HAZARDS IN THE CHEMICAL PROCESS INDUSTRIES 85
Table 9. Threshold Limit Values (mg/m3) of Various Insecticides Substance
Aldrin (1, 2, 3, 4, 10, 10-hexachloro- 1,4,4a,5,8,8a-hexahydro-l,4,5,8- dimethanonaphthalene)
Arsenic Calcium arsenate
Chlordane (1, 2, 4, 5 , 6, 7, 8, 8-octachloro-3a, 4, 7, 7a-tetrahydro-4, 7- methanoindane)
Chlorinated camphene, 60%
2, 4-D (2, 4-dichlorophenoxyacetic acid
DDT (2, 2-bis(p-chlorophenyl)
-
1, 1, 1 -trichloroethane)Dieldrin (1, 2, 3, 4, 10, lO-hexachloro-6,7, epoxy - 1, 4, 4a, 5, 6, 7, 8, 8a - octahydro - 1, 4, 5, 8 -dimethan0 -naphthalene)
Dinitro-o-cresol
Ferbam (ferric dimethyl dithiocarbamate) Lead arsenate
Lindane (hexachlorocyclohexane gamma isomer)
Malathion (0, 0-dimethyl dithiophosphate of diethyl mercaptosuccinate) Methoxychlor (2, 2-di-p-methoxyphenyl-1 , 1, 1- trichloroethane) Nicotine
Parathion (0, 0-diethyl-0-p-nitrophenyl thiophosphate) Pentachlorophenol
Phosphorus pentasulfide Picric acid
Pyrethrurn Rotenone
TEDP (tetraethyl dithionopyrophosphate) TEPP (tetraethyl pyrophosphate) Thiram (tetramethyl thiuram disulfide)
Warfarin (3-(a-acetonylbenzyl) 4- hydroxycoumarin)
TLV
0.25
0.5 1 0.5
0.5 10 1 0.25
0.2 15 0.15
0.5 15 15 0.5 0.1 0.5
1 0.1
5 5 0.2 0.05
5 0.1
HAZARDS IN THE CHEMICAL PROCESS INDUSTRIES 87
Tables 10 through 15 provide a summary of the physical and hazardous properties of some of the common insecticides.
Table 10. Physical and Hazardous Properties of Parathion, Liquid Chemical Designations
-
Synonyms: 0,O-Diethyl O-(p-nitrophenyl) phoshorothioate; 0,O-Diethyl O-(p-nitrophenyl) thiophosphate; Ethyl Parathion; Phosphorothioic acid; 0,O-diethyl O-p-nitrophenyl ester;Chemical Formula: (C,H,0),PSOC6H4N02;
Observable Characteristics
-
Physical State (as shipped) : Liquid; Color:Deep brown to yellow; Odor: Characteristic
Physical and Chemical Properties
-
Physical State at 1.5"C
and I atm. : Liquid; Molecular Weight: 291.3; Boiling Point at 1 atm. : Very high;decomposes; Freezing Point: 43 O F , 6 OC, 279 O K ; Specific Gravity: 1.269 at 25 "C (liquid); Heat of Combustion: -9,240 Btu/lb.
Health Hazards Information
-
Recommended Personal ProtectiveEquipment: Neoprene-coated gloves; rubber work shoes or overshoes; latex rubber apron; goggles; respirator or mask approved for toxic dusts and organic vapors; Symptoms Following Exposure: Inhalation of mist, dust, or vapor (or ingestion, or absorption through the skin) cause dizziness, usually accompanied by constriction of the pupils, headache, and tightness of the chest. Nausea, vomiting, abdominal cramps, diarrhea, muscular twitchings, convulsions and possibly death may follow. An increase in salivary and bronchial secretions may result which simulate severe pulmonary edema.
Contact with eyes causes irritation; General Treatment for Exposure: Call a doctor for all exposures. INHALATION: remove victim from exposure immediately; have physician treat with atropine injections until full
atropinization; 2-PAM may also be administered by physician. EYES: flush with water immediately after contact for at least 15 rnin. SKIN: remove all clothing and shoes; quickly wipe off the affected area with a clean cloth;
follow immediately with a shower, using plenty of soap. If a complete shower is impossible, wash the affected skin repeatedly with soap and water.
INGESTION: if victim is conscious, induce vomiting and repeat until vomit fluid is clear; make victim drink plenty of milk or water; have him lie down and keep warm; Toxicity by Inhalation (Threshold Limit Value): 0.01 mg/m3;
Short-Term Inhalation Limits: 0.5 mg/m3 for 30 min. ; Toxicity by Ingestion:
Grade 4, oral LD,, = 2 mg/kg (rat); Late Toxicity: Birth defects in chick embryos; Odor Threshold: 4.04 ppm.
" .\. " > \ " > , ~ ~,
, \ ' ,., . , . / ,
Table 11. Physical and Hazardous Properties of Pentachlorophenol
1
Chemical Designations
-
Synonyms: Dowicide 7; Penta; Santophen 20;Chemical Formula: C6C1,0H
Observable Characteristics
-
Physical State (as shipped): Solid; Color:Colorless to light brown: Odor: Very weak
- " .
Physical and Chemical Properties
-
Physical State at 15 "C and I atm. : Solid; Molecular Weight: 266.35; Boiling Point at I atm.: 590 O F , 310 'C, 583 O K ; Freezing Point: 370, 188, 461; Specific Gravity: 1.98 at 15 "C (solid).Health Hazards Information
-
Recommended Personal Protective Equipment: Respirator for dust; goggles; protective clothing; Synptoms Following Exposure: Dust or vapor irritates skin and mucous membranes, causing coughing and sneezing. Ingestion causes loss of appetite, respiratory difficulties, anesthesia, sweating coma. Overexposure can cause death;General Treatment for Exposure: Call a doctor! INGESTION: induce vomiting at once. EYES: flush with water for 15-30 min. SKIN: wash well with soap and water; Toxicity by Inhalation (Threshold Limit Value): 0.5 mg/m3; Short-Term Inhalation Limits: Data not available; Toxicity by Ingestion: Grade 3, LD,, 50 to 500 mg/kg; Late Toxicity: Data not available;
Vapor (Gas) Irritant Characteristics: Vapor is moderately irritating such that personnel will not usually tolerate moderate or high vapor concentrations;
Liquid or Solid Irritant Characteristics: Causes smarting of the skin and first- degree burns on short exposure; may cause secondary burns on long
exposure; Odor Threshold: Data not available. .
,I
Production of the toxic substances used in insecticides involves the same
operations employed for general chemical processing. Similarly, chemical- processing equipment, that is, reaction kettles, filters, heat exchangers, and so forth, are the same as discussed in other sections of this chapter. Emphasis is given, therefore, to the equipment and techniques encountered in the
compounding and blending of commercial insecticides to achieve specific
chemical and physical properties. Most commercial insecticides are used as either dusts or sprays. Insecticides employed as dusts are in the solid state in the 0.5 to 10 micron size range. Insecticides employed as sprays may be manufactured and sold as either solids or liquids. The solids are designed to go into solution in an appropriate solvent or to form a colloidal suspension; liquids may be either
solutions or water base emulsions.
HAZARDS IN THE CHEMICAL PROCESS INDUSTRIES 89
Table 12. Physical and Hazardous Properties of Lead Arsenate
Chemical Designations
-
Synonyms: Lead arsenate, acid; Plumbous arsenate;Chemical Formula: PbHASO,
Observable Characteristics
-
Physical State (as shipped): Solid; Color:White; Odor: None
Physical and Chemical Properties
-
Physical State at I5 "C and I atm. : Solid; Molecular Weight: 347.12; Boiling Point at I atm. : Decomposes;Freezing Point: Not pertinent; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 5.79 at 15 "C (solid).
Health Hazards Information
-
Recommended Personal Protective Equipment: Dust respirator; protective clothing to prevent accidental inhalation or ingestion of dust; Symptoms Following Exposure: Inhalation or ingestion causes dizziness, headache, paralysis, cramps, constipation, collapse, coma. Subacute doses cause irritability, loss of weight, anemia, constipation. Blood and urine concentrations of lead increase; General Treatment for Exposure: A specific medical treatment is used for exposure to this chemical; call a physician immediately! Give victim a tablespoon of salt in glass of warm water and repeat until vomit is clear. Then give twotablespoon of epsom salt or milk of magnesia in water, and plenty of milk and water. Have victim lie down and keep quiet; Toxicity by Inhalation
(Threshold Limit Value): (dust) 0.15 mg/m3; Short-Term Inhalation Limits:
Not pertinent; Toxicity by Ingestion: Grade 4,
LD,,
below 50 mg/kg (rabbit, rat).No matter what physical state or form is involved, insecticides are usually a blend of several ingredients in order to achieve desirable characteristics. A convenient means of classifying equipment and their related processing techniques is to differentiate them by the state of the end product. Equipment used to process insecticides where the end product is a solid is designated solid insecticide-processing equipment. Equipment used to process insecticides where the end product is a liquid is designated as liquid-insecticide-processing equipment. Solid mixtures of insecticides may be compounded by either (1) adding the toxicant in liquid state to a dust mixture or (2) adding a solid toxicant to the dust mixture. If the toxicant is in liquid state, it is sprayed into a dust mixture during the blending process. After leaving the rotary sifter, the solid raw materials are carried by elevator to the upper mixer where the liquid toxicant is introduced by means of spray nozzles.
Table 13. Physical and Hazardous Properties of Aldrin
Chemical Designations
-
Synonynzs: endo-, exo-, 1 ,2,3,4,10,1O-Hexachloro- 1,4,4a,5,8,8a-Hexahydro- 1,4,5,8-Dirnethanonaphthalene, HHDN; Che~nical Formula: C,,H,CI,Observable Characteristics - Physical State (as nornlally shipped): Solid;
Color: Tan to dark brown; Odor: Mild chemical
Physical and Chemical Properties - Physical State at 15 "C and 1 atnt. : Solid; Molecular Weight: 364.93; Boiling Point at I atm. : Not pertinent;
Freezing Point: 219, 104, 377; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 1.6 at 20°C (solid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): Not pertinent;
Lcrtent Heat of Vaporization: Not pertinent; Heat of Combustion: Not pertinent; Heat of Decomposition: Not pertinent
Health Hazards Information - Recontnzended Personal Protective Equipment: During prolonged exposure to mixing and loading operations, wear clean synthetic rubber gloves and mask or respirator of the type passed by the U.S. Bureau of Mines for aldrin protection; Symptoms Following Exposure: Ingestion, inhalation, or skin absorption of a toxic dose will induce nausea, vomiting, hyperexcitability, tremors, epileptiform convulsions, and ventricular fibrillation. Aldrin may cause temporary reversible kidney and liver injury. Symptoms may be seen after ingestion of less than 1 gram in an adult; ingestion of 25 mg has caused death in children; General Treatment for Exposure: SKIN CONTACT: wash with soap and running water. If material gets into eyes, wash immediately with running water for at least 15 min.; get medical attention. INGESTION: call physician immediately; induce vomiting, Repeat until vomit fluid is clear. Never give anything by mouth to an unconscious person. Keep patient prone and quiet. PHYSICIAN: administer barbiturates as anti-convulsant therapy. Observe patient carefully because repeated treatment may be necessary; Toxicity by Inhalation (Threshold Limit Value): 0.25 mg/m3; Short-Term Exposure Limits: 1 mg/m3 for 30 min.;
Toxicity by Ingestion: Grade 3; LD 50 to 500 mg/kg (rat); Late Toxicity:
Chronic exposure produces benign tumors in mice; Vapor (Gas) Irritant Characteristics: Vapors cause slight smarting of the eyes or respiratory system if present in high concentration. Effects is temporary; Liquid or Solid Irritant Characteristics: Minimum hazard. If spilled on clothing and allowed to remain, may cause smarting and reddening if the skin; Odor Threshold:
Data not available.
HAZARDS IN THE CHEMICAL PROCESS INDUSTRIES 91
There can be discharge gates at each end of the upper mixer, which permit the wetted mixture to be introduced either directly into a second mixer or into the high-speed fine-grinding pulverizer and then into the second mixer.
Table 14. Physical and Hazardous Properties of Chlordane
Chemical Designations
-
Synonyms: Chlordan, 1,2,4,5,6,7,8,8-0ctachloro- 2,3,3a,4,7,7a-Hexahydro-4,7-Methanoindene, Texichlor; Chemical Formula:C*,H6Cl,
. . , . , . ,
Observable Characteristics
-
Physical State (as normally shipped): Liquid;Color: Brown; Odor: Penetrating; aromatic; slightly pungent, like chlorine Physical and Chemical Properties - Physical State at 15 "C and I atrn. : Liquid; Molecular Weight: 409.8; Boiling Point at 1 atm. : Decomposes;
Freezing Point: Not pertinent; Critical Temperature: Not pertinent; Critical Pressure: Not pertinent; Specific Gravity: 1.6 at 25 "C (liquid); Vapor (Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): Not pertinent;
Latent Heat of Vaporization: Not pertinent; Heat of Combustion: -4,000, - 2,200, -93; Heat of Decomposition: Not pertinent
Health Hazards Information
-
Recommended Personal Protective Equipment: Use respirators for spray, fogs, mists or dust; goggles; rubber gloves; Symptoms Following Exposure: Moderately irritating to eyes and skin. Ingestion, absorption through skin, or inhalation of mist or dust may cause excitability, convulsions, nausea, vomiting, diarrhea, and local irritation of the gastrointestinal tract; General Treatment for Exposure:INHALATION: Administer the victim oxygen and give fluid therapy; do not give epinephrine, since it may induce ventricular fibrillation; enforce complete rest. EYES: flush with water for at least 15 minwes. SKIN: wash off skin with large amounts of fresh running water and wash thoroughly with soap and water. Do not scrub infected area of skin. INGESTION: induce vomiting and follow with gastric lavage and administration of saline cathartics; ether and barbiturates may control convulsions; oxygen and fluid therapy are also recommended. Do not give epinephrine. Since no specific antidotes are known, symptomatic therapy must be accompanied by complete rest.; Toxicity by Inhalation (Threshold Limit Value): 0.5 mg/m3; Short-Term Exposure Limits: 2 mg/m3 for 30 min; Toxicity by Ingestion: oral LD,, = 283 mg/kg (rat); Late Toxicity: Possible liver damage; loss of appetite or weight.;
Vapor (Gas) Irritant Characteristics: No data; Liquid or Solid Irritant Characteristics: No data; Odor Threshold: No data.
92 CHAPTER 2
Table 15. Physical and Hazardous Properties of Benzene Hexachloride (Lindane) Chemical Designations
-
Synonyms: BHC, 1,2,3,4,5,6-Hexachlorocyclohexane Lindane; Chentical Forrnula: C&C&
Observable Characteristics - Physical State (as normally shipped): Solid;
CoZor: Light tan to dark brown; Odor: Characteristic
Physical and Chemical Properties - Physical State at I5 "C and I atm. : Solid; Molecular Weight: 290.83; Boiling Point at I atm. : Not pertinent;
Freezing Point: Not pertinent; Critical Temperature: Not pertinent: Critical Pressure: Not pertinent; Specific Gravity: 1.891 at 19 "C (solid); Vapor
(Gas) Density: Not pertinent; Ratio of Specific Heats of Vapor (Gas): Not pertinent; Latent Heat of Vaporization: Not pertinent; Heat of Combustion:
Not pertinent; Heat of Decomposition: Not pertinent
Health Hazards Information - Recommended Personal Protective
Equipment: Respiratory protection; ensure handling in a well ventilated area.;
Symptoms Following Exposure: Hyperirritability and central nervous system excitation; notably vomiting, restlessness, muscle spasms, ataxia, clonic and tonic convulsions. Occasional dermatitis and urticaria. ; General Treatnzent for Exposure: Gastric lavage and saline cathartics (not oil laxatives because they promote abortion). Sedatives: pentobarbital or phenobarbitol in amounts adequate to control convulsions. Calcium gluconate intravenously may be used in conjunction with sedatives to control convulsions. Keep patient quiet.
Do not use epinephrine because ventricular fibrillation may result; Toxicity by Inhalation (Threshold Limit Value) : 0.5 mg/m3; Short-Term Exposure Limits:
1 mg/m3 for 30 minutes; Toxicity by Iizgestiort: LD,, 0.5
-
5 glkg (Technical Mixture); LD,, 50-
500 mg/kg (rat) (Gamma Isomer-
Lindane); Late Toxicity: Mutagen to human lymphocytes; Vapor (Gas) IrritantCharacteristics: Moderately irritating. Workers will not usually tolerate moderate to high concentrations. ; Liquid or Solid Irritant Characteristics:
Minimum hazard. If spilled on clothing and allowed to remain, the chemical may cause smarting or reddening of skin.; Odor Threshold: No data.
From the second mixer, a discharge gate with a built-in feeder screw conveys the mixture to a second elevator for transfer to the holding bin where the finished batch is available for packaging. For more extensive information and additional chemicals, the reader should refer to the Handbook of Industrid Toxicology and Hazardous Materials (Marcel Dekker Publishers, 1999). Additional references
HAZARDS IN CH&WAL PROCESS INDUSTRIES 93
and resources are cited at the end of this chapter where the reader can find a multitude of safety information and sites to link to on the Internet.