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Occupational Safety and Health1Corrosive Materials Materials that evoke a chemical process which converts minerals and metals into unwanted products

Acidity (HCl, H2SO4, ClSO3H, HF, HCOOH, CHCOOH) Oxidizing agent (HClO4, H2SO4 , HNO3) Hygroscopic (H2SO4), Alkalis (KOH, NaOH)US Department of Transportation Regulation

Occupational Safety and Health2Corrosive MaterialsChemical substances that, by direct chemical action, are injurious to living tissues or corrosive to metal surfacesThe degree of hazard associated with a corrosive material is greatly dependent upon its physical state (solid, liquid, gas)Minor corrosive injury = irritationOccupational Safety and Health3Corrosive LiquidsMost common cause of corrosive injuryCorrosive liquids will destroy any living tissue but the most frequently injured organs are the skin and eyes. Corrosive vapors can also escape from some solutions (check out the interior of any acid cabinet). Fuming acids are particularly hazardousOccupational Safety and Health4Corrosive Liquids: BasesConcentrated alkalies are more damaging to tissues than most strong inorganic acidsAlkaline solutions gelatinize and saponify tissues, producing deeply penetrating, painful burnsEven weak alkaline solutions can dissolve skin fats and weaken the epidermis, making the skin more permeable to other agentsInitial contact may not be painful poor warning property!Occupational Safety and Health5Corrosive Liquids: AcidsChemical action of acids is different from that of bases. Acids burn largely due to thermal action with moisture in tissues. When acids come into contact with skin, the acid reacts to form a (very slightly) protective barrier, whereas bases dissolve proteins.Occupational Safety and Health6Corrosive Liquids: organic solventsA corrosive liquid need not have a very high or low pH to be capable of causing corrosive injury. Many organic solvents can cause severe irritation of skin and mucus membranes by defatting tissues, which paves the way for secondary infections.Occupational Safety and Health7Corrosive Liquids: hydrofluoric acidHF and gaseous hydrogen fluoride merit special discussion. These are easily the most hazardous corrosive materials encountered in the laboratoryHF is extremely dangerous not only because it is an acid but because the fluoride ion is capable of traveling through layers of tissue on its way to the bone, producing severe, slow healing burnsAlways store/use HF solutions and hydrogen fluoride gas in a chemical fume hood never on the lab bench!Occupational Safety and Health8Corrosive GasesMost seriously hazardous of all corrosive materials! Readily absorbed into the body by dissolution in tissue moisture (e.g. in skin and/or respiratory tract and/or eyes).Severity of the corrosive effect and the region o the respiratory tract affected by exposure is greatly dependent upon the aqueous solubility of the chemical (see table on next slide).Always use/store corrosive gases in a chemical fume hood never ever on the bench!Occupational Safety and Health9Corrosive GasesHighly water soluble (upper respiratory tract)Medium aqueous solubility (upper respiratory tract and bronchi)Low aqueous solubility (easily reaches alveoli, causing delayed pulmonary edemaAmmoniaBrominePhosgeneHydrogen chlorideChlorineNitrogen dioxideHydrogen fluorideIodineOzoneFormaldehydePhosphorus pentachlorideSulfonyl chloridePhosphorus trichlorideThionyl chlorideSulfur dioxideOccupational Safety and Health10Improper Acid Storage

Flammables and acids must be segregated Oxidizing acids must be stored separate from all other chemicals, including other acids Must be stored to prevent contact with bare metal/wood Must be stored on a plastic liner/tray to minimize potential contamination/spillsOccupational Safety and Health11HIGHLY TOXICA chemical which has the median lethal dose of: 50 mg per kg when administered orally200 mg per kg by continuous contact for 24 hrsA chemical which has the median lethal concentration of:200 parts per mil of gas or vapor or 2 mg per L of mist, fume or dust when continuously inhaled for one hour IN THE ABOVE DESCRIPTIONS DEATH OCCURS WITHIN THE TIME FRAME DESCRIBED IN LABORATORY ANIMALSOccupational Safety and Health12IRRITANTAn irritant chemical is one which is not corrosive but which causes a REVERSIBLE inflammatory effect on living tissue by chemical action at the site of contactOccupational Safety and Health13SENSITIZERA chemical which causes a substantial portion of exposed people to develop an allergic reaction in normal tissue after repeated exposure to the chemicalOccupational Safety and Health14DEFINITION OF A HAZARDOUS WASTEANY HAZARDOUS LIQUID, SOLID OR GASEOUS MATERIAL WHICH IS NO LONGER USABLE FOR ITS ORIGINAL INTENDED PURPOSE OR WHICH HAS BEEN CONTAMINATED BY A FOREIGN SUBSTANCE.Anondho Wijanarko dan YuliusmanKeselamatan Kerja14Occupational Safety and Health15FLAMMABLE MATERIALS

Occupational Safety and Health16Flammable and combustible liquids are potential fuel sources for fires and are present in almost every workplace. It is actually the vapor created by flammable and combustible liquids that ignites and burns.It is important to understand what materials in your work area are flammable and combustible so that you may properly store and isolate them from ignition sources.Flammable and Combustible LiquidsOccupational Safety and Health17Isopropyl alcoholTolueneDiethyl etherMethyl formateAcetoneEthyl etherKeroseneLacquer thinnerGasolineMEKFlammable and Combustible Liquids

Occupational Safety and Health18NFPA classification systemThe NFPA diamond is an easy way to determine the safety risks associated with hazardous materials. To determine a materials flammability refer to the red section of the diamond. A number in this section will indicate the flammability rating of the material.The following numbering system is used to indicate flammability 0- will not burn1- must be preheated to burn2-ignites when moderately heated3-ignites at normal temperature4-extremely flammable

How do I tell whats flammable?

For example, An NFPA diamond on a can of gasoline would have a 3 in the red section indicating that gasoline could ignite at normal working temperatures.NFPA Diamond

Occupational Safety and Health19Flammable LiquidsFlammable liquids can cause a fire or explosion, and like many other substances, they can also cause serious health effects from overexposure.

Note: On the NFPA diamond label, a fire hazard rating of 3 or 4 denotes a flammable liquid.3

Occupational Safety and Health20Flammable LiquidsThe vapors of flammable liquids often present the most serious hazard.The vapors can easily ignite or explode.Flammable liquid vapors are heavier than air and may settle in low spots, or move a significant distance from the liquid itself.

Occupational Safety and Health21Explosive LimitsThe explosive concentration of vapors in air has a lower and upper limit.The Lower Explosive Limit (LEL) is the lowest concentration that will ignite.The Upper Explosive Limit (UEL) is the highest concentration that will ignite.If the vapor concentration is between the LEL and UEL, there is serious risk of fire or explosion.

Occupational Safety and Health22Explosive LimitsAbove the Upper Explosive Limit, the mixture is too rich to burn

UPPER EXPLOSIVE LIMITExplosive Range

Below the Lower Explosive Limit, the mixture is too lean to burn

LOWER EXPLOSIVE LIMITOccupational Safety and Health23TemperatureLiquidUFLLFLAuto-ignition zoneAITFlash PointGasVapor pressure / concentrationFlammability RelationshipsVapor Pressure CurveAmbient TemperatureLFLUFLOccupational Safety and Health24NFPA Classification System Continued...Where can I find NFPA diamonds?Product labelsMaterial Safety Data Sheets (ask your supervisor for them)How do I determine the flammability of chemicals that dont use the NFPA classification system?The flashpoint of a chemical may be used to determine its flammability. Flashpoint information may be found on product labels or MSDS sheets.Whats a Flashpoint?The flashpoint of a liquid is the lowest temperature at which the liquid gives off enough vapor to be ignited. The lower the flashpoint, the greater the risk for ignition.Occupational Safety and Health25Flammable and Combustible Liquids Continued...Flammable liquids are considered flammable because their flashpoints are < 100F. This means that flammable liquids burn easily at normal working temperatures. Combustible liquids have a flashpoint at or above 100F. These liquids are less hazardous than flammable liquids but still pose a risk.The volatility of flammable and combustible liquids requires special storage and handling requirements. Occupational Safety and Health26ClassificationFlammable and combustible liquids are classified according to their flashpoints.

This is important to know because the quantity of flammable/combustible liquids that can be stored in any one location is determined by the class of the liquid.Occupational Safety and Health27Flammable LiquidsClass 1ALiquids having flashpoints below 73F and having a boiling point below 100F.Class 1BLiquids having flashpoints below 73F and having a boiling point at or above 100F.Class 1CLiquids have flashpoints at or above 73F and below 100F.Occupational Safety and Health28Combustible LiquidsA combustible liquid is any liquid having a flashpoint at or above 100F.Note: Check your Material Safety Data Sheet (MSDS) sheet for the characteristics or classification of a particular liquid.Occupational Safety and Health29Combustible LiquidsClass IILiquids with flashpoints at or above 100F and below 140F.Class IIILiquids with flashpoints at or above 140FClass IIIAThose with flashpoints at or above 140F and below 200F.Class IIIBThose with flashpoints at or above 200F.Occupational Safety and Health30Area Exempt AmountsThere are certain amounts of flammable and combustible liquids stored in each control area that are considered exempt.If these amounts are exceeded, then the area or building may have to be reclassified as a Hazardous Use Group under the building code.Occupational Safety and Health31Storing Flammable and Combustible LiquidsFlammable liquids must be stored away from ignition sources in cool, well ventilated areas away from incompatible materialsLimit the amount of flammable and combustible liquids to the minimum amount necessary.As a general rule, No more than 10 gallons of flammable materials should be outside of approved flammable liquid storage cabinets or approved storage rooms.Room storage limits of flammable and combustible materials depend on various factors such as sprinklers, and storage cabinets. Refer to the table on the following slide for storage guidelines.

Occupational Safety and Health32Storage AreasFlammables should be stored in an approved cabinet in a cool, well ventilated area to avoid pressure buildup and vaporization.

Occupational Safety and Health33Storage AreasThere should be at least one fire extinguisher in the area.Large storage areas should have a fire protection system installed and must be approved for this use.

Occupational Safety and Health34Storage CabinetsUse flammable liquid storage cabinets where greater quantities of liquids are needed.

Contrary to popular belief, these cabinets are not designed to contain a fire, but to prevent an outside fire from reaching the contents for a period of 10 minutes enough time to evacuate the area.Occupational Safety and Health35Flammable Liquid Exempt Amounts (in gallons)ConditionIAIBICInside; unprotected by sprinklers or cabinets.306090Within approved cabinet; unsprinklered structure.60120180Not in approved cabinet; sprinklered structure.60120180In approved cabinet; sprinklered structure.120240360Outside storage.60120180Occupational Safety and Health36Combustible Liquid Exempt Amounts (in gallons)ConditionIIIIIAIIIBInside; unprotected by sprinklers or cabinets.12033013,200Within approved cabinet; unsprinklered structure.24066026,400Not in approved cabinet; sprinklered structure.240660unlimitedIn approved cabinet; sprinklered structure.4801,320unlimitedOutside storage.240660unlimitedOccupational Safety and Health37Limitations on StorageThe maximum storage of flammables and combustibles in any one area under the Virginia Fire Prevention Code is 60 gallons of flammables and 120 gallons of combustibles.These quantities must be in an approved storage area, i.e. a flammables cabinet or other acceptable means.

Anondho Wijanarko dan YuliusmanKeselamatan Kerja37Va. Fire Prevention Code 32-01.4Occupational Safety and Health38There are also limitations on quantities stored in individual containers.

Anondho Wijanarko dan YuliusmanKeselamatan Kerja38FLSP page 44Occupational Safety and Health39Storage ContainersContainers should be tightly sealed when not in use.Approved safety cans are recommended for smaller quantities.The spring-loaded safety cap prevents spillage, prevents vapors from escaping, acts as a pressure vent if engulfed in fire, prevents explosions and rocketing of the can!

Anondho Wijanarko dan YuliusmanKeselamatan Kerja39FLSP page 15Occupational Safety and Health40Flammable Liquid Limitations(in gallons)ContainerIAIBICGlass or approved plastic1 pt.1 qt.1Metal (other than DOT drum)155Safety cans255Metal drums (DOT specifications)606060Approved portable tanks660660660Anondho Wijanarko dan YuliusmanKeselamatan Kerja40FLSP page 44Occupational Safety and Health41Combustible Liquid Limitations(in gallons)ContainerIIIIIGlass or approved plastic11Metal (other than DOT drums)55Safety Cans55Metal drums (DOT specifications)6060Approved portable tanks660660Anondho Wijanarko dan YuliusmanKeselamatan Kerja41FLSP page 44Occupational Safety and Health42PrecautionsThe unsafe use, storage, dispensing, or disposal of flammable materials can be a prime source of fires and explosions.Read labels of all spray cans to identify those with flammable gas-propellants.

Ex. Butane and PropaneAnondho Wijanarko dan YuliusmanKeselamatan Kerja42FLSP page 12Occupational Safety and Health43PrecautionsSome flammable liquids have a tendency to accumulate a static electric charge, which can release a spark that ignites the liquid.Always bond metal dispensing and receiving containers together before pouring.xylenetoluenebenzenegasolineAnondho Wijanarko dan YuliusmanKeselamatan Kerja43FLSP page 15Occupational Safety and Health44PrecautionsTo bond containers, each container is wired together and one container is connected to a good ground point to allow any charge to drain away safely.Because there is no easy way to bond plastic containers, their use should be limited to smaller sizes (no more than 4L).

Anondho Wijanarko dan YuliusmanKeselamatan Kerja44FLSP page 15Occupational Safety and Health45PrecautionsOverexposure to flammable liquids may present health hazards.Consult the Material Safety Data Sheet (MSDS) on the material you will be using to identify health hazards and protective measures to be taken.

Occupational Safety and Health46PrecautionsEffects of overexposure to flammable liquids includes:Inhalation: Irritation to respiratory passages, nausea, headaches, muscle weakness, drowsiness, loss of coordination, disorientation, confusion, unconsciousness, and death.Anondho Wijanarko dan YuliusmanKeselamatan Kerja46From Toolbox TopicOccupational Safety and Health47PrecautionsSkin Contact: irritated, dry, cracked skin, rashes, dermatitis.Eye Contact: burning, irritation, eye damage.Ingestion: irritated digestive tract, poisoning, death. Anondho Wijanarko dan YuliusmanKeselamatan Kerja47From Toolbox TopicOccupational Safety and Health48

I.S.U. Flammable Liquid Storage LimitsOccupational Safety and Health49FIRE BEHAVIOR

Occupational Safety and Health50Law of Conservation of MassMass and Energy are neither created nor destroyed, only changed in state Why Fire Load is a crucial part of scene size up

Occupational Safety and Health51Fire vs. CombustionCombustion Self-sustaining chemical reaction yielding energy or products that cause further reactions of the same kindFire rapid, self sustaining oxidation process accompanied by the evolution of heat and light of varying intensities

Occupational Safety and Health52Ignition TemperatureMinimum temperature to which a fuel, in air, must be heated to start self-sustained combustion without a separate ignition source.

Occupational Safety and Health53Fire TriangleHeatOxygenFuelAppropriate Model for Smoldering Fires

Occupational Safety and Health54Fire TetrahedronReducingAgent(Fuel)OxidizingAgentHeatChemicalChain React.

Occupational Safety and Health55Oxidizing AgentO2 or materials that yield oxidizing gasses

Oxygen Concentration21% Normal Concentration at 70 F31% Nomex Burns17% Some Impairment of Coordination9% Unconsciousness2% can support combustion if temp is high enough6% Death within a few minutes14% at 70 F lowest point of Combustion

Occupational Safety and Health56Reducing Agent (Fuel)Now fuel must normally be in a gaseous state to burn, putting solids and gasses into this state requires energy.Pyrolosis When a solid is heated, the combustible materials are driven from the material

Occupational Safety and Health57Notes on Gaseous FuelsThese tend to be the most dangerous, because no energy is necessary to convert them for ignition.

Notes on Liquid FuelsGasses are created by vaporization rather than pyrolosisRequire less energy to convert to gas than pyrolizing solidsRate of evaporation is influenced by the material and the temperature The surface to mass ratio is inversely proportional to the amount of energy needed for ignitionPlacement of fuel (Horizontal vs. Vertical)

Notes on Solid FuelsOccupational Safety and Health58FLAMMABLE LIMITSFlammable RangeUpper Flammable Limit (UFL) Lower Flammable Limit (LFL)Too Lean, nothing burnsToo Rich, nothing burns

Occupational Safety and Health59HEATCauses pyrolosis, vaporization, or production of ignitable vaporsProvides the energy necessary for ignitionCauses the continuous production and ignition of vapors so that the reaction can continue.

Occupational Safety and Health60Types of HeatChemical Most Common. When combustible is in contact with oxygen oxidation occurs and heat is generated.Electrical include resistance heating, overcurrent/overload, arcing, static, lightning etc.Mechanical Heat of friction (causing a belt on a pulley to burn), or heat of compression (why SCBAs are hot following filling)Nuclear

Occupational Safety and Health61Self Sustained Chemical ReactionThe complex reaction that causes each of the other parts of the system to combine in precisely the right amounts and at the right times to continue

Occupational Safety and Health62Products of CombustionHeatLightSmokeFire GassesCO (Carbon Monoxide)HCN (Hydrogen Cyanide)CO2 (Carbon Dioxide)N2 (Nitrogen)And MANY others

Occupational Safety and Health63LAW OF HEAT FLOWHeat tends to flow from a hot substance to a cold substance

Occupational Safety and Health64CONDUCTIONOccurs when a body is heated as a result of direct contact with a heat sourcePrimary cause for fire spread early in firesFire spread by heating a pipe in one room and starting a fire in another room

Occupational Safety and Health65CONVECTIONTransfer of heat energy by movement of heated liquids or gassesHeat you feel when your hand is above a candle/matchProduces thermal layeringAlso can cause fire extension between floors Occupational Safety and Health66RADIATIONTransfer of heat energy w/o intervening mediumHolding you hand to the side of a candleMajor problem. This is frequently what causes fire extension to other buildings

Occupational Safety and Health67How is this fire transferring?

Occupational Safety and Health68PHASES OF FIREIncipient PhaseRolloverSteady State Burning (Free Burning)Flashover

Occupational Safety and Health69Hot Smoldering PhaseAfter Steady StateMinimal FlamesHigh TempVentilation Limited (>15% 02)May be pre backdraft

Occupational Safety and Health70BackdraftLow O2, High Heat, Smoldering Fire, High Fuel vapor concentrationsPressurized smoke exiting small openingsDense, gray yellow smokeLittle or no visible flameSmoke stained windowsImproper ventilation leads to explosionOccupational Safety and Health71Thermal Layering

Extreme HeatModerate HeatOccupational Safety and Health72Extinguishment TheoryRemove any part of the Tetrahedron and the fire goes outReducingAgent(Fuel)OxidizingAgentHeatChemicalChain React.Occupational Safety and Health73Maintaining Fire BarriersFire doors need occasional maintenance and repairs to function properly and should be periodically checked. To test a fire door:Open the door fully and allow it to swing shut. The door should close and latch completely by itself. Give the door a push after it closes to ensure that the latch has engaged.If the door is not operating properly contact FP&M for repairs.Ceiling, Floor, Wall PenetrationsAll areas should be properly sealed to prevent the escape of fire, heat and smoke.Common penetrations include holes in walls, around ducts, pipes, etc. These types of penetrations should be sealed with appropriate fire-stopping material.Occupational Safety and Health74CompartmentalizationBuildings are designed to prevent fire, heat, and smoke from spreading beyond locations of origination. Building elements such as fire walls, fire dampers, and fire doors, are designed to seal off one location from the next. This system is called compartmentalization. Compartmentalization increases the safety of evacuating building occupants because smoke and fire are not able to escape into exit passageways. Containment of fire and smoke reduces property damage and prevents small fires from growing into large fires.In order for compartmentalization efforts to be effective fire barriers must be maintained.Occupational Safety and Health75Whats A Fire Door?Fire doors are designed to withstand fire, heat and smoke for a period of 20-minutes to 3 hours.Did you know that corridor office doors are fire doors and should have a 20 minute rating?Corridor laboratory doors should have a 60 minute rating.Fire Doors are required to:Be Self Closing: fire doors should have a door closure that pulls doors completely shut after the door has been openedHave Positive latching: a positive latch locks a door in place so can open swing open freely.

Occupational Safety and Health764 Reasons Not to Wedge Open Fire DoorsFor the safety of your buildings occupants. If a fire occurs in a location where the fire door has been wedged, smoke and heat will travel freely into exit corridors hindering or preventing occupant evacuation. Its State LawPeriodically Iowas State Fire Marshal inspects our campus and issues numerous citations for wedging or blocking open doors.

To reduce or prevent damage to property, research, personal belongings, etc.Keeping your door shut will keep out smoke or fire originating in other locations.

To hold open your door you may have an electro-magnetic device installed.This device releases a fire door upon activation of the fire alarm allowing it to close and latch.Occupational Safety and Health77Toxic MaterialsMaterials which, upon entering an human body is capable of producing disease or death

Toxicity factor consist of (1) The quantity of the material (2) The rate and extent to which the material is absorbed into the bloodstream via intravenous, inhalation, intraperitoneal, intramuscular, subcutaneous, oral or cutaneous (3) The rate and extent to which the material is biologically transformed in the body to breakdown product.US Department of Transportation Regulation

Occupational Safety and Health78Toxic MaterialsHEAVY METAL POISONS (Arsenic, Lead, Mercury salts) DISEASE AGENT (BIOHAZARD) Botulinum Toxin, Ricin toxin, Epsilon toxin, Staphlococcus enterotoxin B, Shigella toxin (Shigella dysenteriae toxin or Stx , CAS # 75757-64-1), Shigella-like toxins produced by Escherencia coli O 157(Shiga-like toxin 1, verotoxin 1, or Stx-1, and Shiga-like toxin 2, verotoxin 2 or Stx-2 )TOXIC GASES Asphyxiant (CO, HCN, NO), Irritant (NO2, H2S, SO2) Anesthetic (diethyl eter, N2O2) ORGANIC PESTICIDES INSECTICIDE Aldrin, DDT, Parathion, Chlordane, Diazinon, Dieldrine, Lindane, Malathion, Methoxychlor, CarbylUS Department of Transportation Regulation

Occupational Safety and Health79TOXIC CHEMICALSAll substances are intrinsically toxic (hazard) whether or not the inherent toxicity will become a risk depends on the Dose received and the Recipients sensitivity to the chemical concentrationThe Dose received and the Recipients sensitivity can be combined in a dose/response curves to examine the response of a population to different levels of a toxinOccupational Safety and Health80TOXIC CHEMICALS

Occupational Safety and Health81CHEMICALSThe dose/response curve shows that some exposure is necessary before most individuals respond. Hence, toxic effects of chemicals are concentration dependent

Occupational Safety and Health82CHEMICALS: Major Types of ToxicityAcute toxicity: It involves lethal concentrations and short-term exposures Acute effects of a toxin appear immediately after exposure.The end point is usually death, hence it is used to derive LD50An LD50 is a dose of a toxic chemical that kills half of the population.LD50 is obtained by plotting, for a given dose the proportion of the population that responded to that dose and all lower dosesOccupational Safety and Health83CHEMICALS: Major Types of Toxicity

Occupational Safety and Health84CHEMICALS: Major Types of ToxicityChronic toxicity: It involves Sub-lethal concentration and long-term exposureChronic toxicity test is used to derive Effective Dose (ED50): Is the dose by which half of the population has been affectedEffect could be anything but deathED50 is obtained by plotting, for a given dose the proportion of the population that responded to that dose and all lower dosesChronic effects of a toxic response can last a long time or be permanent.Occupational Safety and Health85CHEMICALS: Major Types of ToxicityThe end points of chronic toxicity could be: biochemical physiological These ends points may lead to responses at organism level (e.g. behavioral and production changes) Responses at organism level could lead to effects on population which could have implications at the community level Responses at community level could also be implicated at ecosystem level. Occupational Safety and Health86CHEMICALS: Major Types of ToxicityUnder chronic conditions the organism survives but production or gene frequency could be affected.This is the level (sublethal) of interest in ecotoxicology.Typical example is the effect of DDT on egg shell thinning in birds. Here the birds survived DDT exposure but their reproduction mechanisms was affectedUnlike transient pollution which has a passing effect on gene frequency, chronic pollution changes the environment. Occupational Safety and Health87Intentional Poisoning*

AdvantagesGenderSilent Male46%Precise targeting Female39%Depersonalized Unknown16%Safe for attacker

ProfileBackgroundCaucasianPublic71%MalePhysician 8%Average or above intelligencePolitical 4%UnderachieverNurse 4%Personality defectOther 5%Cowardly, nonconfrontationalUnknown 9%NonathleticNeat and orderly, meticulousCareful planner*Source: Criminal Poisoning (2000)LonerJ. H. Trestrail, Humana Press

Occupational Safety and Health88Properties of Ideal Poison

Undetectable by sensesSolubleDelayed effectEasily obtainedNot traceableSymptoms mimic actual diseaseChemically stable (?)Undetectable by instrumentationPotent

Occupational Safety and Health89

The dose makes the poison

Potencies of Poisons

AgentLethal dose

Botulinum toxin 0.05 mg

Ricin 0.5 mg

Strychnine 100 mg

Sodium arsenite 200 mg

Sodium cyanide 250 mg

Thallium1000 mg

NB: A dime is 2300 mgOccupational Safety and Health90Sources of Poisons

Commercial

Laboratories

Underground catalogs

Antique drug collections

Hobbies/natural sources (e.g., plants)

Occupational Safety and Health91Pesticide Poisons of Note

Synthetic OrganophosphatesCarbamates Paraquat Fluroacetate (1080 bait)

Plant-derived Oleander Poison hemlock Mushroom Ricin Atropine/belladonna Nicotine Strychnine Cyanogenic glycosides

Occupational Safety and Health92

Poison plants readily available from nurseries, arboreta, backyards, wild areasFoxglove Datura Oleander Autumn Poison Lantana Ricinus communispurpurea crocus hemlock (Castor bean)

digitalis atropine cardiac colchicine coniine lantadene ricin glycosides

Not visible: Lupine (lupanine)Occupational Safety and Health93

Top 5 Homicidal Poisons

Agent FrequencyTarget

Arsenic 31%Energy generation

Cyanide 9%

Strychnine 6%Nervous system

Morphine 3%

Chloroform 2%Occupational Safety and Health94

Toxin Background Analysis

Evidence in vicinity of victimPill bottle, drug paraphernaliaFood, beverage leftoversSymptomsAcuteChronicSamplingOrgans, fluidsAccessory materialDetectionAnalytical instrumentationHPLC, GC, Mass SpecMotivationLove, money, powerDisguised as randomOccupational Safety and Health95

Poison Symptoms

Constricted/dilated pupils (opioids, organophosphates)

Breath odor (arsenic garlic)

Hair loss (thallium)

Convulsions (strychnine)

Paralysis (botulism)

Coma (depressants, hypnotics)

Skin color (CO cherry red; nitrites blue)

Skin appearance (arsenic hyperkeratosis, warts) (dioxin chloracne)Occupational Safety and Health96

Occupational Safety and Health97ArsenicCan be used as pesticideAffects skin, liver, nervous systemIs a risk factor for lung cancerHistory and physical examUrine test (can be affected by seafood consumption)

Occupational Safety and Health98Arsenic As at. No 33 m.p. 613oAbundance & Userelatively rare, no nutritional roleuses include pesticides, pigments, wood preservatives, marine paintfound in WI H20, added to chicken feedPharmacologytoxicity: As+3 > As+5 > organic (shellfish)salts > oxidesefficiently absorbed from gutexcreted in urine, does not accumulatebinds to SH groups

Occupational Safety and Health99Effectsarsine gas = hemolysis/renal failureG.I. = bloody vomiting & diarrhearenal & vascular necroses--gangrenealopecia, mees lines, bronzing, garlic odor

Assessmenturine, hair semi-reliablemeasured by AA, ICP, colorimetrytreated with dimercaprol (BAL), DMSA

Occupational Safety and Health100Arsenic Trioxide1 to 2.5 mg/kg - potentially fatal dose binds to cellular proteins containing sulfhydryl groupsdecrease in glutathione necessary for the metabolic detoxification of arsenicCommon toxidrome:Abdominal pain, nausea/vomiting,malaiseNeuropathiesPancytopeniasHepatitisPeripheral vascular diseaseCardiovascular collapse

Occupational Safety and Health101Arsenic Trioxide>500 years use in traditional Chinese medicine1970s investigators in China reported its use in APL but were ignored by mainstream medicineDual apoptotic and differentiation inducing propertiesDoses 0.06-0.2 mg/kg (~1/3 fatal dose)CR rates ~90% in de-novo APL

Occupational Safety and Health102And if you change your mind?the earlier the betterChelation therapy Dimercaprol (BAL)DMSOContraindicationspre-existing renal disease, pregnancy, concurrent use of iron, G6PD

Occupational Safety and Health103Cadmium Cd at. No 48 m.p. 321oAbundance & Usefound w/Zn in 1:70 rationo nutritional roleused in electroplating, batteries, solder, plasticsPharmacologybiological 1/2 life >10 yearstoxicity inhaled > ingestedstrong emeticinternal metallothionen chelationsubstitutes for Zn in enzymes

Occupational Safety and Health104Effectsemphysemanephrotoxicity, increased Ca excretionosteomalacia, itai-itai disease, kidney stones

Assessmentblood, urine, urinary proteinsmeasured by AA, ICPZn administration confers protectionchelation may increase bioavailability

Occupational Safety and Health105

Occupational Safety and Health106DioxinsDioxinsWhat are they?Dioxin is a general term for hundreds of chemicals formed by burning chlorine based compounds with hydrocarbons (www.ejnet.org/dioxin, 2002)What do they do?They get into the air, then soil and water, and then our food chainThey attach and accumulate in our fat cellsDioxin is passed onto our childrenThrough placenta, and breastfeedingWe have no defense because it is not metabolized in our bodiesIt can cause serious health problems at parts per trillion (www.acereport.org,2003)

Occupational Safety and Health107(www.ejnet.org/dioxin,2002)

Occupational Safety and Health108Harmful Effects of DioxinCauses cancerDisrupts hormonesMay shrink penis size and sperm countMiscarriage, reproductive disorders, birth defects, low birth weightLearning disabilitiesShort term memory and attention spanDamage to nervous and immune systems (www.acereport.org,2003)

Occupational Safety and Health109TCDD (dioxin) Chloracne

Poisoning of Victor Yushchenko just before Ukraine presidential election

Occupational Safety and Health110Dioxin (TCDD) Sensitivities

SpeciesLD50 (g/kg)

Guinea pig 2Rat 40Monkey 50Human ?Mouse 130 Rabbit 200Hamster4000

Occupational Safety and Health111Autopsy samples

Organs (brain, liver, kidney, muscle)Blood (heart, peripheral)Vitreous humor Bile (insoluble metabolites)Urine (soluble)Gastric contents (alkaloids)

HairBoneMaggots

Occupational Safety and Health112Environmental/Accidental Contamination

Differential diagnosisAccidental death or homicide?Compensable injury or carelessness?Background that could confound interpretation

Verify authenticity/natural source or show adulterationHow did the mass poisoning occur?Substitution of inferior/contaminated component?

Track source of environmental contaminationEnvironmental justice for underserved?Safeguards not enforcedChildren often victimsWhich companies are breaking the law?

Occupational Safety and Health113Marine Toxins in Food

PufferfishDelicacy in Japanese restaurantsGives tingling of lips when properly preparedTetrodotoxin concentrated in liver and ovary (removed)Blocks sodium channel in nervesFatal in excess (lethal dose 1 mg)

Shellfish Tainted by Red Tide (3 examples)Saxitoxin Paralytic shellfish poison (blocks sodium channel), potentially fatalDomoic acid Amnesic shellfish poison (glutamate neurotransmitter analog)Disorientation, loss of short term memory at moderate dosesFatal excitotoxin activity at higher dosesOkadaic acid Diarrhetic shellfish poison (phosphatase inhibitor), nonfatal

Harmful Algal BloomsThought increasing due to coastal pollution, ocean warmingOf 4,400 known algal species, >1% produce toxinsKnown causes of wildlife epidemicsMarine mammal mortality off California coast from domoic acid

Occupational Safety and Health114 Accidental Food Contamination

Iraq 1972: 5-6,000 people hospitalized, 10% died.Seed grain donated with methyl mercury antifungal agent.Distributed 100,000 tons to farmers, improperly identified.Grain (wheat, barley) mistakenly used to make bread.

Michigan 1973: Nearly 2 million livestock destroyed.Several hundred pounds PBBs mixed with dairy feed.Coverup by company and state officials compounded problem.

Spain 1981: 11,000 people hospitalized, >500 died.Industrial rapeseed oil from France containing aniline refined.Refining process produced toxic components.Resold fraudulently as cooking oil (59 tons) after mixing olive oil.

Adulturation of vegetable oils (soybean/canola in olive) frequent.Biochemical components becoming available for detection.

Occupational Safety and Health115MercuryUsed as pesticide, pigment or preservativeCan cause central nervous system, behavioral and renal effectsHistory, physical examUrine testing

Occupational Safety and Health116Mercury Hg at. No 80 m.p. -39oCharacteristics & Useliquid at RT, high vapor pressureGood electrical conductorAll forms toxicmany usesdental amalgamsseed, paint, wood preservative (mostly banned)lamps, switches, thermometersindustrial catalystmedicines (mostly historical)

Occupational Safety and Health117Hg Chemistry & PharmacologyChemical form importantall toxic, but:effects and pharmacology differinfluences best samples for assessmentMetallic mercury Hgoinhaled vapor ~80% absorbedingestion is nontoxicexcreted in urine (& respired air)urine best test sample

Occupational Safety and Health118Hg Chem & Pharm, contInorganic mercury (Hg salts) Hg++G.I. absorption 2-38%excreted in bile and urinetest urine or bloodOrganic mercury Ch3Hg+nearly 100% G.I. absorbedpossible dermal absorptionexcreted in bile, some reabsorbedtest blood or hair

Occupational Safety and Health119Sources of HgNatural sources = 33-50% of totalvolcanoes weathering of mercury-containing rocksAnthropogenic sources = 50-67% of totalmining and smeltingcinnibar ore, HgScombustion of coal 80% anthrowaste incinerationOther municipal/industrial releases

Occupational Safety and Health120Hg Exposure PathwaysHg vapor precipitates, enters waterwaysSediment bacteria methylateMethylmercury biomagnifies in fish

Dietary intake biggest exposure source

Occupational Safety and Health121

Commercial Activity - Mercury A woman holds a victim of "Minamata Disease", or mercury poisoning, in Minamata, Japan, in 1973. The girl has a malformed hand, like many victims of the disease who suffer from physical deformities and mental retardation. Chisso Corporation, a Japanese fertilizer, petrochemical and plastics company, dumped an estimated 27 tons of mercury compounds into Minamata Bay between 1932 and 1968. Up to10,000 people were affected byeating seafood from the bay.Many sources of mercury exist, either natural (fish) or associated with human activity (chloralkali plants, gold mines, effluent from power plants).Elemental form is methylated by micro-organisms in the environment.

Occupational Safety and Health122Hg Exposure Pathways, contHg vapor from household products

Occupational Safety and Health123Hg Health EffectsMetallic Hgprimarily affects CNS, kidneys, & lungstremor, personality changes, deleriumfatigue, anorexia, excess salivationacrodynia, pink diseaseeffects often reversible

Occupational Safety and Health124Inorganic HgG.I. tract necrosiscramps, bloody diarrhea, circulatory collapserenal failuretooth & jaw necrosis, black gum linesno major CNS effects

Occupational Safety and Health125Hg Health Effects, contEffects Ch3Hg+potent neurotoxinparasthesias, esp. lips and fingersataxia, slurred speech, blurred visionconfusion & agitationpenetrates skin and latex

Table 1. Room Storage Limits for Flammable and Combustible Liquids

Class of LiquidFlash point (F)Boiling

point (F)Non

Sprinkled BuildingNon

Sprinkled Bldg. & Flammable Liquid Storage CabinetSprinkled

BuildingSprinkled Bldg./Flammable Liquid Storage Cabinet

Class 1A,

Flammables