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Chemical Safety Data Sheet SD-18
PROPERTIES AND ESSENTIAL INFORMATION FOR
SAFE HANDLING AND USE OF
ETHYLENE DICHLORIDE
Chemical* in ony form can be safely stored, handled or used if the physical, chemical and hazardous properties are fully under stood and the necessary precautions, including the use of proper safeguards and personal protective equipment, ore observed.
REVISED 1971
MANUFACTURING CHEMISTS ASSOCIATION
1825 CONNECTICUT AVENUE. N. W.
WASHINGTON, 0. C. 2000#
Si 2
table of contents
Pago Preface ................................................................................................................. 4
1. NAMES ......................................................................................................................... 5
2. PROPERTIES .................................................................................................................. 5
3. HAZARDS 3.1 Health Hazards ........................................................................................ 3.2 Fire Hazards ............................................................................................. 3.3 Instability Hazards .................................................................................. 3.4 Reactivity Hazards ..................................................................................
6 6 6 6
4. ENGINEERING CONTROL OF HAZARDS 4.1 Building Design ............................................................................................... 4 2 Equipment Design ...................................................................................... 4.3 Ventilation ............................................................................................... 4.4 Air Analysis ............................................................................................ 4.5 Electrical Equipment ......................................................................................
6 7 7 7 7
5. EMPLOYEE SAFETY 5.1 Employee Education and Training ..................................... 5.2 Personal Protective Equipment ...............................................................
8 8
6. FIRE FIGHTING ............................................................................................................ 10
7. SHIPPING, LABELING, HANDLINGAND STORAGE
7.1 Shipping Containers ................................................................................ 10
7.2 Precautionary Labeling or Identification ............................................... 10
7.3 Handling ......................
12
7.4 Small Containers ...................................................
12
7.5 Non-Bulk Containers ................................................................................ 12
7.6 Bulk Containers ......................................................................................... 12
7.7 Storage .............................................................................................................. 13
8. TANK AND EQUIPMENT CLEANINGAND REPAIRS .......................................... 14
9. WASTE DISPOSAL....................................................................................................... 16
10. MEDICAL MANAGEMENT 10.1 Health Hazards ...................................................................................... 16 10.2 Preventive Health Measures ...................................................................... 17
11, FIRST AID ..............................................................................................
18
3
Chemical Safety Data Sheet
ETHYLENE DICHLORIDE PREFACE
Ethylene dichloride is a flammable liquid which produces toxic and flammable vapor when mixed with air. It is toxic by inhalation, by contact with the skin or mucous membranes or by ingestion.
The threshold limit value has been established at 50 ppm. Exposure to higher concentrations of vapor causes irritation to the eyes, nose and throat. Symptoms may also include nausea, vomiting and drowsiness.
Gaseous products of cambusion of ethylene dichloride contain noxious gases such as hydrogen chloride and phosgene. Sources of ignition should be eliminated from work areas.
The full text of this chemical safety data sheet should be consulted for details of the hazards of ethylene dichloride and suggestions for their control.
FIRST AID-SEE PAGE 18
4
-L01022
Cijl'ihiCliI Siijciy DiiLi Sheet
ETHYLENE DICHLORIDE
i-j i
SD-48
1. NAMES
Chemical Names: Common Names: Formula:
1,2-Dichlorocthanc, Ethylene Dichlondc Ethylene Dichloride, Ethylene Chloride, EDC CH,C1-CH,C1
2. PROPERTIES
2.1 GRADES AND STRENGTH Commercial grades in general use.
2.2 PROPERTIES AND CHARACTERISTICS
Physical State.......................................... ,,........ Flammable (Explosive) Limits (%volinair) Flashpoint (open cup) (ASTM D1310).......
(closed cup) (ASTM D56)........,
...Liquid ... 6.2 to (5.9 ... 18.3C, (65F.) ... 13C. (55F.)
Autoignition Temperature (ASTM D286) ...
,...413"C. (775F.)
Boiling Point (ASTM D1078)............
...,81.39C. (182F.)
Color.......------ --------------- -------- --------------
_Clear
Corrosivity.... ______________ _____ - --
...Noncorrosive at normal atmospheric ternperatures when dry (moisture-free). In contact with water at elevated tempera tures ethylene dichloride corrodes iron and certain other metals.
Critical Pressure
...49.2 atin
Critical Temperature............. ....... ......................................... ........ 295.7C. (564F.)
Dcliqucsccnce-Hygroscopicity.............................. ....... ..................No
Density (Liquid, grams/milliiitcr (<i) 2QC., 68F.)............... -- 1.252
Electrical "Group" Classification (NFPA Electrical Code)..........Class 1 Group D
Heat of Combustion (calorics/gram) ......................-................. 2,993.3
Heat of Vaporization (calorics/gram)....................... .................... 77.3
Heat of Fusion (calorics/gram)..................... --............--.............-21.3
Light Sensitivity......................... ...... ........ ........ .......-....................... Yes. Stow decomposition.
Melting Point (Freezing point)............ .......................------------------ 35.3C. (-- 31.5F.)
Odor_____________ ______ ____ ____ _____________________ ____ Chloroform-like odor, sweet teste
5
SI,.-ft
SD-18
Manijiaciijrifuj
Association
Ethylene Dichlondo
Odor Threshold ................................................
HKl ppm (vul.)
Specific Gravity (grams/mtlhliler Ui 20/4oC,)
1.256
>
Vapor Density (air = 1) (grams/litcr).... ........
3.42
< Vapor Pressure if? 20C., 6SF...................... .
67 mm HG
Viscosity (millipoisc) ....................................
8.42
Water Solubility, percent by weight,
ethylene dichloridc in water........................
0 8[ (,,' 20C. (68F.)
water in ethylene dichloridc........'.......... ......
0.15 tif 20'C. (68F.)
Threshold Limit Value ............................. ...........
50 ppm (25"C. and 760 mm Ifg) vapor or en.s: 2(H) mg/nv1 particulate in air (1970 ACGIH)
i,
3. HAZARDS
3.1 HEALTH KAZAKHS
Ethylene dicfilottdo is toxic by inhalation, by pro longed or repented contact with the skin or mucous membrane, or when taken by mouth,
3.1.1Warning lh-openifs
F.thylcnc dichloridc has a sweetish ehlorofoi inlike odor. High concent!alums aie nritalmg to eyes, nose, and thiont. Lower concern rat ions which through cliiomc exposme may pioduce systemic damage are not always detectable by smell.
3.2 1`IKE KAZAKHS
3.2 1 Ethylene dichlonde is a llammahle liquid and produces toxic tind flammable vapor xvhen mixed with air at ambient conditions. Precautions such as eliminating ignition sources, inerting, bond
ing, compliance with National ('ire Codes, etc, should be taken when handling this mateiial. Gaseous products of combustion contain noxious gases such as hydiogen chloride and phosgene.
3.3 INSTABILITY KAZAKHS
Ethylene dichloridc is thermally stable under nor mal conditions.
3.4 KEACTIVITY KAZAKHS
Ethylene dichloridc undergoes no known hazard ous or violent chemical reaction; however, the matclial is a Hummable liipiid (Flash Point 55"F.). Flammable Limits are from 6.2% lo 15.9% in air; and niitoigiiilion temperature is 115^. Sec section 6 on fire fighting.
7
4. ENGINEERING CONTROL OF HAZARDS
(See NFPA No. 30)
4,1 BUILDING DESIGN
4.1.1 Processes and storage facilities should not be located near open flames or lugh-temperaturc operations since ethylene dichloridc is Hummable and decomposes at high temperatures to fonu corrosive, irritating and otherwise undesirable products.
4.1.2 Standard fire walls are recommended for Ihe isolation of larger equipment and storage tanks. Fire partitions having a lire resistance of 1-3 hours may be used to isolate areas involving ethylene dichloridc from other areas.
4.1.3 Not less than two means of exit should be provided front each separate rttom or building in which ethylene dichlonde is stored, handled, or used. No portions of such a room or building should he farther than 75 feel from the nearest exit. Additional exits should be provided depending upon (he number of persons in the building, (See NFPA Standard No. 101 Life Safety Code.)
4.1.4 All exit doors should open out in the direc tion of travel and should be provided with panic hardware. Fire doors should open out in the direction of travel and be of an approved type.
5iSKiVilf
SL 101024
Ethyicne Dichlorido
Manufacturing Chemists Association
v it
SI
4.1.5 Explosion venis arc a safeguard to reduce destruction damage to buildings, ducts, mixers, blend ers, driers, and similar equipment in which flammable vapors arc liable to concentrate. Approved explo sion venting windows, roof and wall panels, skylights, light windows, diaphragms, etc. arc available to relieve pressures caused by burning vapors. Since the required area of explosion vents depends upon such factors as the intensity of an explosion, vapor tem perature, type of structure, the type of vent closure, etc., the determination of vent ratios should be made by experienced engineers and safety and fire protec tion specialists, Consideration may he given to ex plosion suppression systems, (Reference: Guide for Explosion Venting, NFPA No. 68.)
4.1 6 Fire resistive stair enclosures with selfclosing fire doors may be required for multi-storied buildings.
4 1,7 The need for segregating floor drains from sanitary or process sewer systems should be con sidered.
4.2.6 It is essential for safety that the cquipn be used and maintained as recommended by manufacturer.
4.2.7 Clean water m ample quantities slumUi immediately available at unloading stations Stand deluge type safety showers, blankets, and special baths for flushing the eyes are recommended.
43 VENTILATION
4 3.1 The workroom or operating area may provided with general ventilation. However, sin ethylene dichloridc is heavier than air, mechanical c haust ventilation, preferably of the downdiaft typ should be provided. The most important consider; turn in ventilation should be to insure a substanti. air How away from the work area to prevent the ui safe accumulation of explosive mixtures and/or toxi concentrations. When mechanical ventilation is user the electrical equipment should meet National Elet trie Code requirements.
i
4.2 EQUIPMENT DESIGN
4.3.2 Under abnormal conditions, such as leak or spills, emergency ventilating equipment may b necessary. It should be available for immediate use.
4.2.1 Vents from relief valves and process vents should be to a safe locution.
4.3.3 Forced draft ventilating systems should be so arranged that a fire in the building will auto
4.2.2 Totally enclosed systems arc preferable for processes handling ethylene dichloridc. Opening equipment during the operation, or removal of mate rials should be avoided. A commercial combustible gas indicator is usetul for pci iodic inspections, or to
matically shut them down. They should also he pro vided with remote manual controls. Local ventilation at relief points is better than depending on dilution ventilation. All ventilating systems require periodic inspection.
locate leaks.
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4.2.3 Partially enclosed systems: Processes where solid materials arc extracted or treated with ethylene
4.4 AIK ANALYSIS
#3
!
dichloridc are usually totally enclosed, but part of
4.4.1 A program of air analysis will be required
the equipment is opened periodically to remove
to assure control of-iofoilation exposures below the
solids, A method of complete removal of the vapors
threshold limit oC.SO-ppm. Continuous monitoring
from residual materials before the equipment is
will afford an early warning of slow developing leaks
opened should be provided. Positive means of pre
and a record of personnel exposure.
venting a back up of fumes into any central inert gas supply that may be used should be provided.
4 4.2 When checking concentrations of ethylene dichloridc in the air, care is required to make certain
4.2 4 Open container: High concentrations of
that the sample is representative of the air breathed
\
hazardous vapors may be discharged from open or partially open containers. Open equipment should
by the workers, and of the daily fluctuations which may occur.
he avoided, but if such equipment is necessary, the working area should be provided with mechanical ventilation to prevent the accumulation of hazardous vapors.
4 4 3 It should he kept firmly in mind that the use of insliiimcnts and test procedures for the detec tion of ethylene dichloridc in the air requires spe cially named personnel.
4.2.5 Processes where ethylene dichlonde is be
ing used should be designed so that the operator is piotected from contact with this material in any of
4 5 ELECTKICAL EQUIPMENT
its physical states. Adequate ventilation and good operating procedures should be established which assure maximum security and protection for the operator.
4.5.1 To help insure safe operation, wiring should be installed in accordance with the National Electrical Code, Article 500.
7
I
T.ayuwu--w
SL 101025
jai
5D*18
M a n u f Cidur nq ChQ;M- fs AssoocifiOn
Ethylene Dichloride
4,5 2 In areas where ethylene dichloride vapors arc present dunng normal operations, motors, con trols switches, lights, etc., should confonn to Class 1, Group D, Division l (Explosion Proof) electrical classification.
4.5 3 In areas where ethylene dichlonde vapors arc not normally present, or may he present only dur ing emergency Conditions, the electrical equipment should conform to Class 1. Group D, Division II electrical classification, (National Electrical Code, Article 500.)
4 5 4 No healing apparatus capable of reaching the auioigmtmn temperature of 775F, should be used Flash lights, if used, should be a type approved for the exposure.
4.5 5 Ethylene dichloride flowing through or be ing discharged from a line generates static electricity.
In areas wlieie ilammablc vapor-air mixtures may exist, electric,illy isolated sections of metallic piping should be bonded to the icst of the system (or gioimded) to prevent eMcinal spmks which might produce ignition. (See Recommended Practice on Static Electricity, NFPA No. 77.)
4 5.6 Before ethylene dichloridc is poured or dischmgcd ft om one metal container to another, the two vessels should he either grounded or electrically interconnected by bonding. Any ground this is ade quate for power cucuits (or lightning protection) is more than adequate for protection against static electricity. I his applies to all metal and pipe lines. Where drive hells are necessary, conductive "V" belts arc iccommended. Pulley and drive shafts should be grounded. Nonconductivc drive belts arc liable to accumulate a static charge, and their use should be avoided.
5. EMPLOYEE SAFETY
5.1 EMPLOYEE EDUCATION AND TRAINING
5.1.1 Safety in handling ethylene dichloridc de pends upon the effectiveness of employee education, training, and supcivisum. Unauthorized and untriMiied employees should not be permitted in areas where it is being handled.
5.1.2 The education and training of employees to work safely and to use the personal protective equip ment or other safeguards provided for them is a responsibility of supervision.
5 1.3 Employee education and training should emphasize the need of handling ethylene dichloridc according to approved safety methods, in order to avoid spilling or splashing, leaks, inhalation of the vapor, or ingestion.
5.1.4 Before being placed on the job, employees should he instructed thoroughly in the proper han dling of ethylene dichloride. Older employees should be rcinstructed periodically. Each employee should he instructed not to use ethylene dichloridc for per sonal cleaning purposes.
5.1 5 Each employee should know the location, purpose, and maintenance of personal protective equipment and he thoroughly tiained when and how to use this equipment.
5.1 6 Each employee should know the location of safely showers, blankets, eye baths or bubbler drinking fountains for flushing the eyes, and hose lines.
5.1.7 Employees should be trained to report to the proper authority all suspected leaks or equipment failures, and any signs of illness or skin irritation.
5.1.8 Each employee should know what to do in an emergency and should realize the necessity for prompt application of first aid m ease of contact with ethylene dichloridc liquid or exposure to the vapor.
5.2 PERSONAL PROTECTIVE EQUIPMENT
5.2.1 Availability ami U*e
Personal protective equipment is not an ade quate substitute for good, safe working conditions, adequate ventilation, and intelligent conduct on the part of employees working with ethylene dichloridc. It is, however, in many instances the only practical means of protecting (he worker, particularly in emergency situations. One should appreciate that personal protective equipment protects only the worker wearing it, and other unprotected workers in the area may be exposed to danger.
The following personal protective equipment should always be used for (he purposes mentioned and us specified in HEALTH HAZARDS, and in other sections of this Data Sheet.
5.2.2 Eye Protection -
5.2-2.1 Cup-type plastic or rubber framed goggles, equipped with the approved impact resistant glass or plastic lenses, should be worn whenever there is danger of the material coming in contact
8
can
101026 S3j
Sana
with the eyes, sticit as when handling bulk t|u;\ntities, when there is danger of splashing or if the material is under pressure,
5.2.2.2' Metal or plastic rim safety spectacles with side shields may be used when continuous eye protection is desirable, as in laboratories.
5.2.2 3 Plastic shields (full length, 8" tnininiuni) with forehead protection may he worn in addi tion to chemical safely goggles where complete face protection is desirable. Chemical safety goggles should always be worn as added protection where there is danger of material striking the eyes from un derneath or around the sides of the face shield.
5.2.3 Respiratory Protection
5.2.3.1 Respii atoi y protection equipment must be carefully maintained, inspected, cleaned, and sterilized at regular intervals, and always before use by another person. Personnel wearing such equip ment must be carefully instructed in its operation and limitations. Available types arc described below.
(a) Self-contained breathing apparatus which permits the wearer to carry a supply of air compressed in the cylinder allows considerable mobil ity. 7he length of time a self-contained breathing apparatus provides pmtection varies according to the amount of air carried.
(b) Positive pressure hose masks which arc supplied by blowers requiring no internal lubrication. The wearer must be able to use the same route for exit as for entrance and must take precautions to keep the hose line free of entanglement. The air blower must be placed in an area free of contaminants.
(c) Air-line masks, supplied with clean compressed air, suitable for use only where conditions will permit safe escape in ease of failure of the compressed air supply. These masks arc usually sup plied with air piped to the area from a compressor. It is essential that the air is not contaminated by oil decomposition from inadequate cooling at the com pressor. Unless the air supplied from a plant system has been ccitilied as "breathing air" and is under regular coniiol to make sure it is not contaminated, it is usually safer to use a separate compressor of the type not requiring internal lubrication. Pressure re ducing ami relief valves as well as suitable traps and fillers, must he installed at all mask .stations. An alternative airangemenl fiequcnily used is high piessure breathing air fiom stamlaul (200 cu, ft.) cylinders, with a demand type valve and face piece, 'Ibis airungement may also he used wiih 50-100 lb. clean piped plant air and as an additional precaution with the demand mask, a small cylinder of com pressed air may he worn for use as an emergency escape from the area. Consult a reliable safety equip
ment doalei for details on the proper use of Bureau of Mines approved equipment.
(d) Industrial Canister-Type Gas Masks, equipped with full face pieces and approved by the U S, Bureau of Mines, fitted with the proper canister fur absorbing vapor, will allord protection against concentrations mu exceeding 2 inr cent by volume when used in accordance with mamifaeturei's instruc tions. The oxygen content of the air must not be less than 16 per cent by volume. The masks should be
used for relatively short exposure periods only and when there is no odor of ethylene dichloridc inside die
facepiece. They are not recommended for use in an emergency since, at that time, the actual vapor rnnu'litratum is unknown and an oxygen deficiency may exist. I he wearer must he warned to leave the con taminated area immediately on detecting the odor of a harmful vapor. This may indicate that the mask is not functioning pmpcily, that the vapor conecnnniton is loir high, that the canister is exhausted, or that the mask is not properly fitted. Because of the limitations outlined restricted usage of canister masks
is considered appropriate.
NOTE: Where other gas having little or no odor may he encountered in addition to ethylene tlichhnuh', the mask should he equipped with an "all purpose canister" and a "timing device" as approved by the U.S, Bureau of Mines.
(c) Chemical Cartridge Respirators may lie used to avoid inhaling disagreeable but relatively haimlcss concentrations of ethylene dichloride vapor. These respirators, however, arc not recommended for protection where toxic quantities may be en countered.
CAUTION: Filter-type respirators do not
offer protection against gases or O- deficiency and
arc unsuitable for use when working with ethylene
dichloridc,
*
5.2.4 Head I'rotcclioti
5.2.4.! "Hard" hats should be worn where there is danger from falling objects. If "hard" hats are not considered necessary, soft brimmed hats or caps may be worn to give protection against liquid leaks and splashes.
5,2 4.2 "Bump caps" are satisfactory in areas whcie thcie is luile or no ha/.aid Itotn falling objects, they will give pioteelion from liquid leaks and splashes.
5.2.5 Foot I'rotoetiou
5.2.5.1 F.lhylene tlieliloride attacks natural rubber. Leather safety shoes with built in toe caps
9
SL 101027
R
SD-J8
A hoc,c:t< on
ElhySono DicMoride
are recommended for workers hrmtiliny conlamci'5 of ethylene dichlnridc. Overshoes of a moie impervi ous material, such as Neopienc. may he worn over leather safety shoes. Footwear should be thoroughly cleaned and ventilated after contamination.
5.2.6 Body, Skin, and Hand Protection
5 2.6.1 Sustained or intermittent skin contact with liquid ethylene dichloride may produce derma titis at the site of contact. It is imperative that con taminated clothing be removed promptly and laun-
deied or tluuuughly tilted before le-nse. AITectcd areas ol the body should be washed thoroughly with soap and water (except the eyes). As a general hy gienic meastne. facilities for personal cleanliness
should be piovided, and washing before lunch and at the end of the day should be encouraged. Clothing made of Neopienc or other impervious mateiia! may he worn to protect the body against ethylene dichloride splashes. These garments must be cleaned inside and out should they be contaminated. Protec tive clothing should be examined frequently and dis carded at the first evidence of deterioration.
4
6. FIRE FIGHTING
6.1 GENERAL
6.1.1 The following extinguishing agents may be used on ethylene dichlondc hies: water spray or "fog," foam, caibon dioxide, and dry chemical. For large ethylene dichloride fires, the most effective agents are water spray and foam. Exposed equip ment should be cooled with water.
6.1.2 The technique of smothering an ethylene
dichioiidc fire by gently applying water, and then letting it layer out has been used with some success.
6.2 SPECIAL HAZARDS
6.2 1 The products of combustion contained in the smoke contain noxious gases such as hydrogen, chloride and phosgene which arc both toxic and cor rosive. Self contained breathing apparatus should be worn.
7. SHIPPING, LABELING, HANDLING AND STORAGE
SHIPPING CONTAINERS
7.1.1 Ethylene dichloride is classified by the De partment of Transportation as a fkintiiudde liquid. Unless exempted, it must be packed in DOT specifi cation containers when shipped by tail, water, or highway, and all of the DOT Regulations regarding loading, handling, and labeling must be followed. For a complete list of authorized containers sec 173.118 and 173,119 of the Regulations.
7.1.2 Usual Shipping Containers
7 1.2.1 Wooden boxes, DOT Spec. ISA, 1513, ISC. I6A, 19A, or 1913, with inside metal, glass or eaithcnwarc containers, maximum capacity of inside containers is 10 gallons for metal and one gallon for glass or earthenware except that single inside con tainers up to 3 gallons arc permitted. Sec DOT Regulations 173.119(8).
7.1.2.2 Fibcrboard boxes, DOT Spec. 12B, with inside containers of glass, plastic or metal not over one gallon each. Packages may not contain more
than four glass containers if their capacity exceeds live pints each.
7.1.2-3 Metal drums, returnable, DOT Spec. 5, 5A, 513, SC, or 5M. Recommended maximum size: 55 gallons. DOT Regulations 173.119(2).
7.1.2.4 Metal drums, nonreturnablc, DOT Spec. 17C and 17E and 17H. DOT Regulations 173.119 (3) (4).
7.1.2 5 Tank cars, DOT Spec. 103, I03W, 104, 104W, or 105A. DOT Regulations 173.119 (12) and pertinent parts of 179.
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7 2,2 `1 he M.mutnetuiing Chemists Association recommends that a I ] coiit amci s of ethylene diehlonde should bear a label as shown. The text is designed
ethylene didilomle ami other dangcious articles, lank (nicks must he mat bed as required by DOT Regulations 177.823(b).
ETHYLENE DICHLORIDE
WARNING! FLAMMABLE HARMFUL IF INHALED
Keep away frorn heat, sparks, and open flame. Avoid breathing vapor. Keep container closed. Use with adequate ventilation. Avoid prolonged or repeated contact with skin. Do not take internally.
FIRST AID: If inhaled, remove to fresh air. If not breathing give artificial respiration, preferably mouth-to-mouth. If breathing is difficult, give oxygen. Call a physician.
In case of: Fire--Use water spray, foam, dry chemical, or COj. Spill or Leak--Flush area with water spray.
MCA Chemical Safety Data Sheet SO-18 available.
for the product as shipped for industrial use. It should be used in addition to or in combination with tiny specific wording required by law. Since individual statutes, regulations, or oidinances may require that particular information be included in a label, that certain information be displayed and in a particular manner, or that a specific label be allixcd to a con tainer, the use of this label text will not necessarily insure compliance with such laws. Such laws include the Federal I bunrdous Substances Labeling Act, Fedcial Insecticide, Fungicide and Rodenticidc Act, and similar stale and municipal legislation.
7 2 3 The proper shipping name is ctliylcnr dirltliiriile and must show on the outside of shipping containers.
7.2 4 Tank cars and boxcars, must bear the DOT "Dangerous," placard as specified in DOT Regula tion 174,552. Motor vehicles or trailers transporting 1,000 pounds or more gross weight of ethylene dichloride must be marked with the FLAMMABLE placard or with the DANGEROUS placard when transporting 1,000 pounds or more gross weight of
7.2.5 Unless exempted, packages containing in side conitiineis of one quart capacity or larger must lie packed with filling holes up and outside containers must he plainly marked "This Side Up." Refer to DOT Regulation 173.401(c) and 173.118.
7.2.6 Unless exempted by 173.118, drums and each box containing inside containers must bear the DO I' "Red Label" for flammable liquids as set forth in DOT Regulations 173.405(a). Exempt quantities must omit label in accordance with 173.404(b).
7.2.7 DOT Regulations require that the red label for the Hummable liquids must be removed, defaced, desiioycd. or covered by the DOT while "Empty" labels, before empty containers are returned to the shipper. The DO T "Dangerous" placards on the side and ends of cars must be removed or reversed in a manner required by DOT Regulation 174.562 after emptying.
7 2.8 The empty tank car must be offered to the receiving carrier cither without placards, or prefer ably with four (4) "Dangerous--Empty" placards.
11
SL 101029
Wj n,f jrw t^r n J `^OQin ,`y AsiOCiQl`0^
Eihyicnc Diehloridc
7.3 1IANDL1NC--GENERAL
7.3 1 All precaiuions must be taken to guard against health and lire hazards whenever ethylene diehloridc is handled. The area should be posted with NO SMOKING or other appropriate warning signs as required. If leaks or spills occur, only prop erly trained personnel should remain in the area. Leaking containers should be removed to the out doors or to an isolated well ventilated aiea, and the contents transferred to other suitable containers. All spills should be flushed away promptly with water,
7,3.2 I'he unloading dock and the sm rounding men should be considered as a Class l Clump D haz ardous location as defined by the National Electrical Code. Conformance of electrical installation m the aiea to Division 1 or Division 2 requirements of the NEC depends upon such local conditions as prox imity to other hazardous locations, congested areas, etc.; therefore, a qualified tire protection engineer or the lire insurance carrier concerned should be con sulted.
7 3.3 Railroad locomotives and automotive equipment capable of causing ignition should be ex cluded from the dock or vapor areas during both the unloading and loading operations.
7.4 SMALL CONTAINERS
7.4.1 The storage and handling of ethylene diclrloridc in glass containers is not recommended ex cept in small containers for laboratory use. Amber glass containers arc recommended. Five gallon metal cans may also be used. Safety cans with pouring outlets equipped with tight-fitting caps or valves normally closed by springs and with fire baffles in the outlets should be used.
7.4.2 Indoor storage areas should be protected with automatic-sprinklers. See NFPA No. 30.
7.4.3 For waste disposal of small containers of ethylene dichloride and of materials contaminated with it, see Section 9.
7.5 NON-HULK CONTAINERS
7.5.1 Drums, Metal
7.5.1.1 Drums should be unloaded carefully to prevent damage. Do not drop or bump them.
7.5.1.2 Each shipment should be examined carefully for leaking drums. If any are found, they should be bandied will) pniiiculnr e.ue by liuning tlie leaking part up, and should be icmovcd to a safe place where die leakage can be stopped or die con tents transferred to a sound container.
7.5.1.3 Before emptying, substantially support the drums and block them to prevent movement.
Bond die eli urn or discharge nozzle to the receiving container if the discharge system is open. See NFPA No. 77.
7.5.1 4 To remove the body plug, place the bung up, block the drums to prevent movement, and use a bung or plug wrench. Stand to one side and face away during the operation. After the plug starts, give it one full dun. II internal pressure exists, allow it to vent to atmosphciic pressure; then only should the plug be loosened further or removed.
7 5.1.5 'flic preferable safe method for empty ing di urns is by pump. Electrical pumps should have explosion pi oof motors except in freely ventilated areas. If di inns aie emptied by gravity, the faucets should he self closing. Pressure should never be used, especially air pressure.
7.5,1.6 Metal drums to be returned to the sup plier must be completely drained and all openings (for bungs, plugs, ele.) must be closed lightly, DOF regulations concerning return labeling must be ob served. If a metal drum is to be scrapped, it should be steamed to remove traces of ethylene diehloridc vapor and rendered impossible for reuse by crushing or piercing.
76 HULK CONTAINERS
7.6.1 Tank Trucks
7,6.11 The use of tank trucks is authorized by DOT Regulations. Section 173.115 to 173.119 in clusive and Part 177 of those regulations must be followed where applicable. Local rules, regulations and ordinances must be observed.
7.6.1.2 Ordinarily all operations concerning the tank truck and its appurtenances (fittings, pump, hose, etc.) arc the responsibility of the operator. Therefore, loading and unloading operations should be carried out by reliable and properly instructed employees in cooperation with him. The shipper should be consulted for details on proper unloading procedure.
7.6.1.3 Before unloading a tank truck, the en gine must be stopped and not started again during die entire loading or unloading operation. Truck brakes should be set and the wheels blocked.
7.6.1.4 To prevent sparking due to static elec tricity generated by liquid llow a bond should be established between the loading pipe and the cargo lank beloie luuding/unloading operadons are started. See NETA No, 77.
7.6.1.5 It is preferable that truck loading/ unloading facilities be level and paved and so located that the truck can he easily, and safely maneuvered to the unloading spot.
12
0
SI. 101030
cthyionc 0C"or.o
V .jMC.U.'i vfl
Wo^uoi Sh*t
SD-l*
7.6.1.6 Air pressure should never he used for unloading tank trucks of ethylene dichloridc.
7.6.1.7 Dnmagn Enronlr--In ease a tank truck of ethylene dichloridc becomes damaged cnroute so that it cannot proceed safely to its destina tion, every cITort should he made to park it where it will not endanger trafTic or property. The police and fire department should be notified and the public warned to stay away. The truck should be parked, if possible, in a vacant lot and away from an area in which there is a concentration of people, Follow MCA Chem Card precautions as available or contact producer for safe disposal instructions.
7,6.2 Tank Cars
7.6.2.1 For general and detailed instructions regai ding the unloading of tank cars containing flammable liquids, see MCA Manual Sheet TC-4 and the Regulations of the Department of Transpor tation. A few of these instructions follow.
7.6.2.2 Shipper's instructions for unloading should always be followed, and all caution markings on both sides of tank or dome should be read and observed.
7.6.2.3 fn the event of a tank car fitting failure or leak that cannot be stopped by following previous instructions from the shipper, immediately telephone or wire him for further instructions.
7.6.2.4 Sec that the train or engine crew ac curately spots the car at the unloading line. The un loading track should be level. The brakes should be set, wheels blocked by standard rail clamps, blue warning signs placed and other safe practices fol lowed as outlined in MCA Manual Sheet TC-4,
7.6.2.5 Derails should be placed at one or both ends of the unloading track approximately one ear-length from the car being unloaded, unless the car is protected by a closed and locked switch or gate.
7.6.2.6 All tools and implements used in un loading the car should be kept free from oil, dirt, and grit.
1.6.2.1 Before the manhole cover or the outlet valve is opened, the tank car should be relieved of all internal pressure.
7.6.2.8 Tank cars should be unloaded by means of an appiovcd pump through ihe dome con nection rather than through ttic bottom outlet. Air pressure must never be used. The car should be vented through an approved flame art ester during unloading.
7.6.2.9 After tank cars have been moved, it is important that they be inspected carefully, since leaks may develop in transit.
7,6 2.10 As soon as a lank car is completely unloaded, disconnect the unloading line and replace closures on all tank openings. Close and securely fasten the dome cover. DOT Regulations concerning return placarding should be observed.
7,6 2.11 Empty tank cars should be returned as promptly as possible, in accordance with instruc tions received from the shipper. The shipper's rout ing instructions should always be strictly followed.
7.7 STORAGE (Sec NFPA No. 30)
Ethylene dichloridc is noncorrosivc at normal at mospheric temperatures when dry (moisture-free). In contact with water at elevated temperatures ethyl ene dichloridc corrodes iron and certain other metals.
7.7.1 Indoor Storage
7.7.1.1 When filled drums or other containers arc stored indoors, they should be stored in noncombustible, well ventilated structures. Consult your state and city Fire Codes and your insurance carriers.
7.7.1.2 When filled drums or other containers are stored in separate storage rooms, trapped floor drains should be provided. The floors' should be pitched to the drains and the latter should lead to a safe location and be properly trapped. In case no drains arc provided, four inch curbs or a drained gutter, covered with an appropriate grill, should be constructed at door openings. In either ease, only those with proper protective equipment should at tempt to clean up ethylene dichloridc spills.
7.7.1.3 Storage areas should be provided with automatic sprinklers or some adequate extinguishing system desirable on interior storage. (See NFPA No. 30).
7.7.1.4 Oxidizing materials should not be stored nearby.
7.7.1.5 Since ethylene dichloridc is light sensi tive, small quantities should be stored in amber glass bottles.
7.7.2 Bulk Storage
7.7.2.1 Iron and steel arc suitable metals for storage tanks.
7.7.2.2 Atmospheric tanks should he located at least 100 feet and pressure tanks at least 150 feet I mm ignition sources such as boiler houses. Tank suppoits should be of reinforced concrete, brick, or steel. If steel is used, it should be fireproofed. Tanks should be located at distances from property lines, buildings, and fiom each other as required by any governing statutes, regulations, or ordinances, and
13
SL 101031
Sr**# f
so-ia
Ethylene Qicnionde
hy the authority having jurisdiction. (See NFPA No. 30).
7.7.2.3 Where adequate spacing and segrega tion arc not maintained, protection against exposure to fires may be required. The use of automatic sprinklers or water spray systems may be necessary.
7.7.2.4 Electrical installations should conform to the requirements of the National Electrical Code for Class I, Group D hazardous locations.
1.1.2.$ Each tank should he equipped with a vent terminating outdoors and protected hy a flame arrester (flush screen) or pressute vacuum vent.
Emergency lire conditions should be considered in designing storage tank vents. Vents should be sized according to the suggested Flammable Liquids Ordi nance of the NFPA or any local governing ordinances.
7 7 2.6 All openings in the system should terminate outdoors and be protected by flame ar resters (Hash screens).
1.1.2.1 Gauge glasses should be guarded.
7,7 2.X Laige outside abovc-giound storage tanks should be piopeily diked to confine the liquid in the event of tank failure.
8. TANK AND EQUIPMENT CLEANING AND REPAIRS
8.1 JOB EVALUATION AND PREPLANNING
8.1.1 Cleaning or making icpairs inside a tank which contained ethylene diehlondc is particularly hazardous because of its harmful properties ani flammability.
8.1 2 Equipment and lank cleaning and repair should be under the direction of thoroughly trained personnel who are fully familiar with ail of the haz ards and the safeguards necessary for the safe per formance of the work. All pieeautions peimining to education, protective equipment, and health and lire hazards should be reviewed and understood.
8.1.3 The hazardous nature of tank inspection, cleaning, and repair requires that the foreman and crew be selected, trained, and drilled carefully. The preparation of a step by step work pro, cedurc for the entire job, recognizing all possible hazards as they might occur, developing safe pro cedures and designating suitable piotecdvc equip ment, has been found to be particulaily clfective in maintaining work salcty.
8.2 TANK OK EQUIPMENT CLEANING
8.2.J Tanks and equipment, pumps, lines and valves should always be drained and thoroughly cleaned before being repaired. Workmen should never be allowed to attempt to repair equipment while it is in o|ieration and the lines m seivicc.
8 2.2 Post danger signs prominently to prohibit' smoking, use of open flames and unauthorized per sonnel in the area where tank or equipment is to be cleaned.
8.2.3 The tank or equipment to be repaired must first be emptied of all liquids. Then pipe lines into or out of the tank should be disconnected, preferably
by removing a complete small section and providing a blank flange on the open end to protect against human error and unsuspected leaks. Valves and blank flanges in the pipe line must not be relied upon alone.
8.2.4 If pipe sections arc to be removed and flanges opened, (lie lower bolts should be loosened Inst and, although the lines have been flushed, cure should be taken to avoid personal contact with the liquid draining, or diipping from the equipment. All spillage Irom the lines or equipment should be re moved immediately by flushing to the drain with large quantities of water.
8.2.5 Steam is recommended for cleaning ethyl ene diehloridc vapor and accumulations from tanks. After steaming, the tank should be flushed with water. Repeat the steaming and washing until the tank is free of flammable vapor.
8 3 PREPARING EOU TANK,ENTRY
8.3 1 Special ventilation and a continuous fresh air supply are required during the entire time men arc cleaning, inspecting, or repairing the tank. Ven tilation can be accomplished by exhausting or re moving vapors from die bottom of (he tank either ihiough its bottom openings, or by exhausting the vapors I mm die tank bottom (or top) by means of a huge uibbcr hose or flexible duct where tanks have a top opening only. I he blowers or cxhauslcis used for ventilation should Ire cleaned frequently so that moving pints will not scl up diction heat which may cause iyniiion of the vapor. On tanks having only a top opening, care must be exercised to ensure com plete removal of vapors from the entire tank. Care must also he taken to avoid having exhaust gases recycled into the tank.
14
SSjTi* m
SL 101032
Eth /icne OicKiondo
Man ,t-3^Tur,ru (.`icmiws Asjoc o'.on
Sh#*t
SO-U
8.3.2 No workman should cnltr a lank or vessel that does not have a manhole opening large enough to admit him while wearing his safety harness, life line, and respiratory protective equipment. It should be ascertained that the tank or vessel can be left hy the original entrance. In some eases, it is advisable to have a block and tackle positioned on a tripod or otherwise fastened above the manhole.
8.3.3 Proper personal protective equipment should be worn by anyone entering a tank for inspec tion, cleaning, or repairs.
8.3.4 Danger signs should he placed suitably to indicate when workmen are in the tank.
8 3.5 Lock electrical switches in the o(T position, remove duvc bells, and otherwise completely safe guard against accidentally starting the agitating equip ment or other moving parts located inside the tank or adjacent to the entrance.
8.3.6 The portable electric lights and power tools should be suitable for use in classified areas, should be in good condition, and the metal noncurrent carrying parts should be electrically bonded to the ground.
8.3.7 U should be ascertained that all sources of ignition have been eliminated from the vicinity of the tank and that vapor flow from tank is controlled.
8 3.8 In addition to protecting the workmen ac tually engaged in cleaning and repairing the tank, at tention should be paid to the protection of workers in nearby areas.
8.4 ENTRY AND WORK WITHIN TANK
8.4.1 No one should enter a tank or confined space until a work permit has been signed by an authorized person indicating that the area has been tested and found to be safe. Before directing men to enter a tank, an inspection of the interior should be made by the foreman who should be equipped with tin airline mask or self-contained breathing ap paratus, together with rescue harness and life line. Another person should be on guard during the in spection.
8.4.2 Workers entcuug tanks should he equipped with suitable [teisoual protective equipment, pteierably self-contained or airline breathing apparatus. At least one other person should be observing oper ations from outside the tank at all times.
8.4.3 During the course of the work, frequent tests should be made to determine that the atmosphere in the tank is being maintained within the safe range.
This precaution is necessary because residues not completely removed by washing may rccoiUamtnalc the tank atmosphere.
If tiny flammable vapors arc present, the clean ing process should be repeated until the tank or ves sel is free of vapor. The air should also be tested for oxygen content.
If the work extends over a considerable period, or is interrupted, frequent and regular tests of the atmosphere within the tank should be made to de termine whether recontamination has taken place.' A new work permit should be issued before resumption of work.
8 4,4 An attendant should be present at the point of entry whenever another person is in the tank. If woik is being done in an isolated area, arrangements should be made to have at least two additional as sistants available at all times. Each person entering a tank should wear an approved safety harness with a rope attached. An individual rope securely fastened outside the tank must be provided at the manhole cover for each person.
8.5 EMERGENCY RESCUE
8.5.1 A supplied-air respirator (hose mask) or self-contained breathing apparatus, together with res cue harness and life-line should always be located outside the tank entrance for rescue purposes, re gardless of the type of respiratory equipment or air supply which is provided for employees inside the tank. The air intake of the hose mask should be kept in an uncontaminated area.
8.5.2 Under no circumstances should a rescuer enter a lank to remove a victim of overexposure without proper respiratory protection, a safety harness and an attached life line. The free end of the life line should be manned by an attendant lo cated outside the tank. Another attendant should be immediately available to assist in the rescue if needed. The rescuer should be in view of the outside attendant at all times or in constant communication with him.
8.5 3 If a tank cleaner or repairman is overcome by fumes, he should be removed to fresh air immedi ately. Artificial respiration should be applied if breathing has stopped, and a physician summoned at once.
8.6 REPAIRS TO* TANKS OR EQUIPMENT
8 6.1 Repairs to interiors or exteriors of tanks or equipment, including repairs to steam coils, cut ting, riveting and welding, should be permitted only
15
SL 101033
Mnflual Sliodt
50-18 i
MaiWacfurintj OvumUs Association
Ethylene Dichloride
sifter thoroughly cleaning anti testing of (he l;mk to
ehaiges. I'mging should be continued while the repair
I
make sure it is free of vapors and after a work permit has been issued by an authorized person.
work is in progiess. billing empty tanks with inert gas or purging with air are other methods which may
8.6.2 All outside welding or burning on tanks
be used in outside welding or burning.
i
or equipment which have contained ethylene dichloride should be done only after such containers
8.6.3 In all eases, if repair work is interrupted, the tank atmosphere should be checked thoroughly
have been completely purged with steam. Steam lines
anti a new work permit issued before resumption of
should be bonded to prevent accumulation of static
work.
9. WASTE DISPOSAL
9.1 The disposal of waste ethylene dichloride and
atomizing the liquid into an approved type of com
materials contaminated with it is subject to Federal,
bustion chamber equipped with a vent gas water
state, and local regulations regarding health and
scrubber.
pollution.
9.3 Waste mixtures containing ethylene dichloride
)
9 2 Disposal of small quantities may be accom plished by removal of the waste to a safe location
should not be allowed to enter those drains or sewers where there might be danger of the vapor igniting.
away from buildings or other combustible structures,
then pouring the mixture on dry sand, or earth and
9.4 Ethylene dichloride has a low chemical oxygen
then cautiously igniting it. Disposal of large quanti
demand, docs not interfere with biological treatment,
i ties of ethylene dichloride may be accomplished by .and is easily aerated out of water solutions.
i
< 10. MEDICAL MANAGEMENT
10.1 HEALTH IIAZAKDS
throat. There may also be nausea, vomiting and some drowsiness. Ethylene dichloride, like other chlori
10.1.1 Ethylene dichloride is toxic by inhalation, by contact with skin or mucous membranes, or by
nated hydrocarbons, has an anesthetic action.
ingestion. Prolonged, excessive or repented exposure to the product in any form is hazardous.
10.1.2 The signs and symptoms of excessive ab sorption are: headache, mental confusion, depression, fatigue, loss of appetite, nausea, vomiting, cough, loss of sense of balance, and visual disturbances. There may also be diarrhea with bloody stools, sup pression of urine, edema, jaundice, and blood in the urine.
10.1.4.1 Acute Poisoning
10.1.4.1.1 Inhalation of an excessive amount of vapor over a short period of time may cause acute poisoning. The initial effects are irritation of eyes, nose and throat, fullness in the head with mental con fusion. There may be dizziness, nausea and vomiting. If the workman is not immediately removed from the vapor he may become unconscious.
10.1.3 The signs and symptoms of ethylene dichloride poisoning given in 10.1.2 are die result of
10.1.4.1.2 Some conditions under which acute poisoning may occur arc as follows:
injury to the kidneys, adrenal glands, lungs, and di i gestive and nervous systems. The clinical picture
varies with (lie lype and degree of exposure, whether
(a) Spills. (!>) Winking in enclosures or tanks with
single or multiple.
out adequate protection.
10.1.4 Toxic IvITccIh Alice liilmlnlimi
The threshold limit value adopted by the Ameri can Conference of Governmental Industrial Hygien ists is(5t) ppm. Exposure to higher concentrations of vapa^ causes irritation of the eyes, nose and
10.1.4.2 Subacute Poisoning
10.1.4.2.1 Subacute ethylene dichloride poisoning may result from prolonged or repealed work in an atmosphere containing excessive concen trations of ethylene dichloride, but under conditions
TL0 ^ /PLU
16
m
Ethylene Dichloncie
/Mcjnur'ocfur/n^' _hcm/sts >\siOC;o/ion
Manual
Sh*#l SO-J*
in which (he amount absorbed is not sullicient lo cause loss of consciousness.
10.1.4.2.2 Workers with subacute poison ing may become acutely ill and sutler from head aches, fatigue, nausea, vomiting and dizziness with visual disturbances. There may he edema and sup pression of the urine. Jaundice may occur.
10.1.4.2 3 Some conditions under which subacute poisoning may occur in employees arc as follows:
(a) Inadequate ventilation,
(bj Faulty handling or lack of contain ment of the liquid or vapor.
(c) Failure of the individual to observe precautionary measures.
10 1.4.3 Chronic poisimitii!. Tile symptoms would be similar to those encountered in subacute poisoning except there arc no acute symptoms, since the poisoning results from absorption of less material over a longer period of time.
10.1.5 Toxic Effects from External Contact
10.1.5.1 Skin
Ethylene dichloridc is absorbed through (he skin though it takes quite huge doses to cause serious systemic poisoning. When ethylene dichloridc is held close to the skin within a cuff, such as is used in skinabsoiption experiments, quite severe irritation and moderate edema and necrosis may be observed. Ordinary contact with ethylene dichloridc on the skin where it is not held by (he clothing does not cause serious difficulties. Repeated or prolonged contact, however, may cause a rough, red, dry skin due to extraction of fatty materials. It may result in cracking and a "chapped skin."
10.1.5.2 Eyes
Eye exposure to vapor or liquid produces lacrimation, buttling and other symptoms of irrita tion. Immediate eye irrigation will prevent serious injury.
10.1.6 Toxic Effect* Alter Oral Intake
The initial symptoms of toxic amounts of ethyl ene dichloridc taken by mouth are irritation of the gastro-intcstinal tract, with nausea, vomiting and diarrhea with bloody stools. '1 his may be followed by the general symptoms of jioisonmg enumerated above.
10.2 PREVENTIVE HEALTH MEASURES
10.2.1Ventilation
10 2.1.1 The best way to avoid toxic effects is to handle ethylene dichloridc in a closed system. Where tins is impractical, sufficient ventilation should
"didiloridc at hazardous concentrations may not al ways be detectable and does not give adequate warning to prevent injury.
10.2.1.2 General ventilation can be used to avoid overexposure to vapors resulting from small leaks which escape detection. Local ventilation can be used at sites of known release of vapors to the air. However, the use of ventilation to control exposure of woikmcn can result in an air pollution problem if the discarded air reaches an inhabited area.
10.2.2 Employee Education
10 2.2.1 Employees should he instructed to re port any signs or symptoms, and lo seek medical at tention promptly.
10.2.2.2 Anyone with potential exposure to ethylene dichloridc should be made aware of its hazardous properties and instructed to observe proper precautions.
10.2.3 Prepliieeiueiii I'liysiral Examinations
Some people arc more susceptible to chlorinated hydrocarbons than others, The danger to such individuals can We minimized by a preplaccmcnt phy sical examination. Exposures to ethylene dichloridc even in concentrations known to lie nonhazardous to normal individuals should be prohibited in:
(a) Alcoholics
(b) Obese individuals
(c) Undernourished individuals
(d) Those with pulmonary diseases, peptic ulcer, high blood pressure, and diseases of the liver, kidney or heart.
10.2.4 lYi-iodic Physical Examination*
Employees who are exposed regularly to ethyl ene dichloiide should be examined, at least semi annually. Physical examinations should lie required also when any symptoms of poisoning, such as enumerated above are-present in employees. Discov ery of symptoms of ethylene dichloridc poisoning may indicate some defect in operation. This would serve as an indieatiou lo examine other exposed em ployees for early signs of poisoning.
SL 101035
S'! n n u a i
ShoM
SD-U
M a n j r 3 c t ^ r, r g iomi s/5 A>>:) 0TIuH
Ethylene Dicnlorido
11. FIRST AID
11.1 GENERAL PRINCIPLES
II.LI Must important in the case of any poisoning is quick removal from exposure. In the ease of ethylene dichloridc poisoning, this means first removing the patient from the contaminated atmos phere and, insofar as possible, removing the ethylene dichloride from the skin, eyes and gastrointestinal tract.
11 1.2 Give the patient fresh air by moving him to a well ventilated room free of vapors and by dispetsing any crowd. If bieaihtng has ceased, stait artificial respiration at once.
11.13 Adrenalin or similar acting drugs should never be given to a person sutfcimg from ethylene dichloiide poisoning, because these drugs may pre cipitate abnoimal heart rhythms.
II 1.4 Keep the patient quiet and comfortably warm but not hot.
11.2 SPECIFIC ACTIONS
11.2.1 Inhalation
A person showing symptoms of ethylene bi chloride vapor poisoning should be removed promptly from the contaminated aiea. In ease breathing lias stopped, artificial respiration should be started im mediately. If osvgen inhalation apparatus is avail able, oxygen should be administeicd only if one familiar with the operation of the apparatus is pres ent to administer it.
A physician should be called at once.
11.2.2 Skin Contact
All contaminated clothing should be removed
at once. Clothing, including shoes, soaked in ethylene dichloiide should he removed and not worn again until thoroughly dry. All affected areas should be washed thoroughly with abundant water and soap. For set ions or persistent eases of skin trouble and for signs and symptoms of generalized poisoning, a physician should be consulted.
11.2.3 Contact with Eye#
If liquid ethylene dichloridc has cnieicd the eyes, they should be washed promptly with copious quantities of water lor at least 15 minutes. It is ad visable to irrigate the eyes gently with water at room leinperaiuic in order to minimize additional pain or discomfort. Ethylene dichloridc vapor can pioduce injury to the eyes il the exposure is intense or pro longed. Eyes should be irrigated for vapor exposure in the same manner as for liquid exposure. Medical attention should be obtained in all eases of eye exposure.
11.2.4 Taken Internally
If a person has swallowed ethylene bichloride, lie should be made to vomit by drinking a.glassful of mustard water, lukewarm salt water, or soapy warm waier. If necessary, the patient should be en couraged to slick his linger down his throat to induce vomiting. This piocedurc should be repeated at least three times and then followed hy (he administration of a tablespoonful of cpsom salts. A physician should be called at once.
Never give anything hy mouth or attempt to cause vomiting // the patient is unconscious or hav ing convulsions.
18
SL 10X036
62 Martm et ai.t Clinical Feature*, Pathogenesis and Management of Dichloroethane Poisoning
Germ. med, Mtb-.Vol- XIV
(4) Clarke, C. A.: Personal communication (1968).
(5) Gorman, J. G., V. J. Freda: Personal communication (1968).
(6) Jennings, C. R.: Personal commumcanon (1968).
(7) Gorman, J. G.: Personal communication 1967.
(8) Zipursky, A., L. G. Israels: Canad.* med. Ass. J. 97 (1967), 1246. - Lewis, M.i Bowman, J. M.; Peddle, L.;
Kaita, H.f B. Chown; Personal communication (1967).
(9) Robertson, J. G-* Communication read at Europ. Congr. of Perinatal Med., at Berlin, 27.-30. 3. 1968.
(10) Bartsdi, F.- Persona! communication (1968).
(11) Vermylen, C,, Personal communication (1968).
(12) Hamilton, E. G.: Obstet. and Gynec, 30 (1967), 812. - Personal
communication to J. G. Robertson, C. A Clarke.
(U) Hindemann, P.: Bibl. gynaec. (Basel 1966), p. 23.
(14) Pollack, W., H* 0. Singher. J. G. Gorman, V. J, Freda: The prevention of Isoimmunization to the
Rh-Factor by passive immunization with Rho (13) Immune-Globulin (Human). American Association of Blood Banka Oct. 21.-24. 1967 (New York), Scientific Exhibit and abstract in "Transfusion* (N. Y.). To be published.
(Requests for reprints should be addressed to:Universitats-Frauenklinik 78 Freiburg, Germany)
JAN 1 3 1333
Clinical Features, Pathogenesis and Management of Dichloroethane Poisoning1
G. Martin, K. Knorpp, K. Huth, F. Heinrich
and cMiccermaycr
Department of Medicine (Joint Directors: Prof. H. J. Denglcr, Prof. H, A. Kuhn and Prof. H. G, Latch) and the Department of Pathology (Director: Prof. V. Sandr.fter), Uoivcraify of Giessen
Summary:- A 57-year-old man died of therapy-resistant cardiovascular failure 24 hours after ingestion of an dichloroethane-containing embrocation. Apart from gastro-enterocolitis and hepatic necrosis he developed a severe haemorrhagic diathesis. The complex disturbance of the haemostatic mechanism, which included thrombocytopenia and reduced activity of all clotting factors examined (Factor I, II, V, VII and XIII), was ascribed to consumption ("using up") of these substances by disseminated intravascular coagulation ("Verbrauchskoagulopathie") and secondary hyperfibrinolysis. Therapeutic principles for the management of oral dichloroethane poisoning are suggested taking into account thfe likely pathogenesis. They include prompt gastric lavage with addition of paraffin (in which dichloroethane dissolves), measures to protect the liver, continuous supervision and adjustment of blood gases. Incipient consumption of the clotting factors is counter acted by heparin infusions. Cardiovascular function is supervised by continuous registration of the electrocardiogram, even after apparent improvement in the patient's condition or subsidence of the initial stupor. Should renal failure occur, treatment is the same as for other types of acute renal failure.
Some analgesic and anti-inflammatory embrocations in clude dichloroethane (CHj-Cl-CHj-Cl) as their main hyperaemia-inducing constituent. Accidental or deliberate ingestion of such embrocations which are meant solely for external use, may result in severe and sometimes fatal dichloroethane poisoning (2, 3,13),
To the few reports of poisoning by swallowing di chloroethane a further case is added here. It was character ized by very severe cardiac arrhythmias and disturbances of the clotting mechanism causing a haemorrhagic diathe sis due to intravascular consumption of clotting factors.
Case Report
At about 18.30 on November 4, 1966, patient R., a 37-year-old man, swallowed, presumably with suicidal intent, about 40 ml of an initially unidentified embrocation used by him foe the relief of rheumatic complaints. He was admitted to hospital at 20.00 on the same day in a somnolent condition. As the patient could not be roused, information about the poison swallowed was unobtainable.
1 Translated from Dtsch. med. Wschr. 93 (1968;, 2002.
Relatives could not be contacted. The expired air smelled strongly of camphor. A few minutes after admission to hospital the patient vomited about 300 ml of a bilious liquid smelling of camphor and about 30 minutes later voided copious, apparently normal, faeces on three occasions. Otherwise there were no alarming signs of severe poisoning.
Clinical Features and Course
SL 101037
Apart from a postgastrectomy scar external appearance was nor mal. There were no demonstrable neurological defects, cyanosis, dyspnoea, oedema, jaundice, skin rash or haemorrhagic diathesis. Blood pressure was constant at 140/80 mm Hg. The electrocardio gram (ECG) showed sinus tachycardia of about 100/minute and ventricular cxtrasystoles but normal A-V conduction.
Serum glutamic-oxaloacetic transaminase (SGOT) and serum glutamic-pyruvic transaminase (SGFT) activities were normal (4J III and 6.7 IU, respectively). After gastric lavage, whidi produced only small quantities of food residue, infusion of a S'/t Ringer-laevuiose solution combined with itrophanrhin and antibiotics was instituted. Oral paraffin, which binds ethane dichloride and in this way pre vents or delays its absorption, was not given as there was no in formation on the type of poison (9). A gas analyser which would
have immediately detected the presence of halogenated hydrocarbons
No. 2, Februao IH9
Martin et a).. Clinical Features, Pathogenesis and Management of DitWoroethane PoitGntng
63
in the expired air was not available at that time. In view of the con tinued improvement in the patient'i condition no further therapeutic mtasures were adopted.
On the morning of November 5th, twelve hours after admission to hospital, the patient responded to stimuli. It was only then, 14 hours after the accident, that the patient and relatives who had since been summoned by telephone provided the information that he had swal lowed Marament. This embrocation is made up of: 100 g dichloroethane, 2.0 g oil of pine-needles, 02 g methyl salicylate, O.OJ mg cobra (Naja mpudians) toxins and an unspecified emulsifier in 100 ml of the liquid.
At about 8.30, almost immediately after the toxic nature of die remedy had become known, the patient's condition suddenly deteriorated with, dyspnoea, orthopnoea and progressive clouding of consciousness. Blood pressure could no longer be recorded. At E.40, during attempts at improving the circulation, cardiac arrest suddeny supervened.
After successful resuscitation by external cardiac massage for 25 minutes and artificial respiration with oxygen (by intubation) the ECG showed complete atrio-ventricular block with a regular idio ventricular rate of 70/minutc. The P-waves, so far as they were dis cernible, indicated an atrial rate of 7J/minute (Fig. 1).
The ventricular and atrial rates responded to the intravenous in jection of 1.0 mg orciprenaline with a rise to 85/minute and 120/min ute respectively. Finally, complete A-V block subsided and a regular rhythm of 110/minute returned (Fig. 2).
Rapid infusion of Haemaccel, sodium bicarbonate, 5/i Ringerlaevulose solution and noradrenaline succeeded at about 10.40 (two hours after cardiac arrest) in restoring the circulatory state to nor mal. Unaided by adrenergic agents the blood pressure rose to 105/85 mm Hg and the patient responded to stimuli.
ECG recordings (precordial leads) showed episodes of right bundle branch block. 17 hours after the accident the sinus rhythm was again disturbed by occasional ventricular extrasystoles which became more
ftequent in the course of the next half hour (Fig. 3). After a further two hours, P-waves were no longer discernible; but the possibility that they were fused with the preceding T-waves could not be excluded.
-s- -- "
50mm/wc
During the day the ventricular extrasystoles be came more frequent and changes in the site of im pulse origin resulted in episodes of parasystole. 24 hours after ingestion of the poison the blood pressure fell rapidly within 30 minutes and cardiac
arrest occurred.
25mm/sec
During resuscitation attempts prolonged bleeding from venipunctures drew attention to an increased bleeding tendency.
bir7ri-v.-J-*
* -
-i-ij'.ii -'...
:\ T '1- I H.- 'ri 1
25mm/**c
' ic^ ^somm/aec
g. 1. Electrocardiogram recorded on 5 November 1966, after successful resusdta)n: probably complete atrio-ventricular dissociation with (hanging site of paceaker.
after injection of a further 2 ml. orciprenaline
SOmm/tec
At-f0.40, after nodal rhythm and stable circula tory conditions had become re-established and con sciousness was gradually returning, massive haematemesis occurred, presumably due to profuse bleeding from the gastro-intesrinal mucosa. It ef fectively precluded oral administration of paraffin which even then might still have proved beneficial. Up to 14.00 a total of 1,500 ml of blood-containing gastric contents had been evacuated, partly by vomiting and partly by suction catheter. An analy sis of the cloning factors (at 15.00) showed maximal reduction of Factors II, V, VII and XIII and com plete defibrination, fibrinogen being no longer de monstrable in the tyrosine-tryptophan test (12). The platelet count had dropped to 14,300/mm', fibrino lysis (Piper's method [10]) was increased to four times its normal value and pro-activator levels were below 10*/a. The thrombelastogram showed the blood to be incoagulable. Thrombin time after fibrinogen substitution was 59 seconds instead of the normal 12 seconds.
,(.* + (-Lt-V L-5-. 1 i t'lij.-fT,- : 4 .
The complex coagulation disorder with thrombo cytopenia and reduced activity of all coagulation factors was attributed to the consumption of these substances in a process of disseminated. intra vascular coagulation (``Verbraudiskoagulopathie') and to secondary hyperfibrinolysis (5, 7). The patient was given 5,000 U heparin by intravenous drip over a period of two hours and he was also given intravenously Cohn's fraction as a fibrinogen substitute, 4.0 g of e-amino-caproic acid as an antifibrinolytic agent and 2.0 ml Vitamin K, (phytomenadione).
. 2. Electrocardiogram recorded at 10.10-10.47 a. m. on 5 November 1966: sinus nycardia after injection of a total of 6.0 ml of orciprenaline (Alupent*).
A further estimation of cloning factors at 18.00 showed a rise in fibrinogen level to 16 mg/100 ml and in the platelet count to 20,000/mm*. Factors II, V and VII remained low. At was subsequently confirmed at necropsy, the liver at that time was already irretrievably damaged. The steep rise of SCOT to 1,860 IU, of SGPT to 450 IU and of
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64 Martin et *1.: Clinical Feature*, Pacho|eM*i* and Manaftaent oi DidUorocdune Poisoning
Germ. mcd. Mth., Vol! XIV
lactate dehydrogenase to 455 IU and the reduction of serum-albumin concentration to 139 g/100 ml and of plasma-cholesterol to 76 mg/100 ml were presum ably attributable to fulminating yellow atrophy of the liver. The abnormally high lactate-dehydrogenase ac tivity may have possibly been due to haemolysis.
Blood-gas analysis (Astrup's method) after massive infusion of a total of 920 mEq. of sodium bicarbonate revealed extreme acidaemia (pH $,8) which was partly of metabolic (reduced base excess and standard bicar bonate) and partly of respiratory origin (marked in crease in CO, tension). At the time the blood samples were taken the patient was already moribund. He died at approximately 20.00, about 24 hours after ingestion of die poison, of irreversible cardiac and circulatory failure.
.T.
-1
; .r*
' t > , * . :,i:
Necropsy Findings
The most striking feature was acute yellow atrophy of the enlarged (1,800 g) and flabby liver. The cut sur face showed irregular yellowish-brown mottling.
--\r^r,
Through the microscope the lobular structure was discernible only as a shadow outline.
L..' r- r_ Fig. 3. Electrocardiogram taken at 10J3--10.58 a-m. on 5 November 1966. The
The portal canals were crowded closely together. Goldner's stain revealed very dark, homogeneous and lumpy hepatic cells with only a few nuclei.
tracings (the leads were not recorded simultaneously) show, first, sinus tadiycardia with some extrasystoles; on the reight; complete tight bundle branch block has developed which may indicate acute cor pulmonale.
Distended cells, hyaline bodies and large intra
cellular fat droplets were also seen. Only a few hepatic cells were of not develop until after a latent period of 24-48 hours (9).
normal appearance.
Cardiac arrhythmias and particularly ventricular fibrilla
Both ventricles were hypertrophied and die right one was also dilated. On microscopic examination the myocardial fibres were thickened and the cell nuclei enlarged and irregular. There were also recent, predominandy perivascular, focal necroses of the myocardial fibres (Fig. 4*). The coronary arteries were slightly arteriosclerotic but not narrowed.
tions have been observed after poisoning with chloroform and carbon tetrachloride (4) and Friese (3) also noticed in a case of ethane dichloride poisoning a transient in version of the T-wave in leads Vg~Vf such as occurs in rudimentary infarction of the anterior wall. The haemor
The lungs showed bilateral chronic emphysema, membranous rhagic tendency that accompanies carbon tetrachloride
pleural adhesions, considerable congestion ana oedema. Microscopic examination revealed both occluding and non-occluding thrombi in the small lung arteries and capillaries, of not quite recent origin (Figs. 5 and 6).
and dichloroethane poisoning has been ascribed to a mas sive reduction in prothrombin concentration.
The post-mortem examination in our case revealed not
The haemorrhagic diathesis manifested itself in haemorrhages into only the signs of haemorrhagic diathesis but also thrombi
the mucosae of oesophagus, stump of the stomach (after a Billroth II gastrectomy) and rectum, and into the subepicardial, subendocardial and myocardial tissues. Bleeding into the intestinal wall was notice able in some jejunal loops. The attempts at resuscitation had re sulted in fracture of several ribs, subpleural haematoma and haemo-
chorax of minor degree on the left side.
in the pulmonary arterioles and capillaries. Taking into account the complex changes in the haemostatic mechan ism and the not unfavourable effects of heparin admin istration, the assumption appears justified that the drama tic reduction in the platelet count and clotting factors was
a sign of their marked depletion, the substrates having
Discussion
The signs and symptoms presented by this case of dichloroethane poisoning corresponded closely ro the clinical picture described by others. Characteristic features were an initial Stage of stupor followed by the develop ment of gastro-enterocolitis, hepatic necrosis, haemor rhagic diathesis and cardiogenic shock within 48 hours. The frequently observed involvement of the kidneys was absent in our case. Toxic effects of dichloroethane resemble those produced by other halogenated hydro carbons, especially carbon tetrachloride, chloroform and ethane tetrachloride. All these agents have in common that, being fat-soluble, they have narcotic effects and taken orally they cause gastrointestinal damage and necro sis of the liver and kidneys. The renal lesions generally do
been consumed in the process of coagulation (8). This in terpretation receives support from the fact that fibrinogen has a half-life of 3-4 days (1); the drop in the platelet count and plasma Factor I could not, therefore, be ac counted for by the onset of hepatic necrosis and the re sulting interference with the formation and synthesis of plasma clotting factors. As to the accompanying hyper fibrinolysis, this was presumably a reactive process to dis solve the fibrin thrombi as is frequently observed in gener alized intravascular clotting (7).
Whether dichloroethane can trigger intravascular clotting is so far unknown. Being a fat solvent it might damage the platelet membrane and thereby release pla telet Factor III; or it might activate the clotting process by inducing haemolysis and thereby releasing pro-coagulant erythrocytic lipoproteins (erythrocytin [II]). The snake
* Figs. 4-6 are on p. 66.
venom in the embrocation (snake bites may cause intra-
101039
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For the article by Turina et al. (pp. 49-JO)
Crohn's Disease of che Oesophagus
65
Fig. 1. Crohn's disease of the oesophagus. Oesophagram: severe de gree of stenosis with thread-like irregular lumen immediately above the diaphragm. Conical narrowing of the oesophagus above the stenosis.
Fig. 2. Same case as Fig. 1. Resected specimen of the distal oesopha
gus and proximal part of the stomach showing a 2 cm long granu
lomatous stenosis (S) below the upper margin of the resection.
Fig. 3. Same case. Ulcer floor with non-specific granulation tissue and compact lymph follicles in the residual parts of the tunica propria, also in the submucosa which is fibrotic and hyperaemic. Magnification
Fig. 4. Same case. Muscularis propria with compact lymph follicles. Magnification X 88.
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;e
or the article by Martin et al, (pp. 62-67)
Clinical Features, Pathogenesis and Management of Dichloroethane Poisoning
Fig. 4. Heart-muscle necrosis. Goldner's tridiome stain. Magnifica tion X 140.
Fig. J. Hyaline thrombi in lung vessels. Goldner's tridiome stain. Fig. 6. Hyaline thrombus in lung vessels. Goldner's tridiome stain.
Magnification X 140.
Magnification X 240.
For the article by Gedigk et al. (pp. 68-77)
The Morbid Anatomy of Marburg Virus Disease
Fig. 1. Irregularly arranged areas of necrosis (dark) affecting single cells and cell groups in the liver. Case 1 (PM No. 378/67). Formalin, Goldner, X 100.
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o. 2, Febru0'
Minin et it/. Clinical Features, Faihogeneiii and Management of Didiloroetbanc Poisoning
67
iscular dotting) can be excluded as a causal factor as ie poison was taken by mouth. The severe damage to the rgans induced by dichloroethane could possibly bring iout the release of tissue thromboplastins which, in coninction with the excessive acidaemia and circulatory failre, could cause a shift in the physiological balance beveen fibrinolysis and dotting towards the latter.
There is also the possibility that the cardiac arrhythmia id the consequent reduction in cardiac output (cardio;nic shock) played a causal role in the pathogenesis of travascular dotting. On the other hand, the dilatation : the right ventricle and devdopment of acute cor pulonale with cardiac arrhythmia, cardiogenic shock and yocardial necroses could equally well originate from travascular coagulation and the resulting, histologically roven, blocking of the pulmonary circulation by thrombi, this latter hypothesis is accepted the haemorrhagic diaiesi$, the cardiac arrhythmia and the disseminated neoses in the intestine and kidneys could be attributed to ie action of a single mechanism since the fully developed ndrome of intravascular coagulation is characterized by farction of, and haemorrhages into, various organs.
rnclusi ns
The clinical picture presented by dichloroethane >isoning is determined by the quantity of poison ingest. In man the tolerated single dose is not more than ) ml, with a maximal daily dose of 3.0 ml (9). As there no known specific antidote, measures to counteract the ects of orally taken dichloroethane are primarily coned to attempts at reducing or slowing down absorption
the poison from the gastro-intestinal tract. Further irapeuric measures aim at preventing acute hepatic lure and at restoring the disordered haemostatic mecha;m, acid-base balance and cardiovascular function. Selece therapy directed to the restoration of a particular ictional system is impossible. From considerations of : pathogenetic mechanism, published reports and our m observations some general principles for dealing with il dichloroethane poisoning emerge:
1) Alertness to the possibility .of dichloroethane pol ling is important. Inadequate specification of some hloroethane-containing preparations as potentially ngerous is liable to mislead patients, relatives and the ending physician.
1) Analysis of the expired air by a gas analyser for the :sence of chlorinated hydrocarbons, unless this type of ison can be absolutely ruled out
5) Prompt gastric lavage, provided there is no contralication, with addition of paraffin; then administration 100-150 ml of paraffin and saline purges, either by 'Uth or indwelling stomach tube. Paraffin administration epeated every 6-8 hours for the first 24--48 hours.
4) Prompt measures to protect the liver similar to those employed in acute yellow atrophy (6). Repeated laborato ry tests.
5) Supervision and constant adjustment of blood gases and steps to ensure excretion of an alkaline urine. Sodium bicarbonate administration should be supplemented by THAM, because the latter is more effective in counter acting intracellular acidosis.
6) Prompt and continuous analysis of the dotting fac
tors to ensure that an incipient consumption of platelets
and fibrinogen is immediately checked by an infusion of
heparin (20,000 U in 24 hours). This therapy is applicable
even in the presence of gastro-intestinal haemorrhage. If
defibrination has already occurred, heparin combined with
Cohn's fraction I as a fibrinogen substitute is given by
infusion.
v
7) Continuous supervision of cardiovascular function with continuous recording of the ECG-
8) Administration of water and electrolytes as required and symptomatic treatment of the gastro-entcrocolitis which is an almost invariable complication. Intestinal haemorrhages resulting in a critical reduction in haemo globin concentration may require blood transfusion.
9) Renal failure setting in 24--48 hours after ingestion of the poison is a potential complication of the third stage of dichloroethane poisohing. Its occurrence depends on the quantity swallowed, the interval between ingestion and beginning of treatment and the success of the antecedent therapeutic measures. Treatment is the same as for acute failure from other causes.
10) An apparent improvement in the patient's condition after the initial stuporous stage has subsided must not lead to premature slackening of the therapeutic efforts.
Reference!
(1) Amni, A., C. J. Amrii: Thtombot. Diarhca. Hacmorrh. (Snittg.) 11 (1964), 404.
(2) Bran, K.: Drsdi. mcd. Wschr. 74 (1949), 553.
(3) Frieae, G., H. H. Sesmer; Mcd. Well (Siting.) 1961, 102,
(4) Friese, G.: Differeittialdiagflosc dcr Hemtrornkurvc (Bcrlin-HeidelbcrgNew York, 1961).
(5) Hardaway, R. M.; Syndromes of Disseminated intravascular Coagulation (Springfield, 1966).
(6) Knauff, H. G.: MOndt. mcd. Wsdir. 105 (190), 1; 27.
(t) Lasdt, H. G., D. Httfie, JC, Hutfc, W. Sandritter. Amer. J. Cardiol. 20 (1967), 391.
(I) McKay, D., W. Miififcttai; Ardi. inter. Med. 120 (1967), 129.
9) Mocadilin, S.; KJinik und Tlwrapk der VergifniRges (Stuttgart, 1959),
(10) Piper, W., H. C. ^udibergen Med. Wdt (Snittg.) 1965, 315. (II) Quick, A. J., J. G. Georgataoa, C V. Hussey*. Amer. J. med. Sd. 221 (1954), 207,
(12) Ratfloff, O. D.t C. Mender J. Lab. din. Med. 37 (1951), 316.
(13) Stuhlert, H.: Dtsdi. med. Widif. 74 (1949), 1542.
(Authors* addresses:- Dr. G. Martin Universitits-Frauenklinik Humboldtalle, 34 Gdttingen; Dr. K. Knorpp; Privatdozent Dr. K. Huth; Dr. F. Heinrich Medizimsche,Klmiken und Polikliniken Klinikstr. 32 b, 63 Giessen; Dr. C. Mittermayer Pathologisdies Insritut der Univenitat 78 Freiburg/Br^ Germany)
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