occupational safety and health1 corrosive materials materials that evoke a chemical process which...

Occupational Safety and Health 1

Corrosive 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


Corrosive MaterialsChemical substances that, by direct

chemical action, are injurious to living tissues or corrosive to metal surfaces

The degree of hazard associated with a corrosive material is greatly dependent upon its physical state (solid, liquid, gas)

Minor corrosive injury = irritation


Corrosive 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 hazardous


Corrosive Liquids: Bases Concentrated alkalies are more damaging to

tissues than most strong inorganic acids Alkaline solutions gelatinize and saponify

tissues, producing deeply penetrating, painful burns

Even weak alkaline solutions can dissolve skin fats and weaken the epidermis, making the skin more permeable to other agents

Initial contact may not be painful – poor warning property!


Corrosive 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.


Corrosive Liquids: organic solvents

A 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.


Corrosive Liquids: hydrofluoric acid

HF and gaseous hydrogen fluoride merit special discussion. These are easily the most hazardous corrosive materials encountered in the laboratory

HF 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 burns

Always store/use HF solutions and hydrogen fluoride gas in a chemical fume hood – never on the lab bench!


Corrosive Gases Most 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!


Corrosive GasesHighly water soluble (upper respiratory tract)

Medium aqueous solubility (upper respiratory tract and bronchi)

Low aqueous solubility (easily reaches alveoli, causing delayed pulmonary edema

Ammonia Bromine Phosgene

Hydrogen chloride Chlorine Nitrogen dioxide

Hydrogen fluoride Iodine Ozone

Formaldehyde Phosphorus pentachloride

Sulfonyl chloride Phosphorus trichloride

Thionyl chloride Sulfur dioxide


Improper 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/spills


HIGHLY TOXICA chemical which has the median lethal dose of: 50 mg per kg when administered orally 200 mg per kg by continuous contact for 24 hrs

A 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 ANIMALS


IRRITANTAn 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 contact


SENSITIZERA chemical which causes a substantial portion of exposed people to develop an allergic reaction in normal tissue after repeated exposure to the chemical


DEFINITION OF A HAZARDOUS WASTE

ANY 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.


FLAMMABLE MATERIALS


Flammable 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.


Isopropyl alcoholToluene

Diethyl ether

Methyl formate

Acetone

Ethyl ether

Kerosene

Lacquer thinnerGasoline

MEK

Flammable and Combustible Liquids


NFPA classification system The 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 burn

1- must be preheated to burn

2-ignites when moderately heated

3-ignites at normal temperature

4-extremely flammable

How do I tell what’s 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


Flammable Liquids

Flammable 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


Flammable Liquids

The 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.


Explosive Limits

The 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.


Explosive Limits

Above the Upper Explosive Limit, the mixture is too rich to burn

UPPER EXPLOSIVE LIMIT

Explosive Range

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

LOWER EXPLOSIVE LIMIT


Temperature

Liquid

UFL

LFL

Auto-ignition zone

AITFlash Point

Gas

Vap

or

pre

ssu

re /

con

cen

trati

on

Flammability Relationships

Vapor Pressure Curve

Ambient Temperature

LFL

UFL


NFPA Classification System Continued... Where can I find NFPA diamonds?

Product labels Material Safety Data Sheets (ask your supervisor

for them) How do I determine the flammability of

chemicals that don’t 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.What’s 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.


Flammable and Combustible Liquids Continued... Flammable liquids are considered flammable

because their flashpoints are < 100ºF. This means that flammable liquids burn easily at normal working temperatures.

Combustible liquids have a flashpoint at or above 100ºF. 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.


Classification Flammable 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.


Flammable Liquids

Class 1A Liquids having flashpoints below 73°F and having a boiling point below 100°F.

Class 1B Liquids having flashpoints below 73°F and having a boiling point at or above 100°F.

Class 1C Liquids have flashpoints at or above 73°F and below 100°F.


Combustible Liquids

A combustible liquid is any liquid having a flashpoint at or above 100°F.

Note: Check your Material Safety Data Sheet (MSDS) sheet for the characteristics or classification of a particular liquid.


Combustible Liquids

Class II Liquids with flashpoints at or above 100°F and below 140°F.

Class III Liquids with flashpoints at or above 140°F

Class IIIA Those with flashpoints at or above 140°F and below 200°F.

Class IIIB Those with flashpoints at or above 200°F.


Area 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.


Storing Flammable and Combustible Liquids

Flammable liquids must be stored away from ignition sources in cool, well ventilated areas away from incompatible materials

Limit 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.


Storage Areas Flammables should be stored in an approved

cabinet in a cool, well ventilated area to avoid pressure buildup and vaporization.


Storage Areas

There 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.


Storage 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.


Flammable Liquid Exempt Amounts (in gallons)

Condition IA IB IC

Inside; unprotected by sprinklers or cabinets.

30 60 90

Within approved cabinet; unsprinklered structure.

60 120 180

Not in approved cabinet; sprinklered structure.

60 120 180

In approved cabinet; sprinklered structure.

120 240 360

Outside storage. 60 120 180


Combustible Liquid Exempt Amounts (in gallons)

Condition II IIIA IIIB

Inside; unprotected by sprinklers or cabinets.

120 330 13,200

Within approved cabinet; unsprinklered structure.

240 660 26,400

Not in approved cabinet; sprinklered structure.

240 660 unlimited

In approved cabinet; sprinklered structure.

480 1,320 unlimited

Outside storage. 240 660 unlimited


Limitations on Storage

The 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.


There are also limitations on quantities stored in individual containers.


Storage Containers

Containers 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!


Flammable Liquid Limitations(in gallons)

Container IA IB IC

Glass or approved plastic 1 pt. 1 qt. 1

Metal (other than DOT drum) 1 5 5

Safety cans 2 5 5

Metal drums (DOT specifications) 60 60 60

Approved portable tanks 660 660 660


Combustible Liquid Limitations(in gallons)

Container II III

Glass or approved plastic 1 1

Metal (other than DOT drums) 5 5

Safety Cans 5 5

Metal drums (DOT specifications) 60 60

Approved portable tanks 660 660


PrecautionsThe 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 Propane


PrecautionsSome 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.


PrecautionsTo 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).


Precautions

Overexposure 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.


PrecautionsEffects of overexposure to flammable

liquids includes: Inhalation: Irritation to respiratory

passages, nausea, headaches, muscle weakness, drowsiness, loss of coordination, disorientation, confusion, unconsciousness, and death.


Precautions

Skin Contact: irritated, dry, cracked skin, rashes, dermatitis.

Eye Contact: burning, irritation, eye damage.

Ingestion: irritated digestive tract, poisoning, death.


Table 1. Room Storage Limits for Flammable and Combustible LiquidsClass ofLiquid

Flashpoint(°F)

Boilingpoint(°F)

NonSprinkledBuilding

NonSprinkled Bldg. &Flammable LiquidStorage Cabinet

SprinkledBuilding

SprinkledBldg./FlammableLiquid StorageCabinet

Class 1A,Flammables

<73 °F <100 °F 10 gal. 20 gal. 10 gal 40 gal.

Class 1BFlammables

<73 °F >100 °F 10 gal. 40 gal. 10 gal 80 gal.

Class 1CFlammable

> 73 &<100 °F

NA 10 gal. 60 gal. 10 gal 120 gal.

Class IICombustibles

>100 &<140 °F

NA 30 gal. 60 gal. 60 gal. 90 gal.

Class III-ACombustibles

>140&<200°F

NA 50 gal. 100 gal. 100 gal. 150 gal.

Note: Containers other than safety cans shall not be greater capacity than one (1) gallon. The number oftwo (2) gallon safety cans shall not exceed five (5). The number of one (1) gallon safety cans in useoutside storage cabinets shall not exceed ten (10).

I.S.U. Flammable Liquid Storage Limits


FIRE BEHAVIOR


Law of Conservation of Mass

Mass and Energy are neither created nor destroyed, only changed in state

Why Fire Load is a crucial part of scene size up


Fire vs. Combustion

Combustion Self-sustaining chemical reaction yielding energy or products that cause further reactions of the same kind

Fire rapid, self sustaining oxidation process accompanied by the evolution of heat and light of varying intensities


Ignition Temperature

Minimum temperature to which a fuel, in air, must be heated to start self-sustained combustion without a separate ignition source.


Fire Triangle

Heat

Oxygen

Fuel

Appropriate Model for Smoldering Fires


Fire Tetrahedron

ReducingAgent(Fuel)

OxidizingAgent

Heat

ChemicalChain React.


Oxidizing Agent

O2 or materials that yield oxidizing gassesO

xyge

n C

once

ntra

tion

21% Normal Concentration at 70 F31% Nomex Burns

17% Some Impairment of Coordination

9% Unconsciousness

2% can support combustion if temp is high enough6% Death within a few minutes

14% at 70 F lowest point of Combustion


Reducing 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


Notes on Gaseous Fuels These tend to be the most dangerous, because no

energy is necessary to convert them for ignition.

Notes on Liquid Fuels Gasses are created by vaporization rather than pyrolosis Require less energy to convert to gas than pyrolizing

solids Rate 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 ignition

Placement of fuel (Horizontal vs. Vertical)

Notes on Solid Fuels


FLAMMABLE LIMITS

Flammable Range

Upper Flammable Limit (UFL)

Lower Flammable Limit (LFL)

Too Lean, nothing burns

Too Rich, nothing burns


HEAT

Causes pyrolosis, vaporization, or production of ignitable vapors

Provides the energy necessary for ignition

Causes the continuous production and ignition of vapors so that the reaction can continue.


Types of Heat

Chemical – 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


Self Sustained Chemical Reaction

The 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


Products of Combustion Heat Light Smoke Fire Gasses

CO (Carbon Monoxide) HCN (Hydrogen Cyanide) CO2 (Carbon Dioxide) N2 (Nitrogen) And MANY others


LAW OF HEAT FLOW

Heat tends to flow from a hot substance to a cold substance


CONDUCTIONOccurs when a body is heated as a

result of direct contact with a heat source

Primary cause for fire spread early in fires

Fire spread by heating a pipe in one room and starting a fire in another room


CONVECTIONTransfer 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


RADIATIONTransfer 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


How is this fire transferring?


PHASES OF FIRE Incipient PhaseRolloverSteady State Burning (Free Burning)Flashover


Hot Smoldering PhaseAfter Steady StateMinimal FlamesHigh TempVentilation Limited (>15% 02)May be “pre backdraft”


BackdraftLow O2, High Heat, Smoldering Fire,

High Fuel vapor concentrationsPressurized smoke exiting small

openingsDense, gray yellow smokeLittle or no visible flameSmoke stained windows Improper ventilation leads to explosion


Thermal Layering

Extreme Heat

Moderate Heat


Extinguishment Theory Remove any part of

the Tetrahedron and the fire goes out

ReducingAgent(Fuel)

OxidizingAgent

Heat

ChemicalChain React.


Maintaining Fire Barriers

Fire 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 Penetrations All 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.


Compartmentalization

Buildings 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.


What’s 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 opened

Have Positive latching: a positive latch locks a door in place so can open swing open freely.


4 Reasons Not to Wedge Open Fire Doors

1 For 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.

2 It’s State Law Periodically Iowa’s State

Fire Marshal inspects our campus and issues numerous citations for wedging or blocking open doors.

3 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.

4 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.


Toxic 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.



Toxic 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, Carbyl



TOXIC CHEMICALSAll substances are intrinsically toxic

(hazard) whether or not the inherent toxicity will

become a risk depends on the Dose received and the Recipient’s sensitivity to the chemical concentration

The Dose received and the Recipient’s sensitivity can be combined in a dose/response curves to examine the response of a population to different levels of a toxin


TOXIC CHEMICALS


CHEMICALSThe dose/response curve shows that some

exposure is necessary before most individuals respond.

Hence, toxic effects of chemicals are concentration dependent


CHEMICALS: Major Types of Toxicity Acute 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 LD50

An 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 doses


CHEMICALS: Major Types of Toxicity



Chronic toxicity: It involves Sub-lethal concentration and long-term exposure

Chronic toxicity test is used to derive Effective Dose (ED50): Is the dose by which half of the population has been affected

Effect 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 doses

Chronic effects of a toxic response can last a long time or be permanent.


CHEMICALS: 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.



Under 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 affected

Unlike transient pollution which has a passing effect on gene frequency, chronic pollution changes the environment.


Intentional Poisoning*

Advantages GenderSilent Male 46%Precise targeting Female 39%Depersonalized Unknown 16%Safe for attacker

Profile BackgroundCaucasian Public 71%Male Physician 8%Average or above intelligence Political 4%Underachiever Nurse 4%Personality defect Other 5%Cowardly, nonconfrontational Unknown 9%NonathleticNeat and orderly, meticulousCareful planner *Source: Criminal Poisoning (2000)

Loner J. H. Trestrail, Humana Press


Properties of Ideal Poison

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


“The dose makes the poison”

Potencies of Poisons

Agent Lethal dose

Botulinum toxin 0.05 mg

Ricin 0.5 mg

Strychnine 100 mg

Sodium arsenite 200 mg

Sodium cyanide 250 mg

Thallium 1000 mg

NB: A dime is 2300 mg


Sources of Poisons

Commercial

Laboratories

Underground catalogs

Antique drug collections

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


Pesticide Poisons of Note

Synthetic – OrganophosphatesCarbamates

Paraquat Fluroacetate (1080 bait)

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


Poison plants readily available from nurseries, arboreta, backyards, wild areas

Foxglove Datura Oleander Autumn Poison Lantana Ricinus communispurpurea crocus hemlock (Castor bean)

digitalis atropine cardiac colchicine coniine lantadene ricin glycosides

Not visible: Lupine (lupanine)


Top 5 Homicidal Poisons

Agent Frequency Target

Arsenic 31% Energy generation

Cyanide 9% “

Strychnine 6% Nervous system

Morphine 3% “

Chloroform 2% “


Toxin Background Analysis

Evidence in vicinity of victimPill bottle, drug paraphernaliaFood, beverage leftovers

SymptomsAcuteChronic

SamplingOrgans, fluidsAccessory material

DetectionAnalytical instrumentationHPLC, GC, Mass Spec

MotivationLove, money, powerDisguised as random


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)


Arsenic

Can be used as pesticideAffects skin, liver, nervous system Is a risk factor for lung cancerHistory and physical examUrine test (can be affected by seafood

consumption)


Arsenic As at. No 33 m.p. 613o

Abundance & Use relatively rare, no nutritional role uses include pesticides, pigments, wood

preservatives, marine paint found in WI H20, added to chicken feed

Pharmacology toxicity: As+3 > As+5 > organic (shellfish)

salts > oxides efficiently absorbed from gut excreted in urine, does not accumulate binds to SH groups


Effects arsine gas = hemolysis/renal failure G.I. = bloody vomiting & diarrhea renal & vascular necroses--gangrene alopecia, mees lines, bronzing, garlic odor

Assessment urine, hair semi-reliable measured by AA, ICP, colorimetry treated with dimercaprol (BAL), DMSA


Arsenic Trioxide

1 to 2.5 mg/kg - potentially fatal dose binds to cellular proteins containing sulfhydryl groups decrease in glutathione

necessary for the metabolic detoxification of arsenic Common toxidrome:

Abdominal pain, nausea/vomiting,malaise Neuropathies Pancytopenias Hepatitis Peripheral vascular disease Cardiovascular collapse


Arsenic Trioxide

>500 years use in traditional Chinese medicine 1970’s investigators in China reported its use in

APL but were ignored by mainstream medicine Dual apoptotic and differentiation inducing

properties Doses 0.06-0.2 mg/kg (~1/3 fatal dose) CR rates ~90% in de-novo APL


And if you change your mind?

……the earlier the better

Chelation therapy Dimercaprol (BAL) DMSO

Contraindications pre-existing renal

disease, pregnancy, concurrent use of iron, G6PD


Cadmium Cd at. No 48 m.p. 321o

Abundance & Use found w/Zn in 1:70 ratio no nutritional role used in electroplating, batteries, solder,

plasticsPharmacology

biological 1/2 life >10 years toxicity inhaled > ingested

strong emetic “internal metallothionen chelation”

substitutes for Zn in enzymes


Effects emphysema nephrotoxicity, increased Ca excretion osteomalacia, itai-itai disease, kidney

stones

Assessment blood, urine, urinary proteins measured by AA, ICP Zn administration confers protection chelation may increase bioavailability


Dioxins Dioxins What 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 chain They attach and accumulate in our fat cells Dioxin is passed onto our children

• Through placenta, and breastfeeding We have no defense because it is not metabolized in

our bodies It can cause serious health problems at parts per

trillion (www.acereport.org,2003)


(www.ejnet.org/dioxin,2002)


Harmful Effects of Dioxin

Causes cancer Disrupts hormones May shrink penis size and sperm count Miscarriage, reproductive disorders,

birth defects, low birth weight Learning disabilities Short term memory and attention span Damage to nervous and immune

systems (www.acereport.org,2003)


TCDD (dioxin) – ChloracnePoisoning of Victor Yushchenko just before Ukraine presidential election


Dioxin (TCDD) Sensitivities

Species LD50 (µg/kg)

Guinea pig 2Rat 40Monkey 50Human ?Mouse 130 Rabbit 200Hamster 4000


Autopsy samples

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

HairBoneMaggots


Environmental/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 victims

Which companies are breaking the law?


Marine 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 doses

Okadaic 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 epidemics

Marine mammal mortality off California coast from domoic acid


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.


Mercury

Used as pesticide, pigment or preservativeCan cause central nervous system,

behavioral and renal effectsHistory, physical examUrine testing


Mercury Hg at. No 80 m.p. -39o

Characteristics & Use liquid at RT, high vapor pressureGood electrical conductorAll forms toxicmany uses

dental amalgams seed, paint, wood preservative (mostly banned) lamps, switches, thermometers industrial catalyst medicines (mostly historical)


Hg Chemistry & PharmacologyChemical form important

all toxic, but: effects and pharmacology differ influences best samples for assessment

Metallic mercury Hgo

inhaled vapor ~80% absorbed ingestion is nontoxic excreted in urine (& respired air) urine best test sample


Hg Chem & Pharm, cont’ Inorganic mercury (Hg salts) Hg++

G.I. absorption 2-38% excreted in bile and urine test urine or blood

Organic mercury Ch3Hg+

nearly 100% G.I. absorbed possible dermal absorption excreted in bile, some reabsorbed test blood or hair


Sources of Hg

Natural sources = 33-50% of total volcanoes weathering of mercury-containing rocks

Anthropogenic sources = 50-67% of total mining and smelting

cinnibar ore, HgS combustion of coal 80%

anthro waste incineration Other municipal/industrial releases


Hg Exposure PathwaysHg vapor precipitates, enters waterwaysSediment bacteria methylateMethylmercury biomagnifies in fish

Dietary intake biggest exposure source


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.


Hg Exposure Pathways, cont’Hg vapor from household products


Hg Health EffectsMetallic Hg

primarily affects CNS, kidneys, & lungs tremor, personality changes, delerium fatigue, anorexia, excess salivation acrodynia, “pink disease” effects often reversible


• Inorganic Hg–G.I. tract necrosis

• cramps, bloody diarrhea, circulatory collapse

–renal failure

–tooth & jaw necrosis, black gum lines

–no major CNS effects


Hg Health Effects, cont’

Effects Ch3Hg+

potent neurotoxin parasthesias, esp. lips and fingers ataxia, slurred speech, blurred vision confusion & agitation penetrates skin and latex

occupational safety and health1 corrosive materials materials that evoke a chemical process which...

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