. 8. Carefully check the label of any medicine before taking. 9. When handling, preparing, storing or using substances, appropriate personal protective clothing and devices must be used. 10. 10. Toxic materials must be transported in enclosed conveyors if possible. Education

1.
2. 3.

All responsible persons in the household, offices and factories must be educated to the dangers present in medicines and chemicals. A poison label should be placed in all dangerous medicines, including aspirin, soluble salts, and barbiturates. Proper education and training in first aid or emergency treatment involving cases of poisoning must be conducted.

Protective Clothing and Equipment 1. Use masks and exhaust ventilation during dry mixing. 2. Wear protective clothing, goggles, and oil resistant neoprene gloves when prolonged handling of poisons in petroleum oils or organic solvents. 3. Protective clothing should be stored properly after use and exposed skin washed thoroughly before eating. 4. Respirators, goggles, protective clothing and gloves must be worn during preparation and use of sprays, mists, or aerosols to prevent skin contamination or inhalation. 5. Protective equipment made of rubber should be used in the handling of chlorinated hydrocarbons and equipment made of neoprene or other oil resistant materials should be used for handling poisons in organic solvents.

Chemical Carcinogens The ability to induce cancer is the most mystifying and insidious of all toxic responses that can be evoked in the body. In spite of many years of research, which yielded numerous information on cancer, solution to this problem is still wanting. It is now believed that at least 80 percent of human cancer is the off shot of exposure to chemicals that are met in our work, food from a combination of smoking tobacco and drinking alcohol and from breathing polluted air. Conclusions on Cancer 1. Some human cancers result from substance formed by normal processes in the body 2. In theory, majority of human cancers are preventable 3. Until a fundamental understanding of cancer cause and control is attained, a policy of prevention rather than cure must be the occupational standard. Cancer IS known as the formation of a lump or tumor caused by the uncontrolled growth of abnormal cells which eventually spread at the expense of normal cells can, unless it is stopped cause death. Carcinogens refer to agents consisting of either chemical, physical or viral that have the ability to induce cancer. It is generally accepted that formation of cancerous cells results from the attack of the mechanism that controls the reproduction of normal cells by carcinogens Difference between carcinogens from simple toxic substances: 1. Carcinogens affect certain fundamental cell reactions within the cell structure while simple toxic substance simply upset the body metabolism that prevents cells from functioning normally. 2. Effect of carcinogens will not appear for many years (latency period) varying from 5 to 50 years during which there is little or no warning of the eventual lethal outcome while simple toxic substances manifest almost immediate effects. 3. Carcinogens produce irreversible toxic effects that continue after the exposure has ceased while the action of simple toxic substance will stop when exposure stops followed by recovery.

Controlling Carcinogenic Substances If substances are found to be carcinogenic to humans, there are two ways of controlling them. 1. Permitting their use under close hygienic control 2. Banning their use and changing to sager substitutes In some countries like the United Kingdom, certain aromatic amino and nitro-compounds have been banned and vinyl chloride can only be manufactured and used under strictly controlled conditions. Unluckily, this approach is more the exception than the rule as a large number of carcinogens are used every day in laboratories, workshops and in plants without the exacting hygiene controls that such use demands. For longer life expectancy, exposure to chemical carcinogens must be avoided. The safe use of carcinogens is debatable. It can be argued that with efficient physical controls, the use of personal protection and strict personal hygiene, risk can be eliminated. This, however, implies that a carcinogen is known of being used. Unfortunately, this is not so, since many carcinogens are being used in ignorance. No listing of chemical carcinogens is complete due to limited knowledge about them. However, as a guide to managers and safety engineers, the following list of carcinogenic cubstances was published by the Health and Safety Executive: A. Substances Prohibited in the United Kingdom 1. Beta-naphthylamine 2. Benzedine 3. Salts of these compounds 4. 4-aminodiphenyl 5. 4-nitrodiphenyl

B. Substances Controlled in the United Kingdom 1. Alpha-naphthylamine 2. Dianisidine 3. Salts of these compounds 4. Auramine 5. Ortho-tolidine 6. Dichlorobenzidine 7. Magenta C. Substances and Processes Carcinogenic to Humans 1. Arsenic trioxide production 2. Dis (chloromethyl) ether (BCME) 3. Chromite ore processing 4. Nickel sulphide roasting fume and dust 5. Particulate polycyclic aromatic hydrocarbons 6. Vunyl chloride D. Substances and Processes Suspected as Carcinogenic to Humans 1. Antimony trioxide production 2. Benzene 3. Benz (a) pyrene 4. Cadmium oxide production 5. Beryllium 6. Chloroform 7. Chromates of lead and zinc 8. 3, 3-dichlorobenzidine 9. Dimethylcarbamyl chloride 10. 1, 1-dimethylhydrazine 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. Thallium Dimethyl sulphate Epichlorhydrin Hexamethyl phosphoramide Hydrazine 4, 4-ethylene bis (2-chloroaniline) 4, 4-ethylene dianiline Monomethyl hydrazine Nitrosamines Propane sultane Beta-propiolactone Vinyl cyclohexene ethyl sulphate

Identifying Carcinogenic Substances Deficiency of scientific knowledge on the formation of cancer and chemical that are human carcinogens is responsible for the difficulty of controlling chemicals that cause cancer. Nevertheless, three techniques have been developed to resolve the problem. Animal Testing. This method calls for the exposure of animals to the chemical to determine if the substance is a potential carcinogenic risk to humans. Risk involved is only considered potential since animals do not have the same metabolic structures as humans. Almost all substances that cause cancers to animals however cause cancer also to humans. Epidemiological Surveys. This method concerns with the analysis of medical records to determine if there is a statistical increase of cancer in people exposed to a certain substances or process in comparison to people who are not exposed. The relationship between smoking tobacco and lung cancer was established using this method. Short-Term Screening Tests. This is a new method which utilizes animal tissue as a test system. It has been found out that abnormal reactions can be produced by carcinogenic substances when tissues containing them are cultured. This technique will hopefully help in hastening the screening of suspected carcinogenic substances. Dermatitis Substances A non-infectious, inflammatory condition of the skin caused by prolonged contact with chemical or physical agents is known as Dermatitis. In many instances, the condition causes only minor inconvenience, but in others it may create a serious and unsightly problem. The creation of numerous chemical compounds due to the advancement of science and technology has cause the exposure of people to a number of these deleterious substances. As such dermatitis can be acquired not only from employment, but at home and outdoors. A glandular excretion of greasy protective coating in combination with the formation of a hard outer cellular layer furnishes the skin with a good defensive mechanism against the attack from the environment. Unfortunately, this protection is greatly lessened by chemical or physical agents which destroy the outer protective layer or dissolve the greasy coating. As such irritation and dermatitis occur causing loss of thousands of man-days yearly. There are generally two categories of occupational

Contact Dermatitis. Generally, this condition is caused by substances known as primary cutaneous irritants. These substances directly attack the skin causing tissue destruction or degreasing. Prolonged exposure to a sufficient concentration causes irritation, but recovery follows after removal of the same. Sensitization Dermatitis. Generally, this condition is caused by substances known as cutaneous sensitizers. Such substances do not necessarily cause inflammatory response on first contact, but may cause an allergic response in the metabolic reaction of the skin. Once the response has developed, dermatitis will occur and will take place for a period of several days or months. Usually recovery from dermatitis condition occurs when contact is removed but the allergic response will remain. However, a further small exposure may cause a quick development of severe dermatitis. For some people, substances that are considered as primary irritants can cause a sensitization reaction or allergic dermatitis response to others. Sensitization Dermatitis. Generally, this condition is caused by substances known as cutaneous sensitizers. Such substances do not necessarily cause inflammatory response on first contact, but may cause an allergic response in the metabolic reaction of the skin. Once the response has developed, dermatitis will occur and will take place for a period of several days or months. Usually recovery from dermatitis condition occurs when contact is removed but the allergic response will remain. However, a further small exposure may cause a quick development of severe dermatitis. For some people, substances that are considered as primary irritants can cause a sensitization reaction or allergic dermatitis response to others. Primary Cutaneous Irritants: 1. Mineral oils 4. Strong alkalis and acids 2. Greases 5. Cement 3. Solvents like petrol 6. Physical agents heat, cold a. White spirit 7. Radiation b. Chlorinate hydrocarbons 8. Friction c. Ethoxyethane d. Propanone

Primary Cutaneous Sensitizers 1. Photographic developers 2. Rubber additives 3. Epoxy and phenol-formaldehyde 4. Nickel compounds 5. Hair dyes containing 1, 4-diaminobenzene 6. Methanol solutions 7. Chromates (VI) 8. Wood dust-african or teak 9. Antibiotic, penicillin and streptomycin Preventive Measures for Dermatitis 1. Limit exposure to minimum 2. With dust and vapors, use efficient ventilation 3. Move offending substance to safe place 4. When liquids, paste or solids are being used, suitable protective equipment should be worn like gloves, boots, apron, etc. 5. Use correct barrier cream against primary irritants. 6. Adhere to personal hygiene. 7. Strict compliance to safe working methods and instructions.

Accident by Gassing One very common occupational occurrence is accidents from gassing. This consists of the inhalation of air containing toxic or corrosive gas. When such gas is absorbed in the respiratory system it produces acute response. One of the most common types of gassing accidents is anoxia or lack of oxygen which happens in two ways, viz.: 1. Simple anoxia the amount of oxygen in the air has been reduced to a level which can not adequately support respiration; they arise from the following: a. During fire when oxygen in air is rapidly reduced to support rapid combustion. b. Evaporation of an inert liquid such as liquefied nitrogen, displacing oxygen in air. Toxic anoxia this occurs when oxygen is prevented from travelling through the body in the blood. This may due to: a. Inhalation of carbon monoxide, hydrogen sulphide, hydrogen cyanide or arsine. b. Contact of sulphide, cyanides, arsenides with acids.

2.

Some gases, called irritant gases, attack the respiratory system causing severe corrosive or inflammatory reaction. They include the following gases: 1. Acid gases like: a. Sulphuric acid mist b. Hydrochloric acid c. Hydrofluoric acid d. Sulphur dioxide e. Oxides of nitrogen 2. Neutral Gases a. Halogens b. Carbonyl chloride c. Trioxygen 3. Alkaline a. Ammonia

Hypoxia.

Oxygen deficiency that results from any interference with oxygenation of blood or inability of tissues to absorb oxygen. The type and magnitude of tissue damage caused by hypoxia depend on rapidity with which deprivation of oxygen takes place and its duration. The most sensitive to oxygen deficiency is the brain and manifests itself by decrease in mental capabilities. Irreversible damage occurs is oxygen supply is cut 5-7 minutes or more. Hypoxia causes an increase in reaction time. Individual concentration is not only impaired but also individual mood. Moreover, heart failure may occur when oxygen tension drops below 45 mm Hg resulting in rapid drop in blood pressure and pulse rate. Affected person grows pale, begins to perspire, may have headache, dizziness, suffers from nausea and fainting. Furthermore, there may be decrease in ability to control eye muscles and visual range. Other kinds :
1. Hypoxic hypoxia this is due to low oxygen tension in the blood. It is primarily due to inadequate oxygen source experienced in high altitudes. Can also be due to leakage of inert gas as nitrogen into a confined apace or replacement of oxygen by carbon dioxide during fires. Hypemic hypoxia a disturbance impairing the ability of the blood to carry oxygen to the tissues, like in hemorrhage and anemia which involves loss of red cells and reduction of total quantity of hemoglobin. Stagnant hypoxia caused by insufficient circulation of blood and therefore oxygen in the body. Excessive perspiration without sufficient liquid intake reduces the fluid volume, sodium and potassium the loss of which interferes with the absorption and release of oxygen and carbon dioxide by the blood. Historic hypoxia the inability of tissues to absorb and utilize oxygen carried to them by the blood. Owing to presence of toxic materials like: alcohol, narcotics or poison.

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Effect of Oxygen Deficiency in People Oxygen content of air, % 20.9 15 10 Effect Normal, no effect No immediate effect Dizziness, short breath, rapid breathing Stupor sets in Minimum amount to support life Death within 1 minute

7 5 2-3 Carbon dioxide as a Hazard. This is a gas resulting from combination of carbon and oxygen during combustion. As an air pollutant, it can cause varying discomfort
% Carbon dioxide in air 0.04 2 4 4.5-5 7-9 10-11 15-20 25-30

Normal air, no effect Deeper breathing, 30 % increase in respiratory volume Much deeper breathing, much discomfort Labored breathing, almost unbearable, nausea may occur Limit of tolerance Inability to coordinate, unconsciousness after 10 minutes Symptom increase in severity, may not be fatal within 1 hour exposure Diminished respiration, fall of blood pressure, coma, loss of reflexes, gradual death

Fume fever Another gazing situation which produces a symptom similar to an attack of influenza. This happens when fumes containing zinc, copper or brass are inhaled. Polymer fume fever can be produced when polyvinyl chloride (PVC), polytetraflourethylene (PTFE) fumes are inhaled. The condition can be very severe lasting for several days. Recovery may be attained without any lasting effects. First Aid for Inhaled Gas (except Hydrogen Cyanide) 1. Loosen tight clothing like ties, collar, belts, etc. 2. If victim is unconscious and breathing has stopped apply artificial respiration. 3. If victim is unconscious but breathing, lie with body in face-down position, with head turned to one side to permit easy breathing 4. Call physician to give medical attention to victim or sent him to the nearest hospital. If possible sent to hospital details of gassing incident and any treatment given. Corrosive Substances These substances can cause chemical burns. They cause rapid destruction of the body at point of contact. They are classified as follows: A. Dehydration due to: 1. Acids like: concentrated sulphuric acid 2. Alkalis like: sodium hydroxide and solutions 3. Acid anhydrides like: ethanoic acid anhydride B. Reduction caused by reactive reductants 1. Sodium and potassium metals. These metals cause dehydration burns due to formation of concentrated alkali. C. Oxidation caused by reactive oxidants 1. Nitric acid 2. Chromium trioxide (solid or in solution) 3. Bromine

D. Denaturation of proteins as caused by phenol The skin and the eyes are the parts of the body most vulnerable to corrosive action of chemicals, followed closely by the irritation of the respiratory track. The gastro-intestinal tract is usually the least vulnerable. Severity of the corrosive action of concentrated sulphuric acid is increased by the heating effect produced as the acid is diluted by the fluid from the eye and as tissue is destroyed by the dehydrating action of the acid. Liquid sulphur dioxide when under pressure can cause severe eye damage if a jet of the liquid strikes the cornea. Sulphurous acid (H2SO3) is formed by hydrolysis of sulphur dioxide by the water on the cornea and also within the cornea after sulphur dioxide has been absorbed. Severity of damage of alkali solution is related to the pH of the solution and time of exposure. Generally, the higher the pH value, the lower is the exposure required to produce the damage. When calcium oxide is in contact with the eye, hydrolysis to calcium hydroxide occurs, with the resulting potential for an alkali burn This condition is further aggravated by the law of solubility of calcium hydroxide and a secondary reaction with protein, which forms little clumps of insoluble substances. Removal of these clumps is very difficult and while they remain they provide a source of calcium hydroxide and persistent alkaline attack. Eye damage due to organic compounds is increased by compounds which are readlily absorbed into fat tissue, causing deep tissue damage. Their mode of action fall under two categories: 1. Reactive substances which cause physical destruction of tissue, like: benzenecarbonylchloride. 2. Compounds whose reactions are less severe, like: solvents. The second group causes slight loss of sight, but full vision returns after a short time. Tissue damage heals without impairment of vision. On the other hand, detergents with their fat solubilizing properties are readily absorbed into the eye tissue and produce severe burns if not quickly washed.

Mechanisms of Some Toxic Agents 1. Aromatic amino and nitro compounds these substances oxidize the iron (II) in the hemoglobin to iron (III) which reduces the efficiency with which oxygen passes through the blood as the oxidized hemoglobin becomes inactive. 2. Cyanide ion, CN this substance produces toxic action by deactivating enzymes that take part in the reaction which allows O2 to be used by the cell tissue. First aid treatment of cyanide is inhalation of amyl nitrite vapor followed by rapid treatment with Kelo-cyanor , resuscitation. 3. Hydrogen fluoride this is one of the most corrosive agents. Its corrosive action is related to the fluoride rather than to the acidic nature of the substance. Fluoride is readily absorbed by the skin and rapidly penetrates deep into the tissue layer causing necrosis (death) of cells of the soft tissues. Decalcification and corrosion of bone can also happen. 4. Hydrogen sulphide this substance acts directly on the nervous system causing paralysis of the respiratory center. It paralyses also the olfactory system (sense of smell). 5. Mercury vapor if it is inhaled, it is absorbed by the lungs and oxidized into mercury ions. Then it is distributed uniformly through the body, eventually lodging in the kidneys. 6. Phenol, C6H5OH a highly toxic substance capable of killing all types of biological cells, in two ways: 7. Corrosive agent when in contact with the skin it denatures proteins, causing skin to turn white, then red resulting in dad skin. 8. Toxic agent it is rapidly absorbed into the blood stream producing toxic action. The kidney are preferentially attacked causing possible death.