Barnstable County Water Utilities Association

Safe Chemical Handling and Initial Spill Response

June 16, 2011

David P. Horowitz, P.E., CSP

Tighe & Bond, Inc.

413.572.3211

dphorowitz@tighebond.com

@dphorowitz on Twitter & YouTube

Take Away Message

■PROTECT YOURSELF■PROTECT OTHERS■PROTECT THE ENVIRONMENT

Introduction / Objectives

■ Specific water treatment plant chemical hazards■ Means of hazard recognition

– Normal handling– Spill / release situations

■ Evaluate Risk■ Protect Yourself

– Use of personal protective equipment– Safe distance / places of refuge

■ Protect Others■ Protect the Environment

Common Chemical Uses

■ Coagulation■ Filter and Floc Aids■ Taste and Odor

Control■ Disinfection■ pH Adjustment■ Fluoridation■ Corrosion Control

Select only the closest or the best answer

■ What does MSDS stand for?

A. Massachusetts Safety Data SystemB. Material Safety Data SheetC. Material Safety Database SystemD. Mine Safety Data System

Material Safety Data Sheet

■ Expanded Label Information

■ Accessible■ Provide Copies During

Emergency Response– Outside Agencies– Hospitals, on Injury

■ They’re Changing!– Globally Harmonized

System (GHS)

MSDS - Key Sections

■ Appearance and Odor– State of Material (Gas, Liquid, Solid)– Warning Properties

■ Physical Characteristics– Specific Gravity– Vapor Density

■ Fire and Explosion– Flashpoint– Flammable Limits– Extinguishing Media

MSDS - Key Sections

■ Reactivity Data– Incompatibles

■ Health Hazard Data– Health Effects (Acute / Chronic)

■ Emergency and First-aid– Decontamination– Ingestion– Medical Information

Hazard Types

■ Physical

– Unstable Chemicals (Water Reactive)

– Flammables or Combustibles

– Explosives

– Stored at High Pressures

– Thermal Effects

■ Health

– Route of exposure

– Target organ

Globally Harmonized Systems

■ The Big Purple Book

WHAT?

■ A rule has been proposed by OSHA proposed by OSHA to align the Hazard Communication Standard 29 CFR 29 CFR 1910.12001910.1200 with provisions of the United Nations Globally Harmonized System of Classification and Labeling of Chemicals.

■ Published in the Sept. 30, 2009 Federal Register■ Phase-in period for the proposed rule will be 3 3

years after the final rule is publishedyears after the final rule is published■ Phase-in for the implementation of training and

education programs expected within 2 years of 2 years of the final rule being publishedthe final rule being published

WHEN?

ANTICIPATED IMPLEMENTATION

■ Quote from acting Assistant Secretary of Labor for OSHA Jordan Barab

“Although no date has been established for the publication of the final rule, Jordan said, “We think we have a pretty good proposal, so we’re hoping to move it along with all due speed ….”

■ Anticipated for early 2010■ May publish in August 2011

WHY?

■ “The proposal to align the hazard communication standard with the GHS will – improve the consistency and

effectiveness of hazard communications

– reduce chemical-related injuries, illnesses and fatalities

WHO?

■ Number of workers affected by the proposed HCS: – Over 40 million workers

■ Affected Industries:– Over 5 million workplaces

INTERNATIONAL PARTICIPATION

■ Countries that have already implemented the system include:– Japan– Korea– New Zealand – Taiwan

■ Countries/regions that have incorporated UN GHS into their local regulations include:– European Union (EU)– China– Singapore– Thailand

PROPOSED MODIFICATIONS

■ Four major proposed modifications to HazComm– Revised criteria for

classification of chemical hazards» Revised labeling

provisions» Single words

– Pictograms– A specified format for

safety data sheets– Define terms

SAFETY DATA SHEETS

■ Safety data sheets will now have a specified 16-section format. (ANSI Z400.1-1993)

■ The term Material Safety Data Sheet (MSDS) has been replaced with Safety Safety Data SheetData Sheet

It’s Movie Time!

Chemical Specifics

■ Water Treatment– Acid / Caustic– Fluoride– Permanganate– Alum– Disinfectants (chlorine / hypochlorite)

■ Fuels and Maintenance– Diesel / Heating Oil– Natural Gas / Propane– Coolants– Lubricants– Flammables

Potassium Permanganate

■ Warning: corrosive, oxidizer■ Routes: eye, skin, inhalation,

ingestion■ Symptoms: irritation, possible

chemical burns, pulmonary edema, managanism

■ Hazards– Strong oxidizer (avoid combustibles,

wooden pallets, acids)– Large quantities of dust presents

inhalation hazard– Chronic neurological effects

Aluminum Sulfate

■ Warning: irritant■ Routes: eye, skin, inhalation, ingestion■ Symptoms: irritation, shortness of breath,

vomiting, diarrhea■ Hazards:

– Avoid ingestion– Hydrolyzes in water forming sulfuric acid

■ What is the main safety hazard of polyelectrolytes (polymers used in water treatment)?

A. Explosive

B. Slippery

C. Corrosive

D. Toxic

Select only the closest or the best answer

Sodium Hypochlorite

■ Warning: oxidizer, corrosive (caustic)

■ Routes: eye, skin, inhalation, ingestion

■ Symptoms: irritation, chemical burns, blood disease on chronic overexposure

■ Hazards– Reaction could generate chlorine gas– Slippery– Oxidizing will cause accelerated

burning

Chlorine Gas / Liquid

■ Corrosive / toxic by inhalation– Vapors condense to form hydrochloric acid– Toxic at relatively low airborne concentration– Can cause pulmonary edema

■ Cryogenic as a liquid■ Reactives

– Ammonia and fuel gas– Explosive compounds

■ Strong odor, good warning properties

What does OSHA say about a chlorine spill?

■ http://www.osha.gov/SLTC/healthguidelines/chlorine/recognition.html

■ In the event of a spill or leak involving chlorine, persons not wearing protective equipment and fully-encapsulating, vapor-protective clothing should be restricted from contaminated areas until cleanup has been completed. The following steps should be undertaken following a spill or leak:– Notify safety personnel. – Remove all sources of heat and ignition. – Keep all combustibles (wood, paper, oil, etc.) away from the

leak. – Ventilate potentially explosive atmospheres.

What Does OSHA Say? Chlorine (Continued)

– Evacuate the spill area for at least 50 feet in all directions.

– Find and stop the leak if this can be done without risk; if not, move the leaking container to an isolated area until gas has dispersed. The cylinder may be allowed to empty through a reducing agent such as sodium bisulfide and sodium bicarbonate.

– Use water spray to reduce vapors; do not put water directly on the leak or spill area.

Sodium Hydroxide

■ Warning: corrosive (caustic)■ Routes: eye, skin, inhalation, ingestion■ Symptoms: irritation, chemical burns, hair loss■ Hazards:

– Extremely slippery– Difficult to remove– Reacts with acids

Hydrofluosilic Acid

■ Warning: corrosive■ Routes: eye, skin, inhalation, ingestion■ Symptoms: irritation, chemical burns, fluorosis■ Hazards

– Irritation effects– Chronic effects– Reacts with caustics

Sulfuric Acid

■ Warning: corrosive■ Routes: eye, skin, inhalation,

ingestion■ Symptoms: irritation, chemical

burns, pulmonary edema■ Hazards

– Highly reactive / generates fumes– Inhalation effects may be delayed– Neutralization enhances the reaction– Adding water may not be effective

True/False

■ Add acid to water but NEVER the reverse

a. True

b. False

Ammonia – Aqueous / Anhydrous

■ Warning: corrosive■ Routes: eye, skin, inhalation,

ingestion■ Symptoms: severe skin, eye and

upper respiratory irritant ■ Hazards

– Irritation and burns at the site of contact– Possible systemic effects– Fires release hydrogen gas– Reacts with most water treatment chemicals

■ Anhydrous– Rapidly expands to toxic concentrations– Cryogenic liquid

Fuel Oil – Diesel or Heating

■ Warning: carbon monoxide & limited oxygen

■ Routes: eye, skin, inhalation, ingestion

■ Symptoms: skin reddening, headache, dizziness, drowsiness, fatigue

■ Hazards– Combustible liquid– Avoid using direct water streams

What’s the best way to respond to a spill?

PREVENT IT FROM HAPPENING!!

Chemical Feed System Designs

■ Good Engineering Practices– Regulatory Agencies– Utility Standards– Operator Preferences– Economics– Spatial Constraints

Design Considerations/Flexibility

■ Bulk Tanks■ Transfer Pumps■ Day Tank■ Metering Pumps■ Containment

Chemical Compatibility

■ ALWAYS check wetted material for compatibility

■ Effect Ratings– None – excellent– Minor – good– Moderate – fair– Severe – not recommended

■ Resistance Charts

Simple System (Manufacturer Provided)

Transfer Pump Design Considerations

■ Fill Time■ Flooded Suction■ Compatible Material■ Viscosity of the

Chemical■ Siphoning

Metering Pump Design

■ Concentration■ Specific gravity■ Viscosity■ Temperature■ Suction Lift or

Flooded Suction■ Injection

Pressure

Chemical Feed System Operation

■ Best Management Practices

■ Standard Operating Procedures

■ Non-Structural Controls

Secondary Containment

■ Concrete Berms with Coating

■ Secondary Containment Pallets

■ Fabricated Containment Systems

■ 110% of Largest Bulk Tank

Five Effective Generic BMPs

■ Good Housekeeping

■ Visual Inspection

■ Employee Training

■ Spill Prevention & Response Procedures

■ Preventative Maintenance

Spill Prevention Measures

■ Frequent Inspections

– Drums, tanks, mix stations, pumps

■ Up to Date Maintenance

■ Proper Oil & Chemical Handling

■ Training

If You Have A Spill - Emergency Chemical Response

■ Remember your priorities■ Separate personnel from the hazard■ Assess risk■ Respond within your capability■ Notify the chain of command■ Follow your Source Protection Emergency

Plan (SPEP)– Spill Prevention Control and Countermeasure Plan

(SPCC)– Stormwater Pollution Prevention Plan (SWPPP)– Integrated Contingency Plan (ICP) or One Plan

Actions

■ Provide Site Control: – Any Responding Personnel

■ Contain and Curtail: – Any Responding Personnel

■ Initiate Regulatory Notification: – ER Coordinator

■ Notify Cleanup Contractor– ER Coordinator

■ Cleanup Only After Regulatory Approval

■ In MA – spilled oil is a hazardous waste

SPEP – General Policy

■ Respond within your capabilities■ Assume hazardous■ Report to the appropriate authorities■ Primary objectives

– Protection of responders– Protection of other personnel (immediate need)– Protection of the water supply

Don’t get tunnel vision

■ Chemical– Physical hazards– Health hazards– Incompatibles– Ignition sources– Heat

■ Other hazards?

The chemical may be the least of your problems

■ Factors– Other hazards in the area– What caused the chemical

to spill?– Hidden hazards that may

be present– Talk to witnesses

RECOGNITION & IDENTIFICATION

■ Know What You’re Dealing With

■ Response Drivers– Chemical Type– Quantity– Location– Other Hazards (E.G., Fire)

■ Response Equipment Selection■ Notification■ PPE

RECOGNITION CLUES

■ Interview

■ Occupancy / Location

■ Container Shapes

■ Marking and Colors

■ Placards and Labels

■ Shipping Papers

■ Senses

PSYCHOLOGICAL FACTORS

■ Inappropriate Emotional

Reaction

■ Bad Habits

■ Laziness

■ Don’t Become Part of the

Problem

KEYS TO SAFE RESPONSE

■ Discipline

■ Command

■ Management

■ Don’t Let Time Become

Your Enemy

■ Don’t Cut Corners

SPEP – Respond Within Your Capabilities

■ First Responders – Operations Level– Defensive containment– From a safe distance

■ Technician Level– Aggressive operations– Only when material is known to be oil,

dilute gasoline or non-hazardous– Appropriate equipment and materials

are in-place

SPEP – Response Procedure

■ ER Coordinator ensures incident is properly reported– Local organizations

» Fire Department» DPW» ConComm

– DEP– DPH

■ Communications coordinator to place internal organizations on standby– Responders– Supervisors– Quality control

SPEP – Actions At The Scene

■ ER Coordinator– Directs responders– Liaison to incident commander– Maintains records at the scene

■ Response– Based on threat to water supply

SPEP – Response To Threats To The Water Supply

■ Actions– Inform appropriate internal organizations– Mobilize resources to the scene– Initiate containment activities to protect the water supply– In concert with incident command

Site Activities

■ Assessment of conditions■ Identify trapped or injured

personnel■ Ensure appropriate notification■ Isolate environmental receptors

– Water– Ground

■ Containment and curtailment■ Defensive measures

Isolate Environmental Receptors

■ As far away as reasonably possible

■ Direction of spill migration■ Drains, doors, etc.■ Spills vs releases■ Air path isolation should wait

until spill is controlled

Site Conditions

■ Do not contact spilled materials■ Illumination■ Heat■ Protrusions■ Physical activity■ Limited time■ Use of stairs and ladders■ Vision■ Communication

Spill Reporting

■ Massachusetts Contingency Plan (MCP)

■ 310 CMR 40.0000■ Bureau of Waste Site Cleanup■ Massachusetts Oil and Hazardous

Material List– 310 CMR 40.1600– CAS #– Reportable Quantities (RQs)– Sudden release – 2 hours

Spill Reporting

Chemical CAS # DEP RQ (Lbs)

Sulfuric Acid 7664-93-9 50

Sodium Hydroxide 1310-73-2 50

Potassium Permanganate 7722-64-7 10

Aluminum Sulfate 10043-01-3 100

Sodium Hypochlorite 07681-52-9 10

Chlorine Gas 7782-50-5 5

Hydrofluorosilicic Acid 16961-83-4 10

    DEP RQ (Gal)

Oil - Diesel & Heating   10

Spill Reporting

Chemical CAS # DEP RQ (Lbs)

Sulfuric Acid 7664-93-9 50

■ How many gallons of a Sulfuric Acid spill would require reporting to DEP?

– 1 Gallon– 10 Gallons– 100 gallons– Need More Information

■ We need concentration & density!

Spill Reporting

Chemical Conc (Typ) DensityDEP RQ (Lbs)

DEP RQ (Gal)

Sulfuric Acid 90% 1.84 50 3.3

Sodium Hydroxide 50% 1.53 50 3.9

Aluminum Sulfate 28% 1.33 100 9.0

Sodium Hypochlorite 12.5% 1.20 10 1.0

Hydrofluorosilicic Acid 25% 1.22 10 1.0

     DEP RQ

(Gal)DEP RQ

(Gal)

Oil - Diesel & Heating     10 10

VAPOR DENSITY

■ Vapor (Gas) to Air Ratio■ < 1 a Floater■ > 1 a Sinker■ Especially Important for Ventilation Controls

and Monitoring

SPECIFIC GRAVITY

■ Liquid’s Equivalent to Vapor Density■ < 1 a Floater■ > 1 a Sinker■ Especially Important in Firefighting and Water

Dilution

Select only the closest or the best answer

■ A gas lighter than air is:

a. Chlorine

b. Gasoline Vapor

c. Hydrogen sulfide

d. Methane

■ A gas lighter than air is:

a. Chlorine 2.47

b. Gasoline Vapor 3-4

c. Hydrogen sulfide 1.19

d. Methane 0.55

■ Need More Info?

Conclusions / Key Points

■ Employee responsibilities– Know the chemical hazards– Use controls to prevent exposure– Review MSDS during non-routine tasks– Take action if symptoms of overexposure are felt

■ Response– Know the 4 core objectives– Chemicals can behave very differently when out in the open– Don’t take anything for granted– Get away and get the right resources to the situation– Mistakes can be costly

Pop Quiz

Hope you were paying attention…

Which of the following is a corrosive chemical

A. PermanganateB. Sodium hydroxideC. AlumD. Fuel oil

Which of the following exposures can be controlled with chemical gloves?

A. FlammablesB. CorrosivesC. ReactivesD. Oxidizers

What is the primary hazard for sodium hypochlorite

A. CorrosiveB. FlammableC. OxidizerD. Irritant

What document should be the primary resource for chemical hazard info

A. National toxicology programB. NIOSH Pocket GuideC. The internetD. Material Safety Data Sheet

Which of the following should be done first in a chemical emergency

A. Contain the spillB. Risk assessmentC. Call the fire departmentD. Evacuate the immediate spill area

Once human health is protected, what is the next objective

A. Protection of treatment systemsB. Prevent chemical infiltration to finished waterC. Protection of water supplyD. Call your lawyer

What should be done with waste generated from spill response

A. Segregate for hazardous waste disposalB. Dispose in trash containerC. Neutralize in the treatment systemD. Place in the residuals pile

If you feel the effects of chemical exposure, what should you do next

A. Finish containing the spill and evacuateB. Evacuate the area immediatelyC. Signal all team members to evacuateD. Call you lawyer

Which of the following is most hazardous when combined with a fuel oil spill

A. Activation of a gas fired heaterB. Mixing with causticC. Absorption with spill padsD. Mixing with gasoline

Questions / Thanks

David P. Horowitz, P.E., CSPTighe & Bond, Inc.413.572.3211dphorowitz@tighebond.com