Cyanide Mitigationand Worker Protection April 28, 2014

Cyanide mitigationand worker protection

April 28, 2014

Presented to: Subgroup of the

Kentucky Chemical Demilitarization

Citizens’ Advisory Commission and

Chemical Destruction Community

Advisory Board

Secondary Waste Working Group

Presented by:

Jeff BrubakerACWA Site Manager

Doug OmichinskiSystems Contractor Project Manager

Roger Thompson, CIH, CSPSystems Contractor Safety & Health Manager

Charlie Satterwhite, CIHSystems Contractor Senior Industrial Hygienist

Dr. John BartonSystems Contractor Chief Scientist

Neil FrenzlSystems Contractor Resident Engineering Manager

A Partnership for Safe Chemical Weapons Destruction

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Agenda

Potential agent and industrial chemical hazards

Health Hazard Assessment methodology and approach

Worker Safety and Occupational Medicine Program

– Personal Reliability Program

– Medical baseline screening

Cyanide challenge for energetics neutralization process

Cyanide treatment during energetics neutralization process

Cyanide exposure limits vs. BGCAPP levels

Questions and Responses matrix

Responses


GB

VX

H

aluminum hydroxide

ammonia

carbon monoxide

carbon dioxide

Dicyclohexyl carbodiimide

diisopropylcarbodiimide

diisopropyl methlyphosphonate

diisopropanolamine

diisopropyl urea

EA2192

ethanol

sulfuric acid

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Potential agent and industrial chemical hazards

tributylamine

tetrytol

tetryl

Composition B

trinitrotoluene

RDX; hexahydro-1,3,5-trinitro-1,3,5 triazine (cyclonite)

M28

HCN

hexane

methylene chloride

compressed air

helium

hydrogen

phosphoric acid

hydrochloric acid

hydrogen fluoride

isopropanol

nitrogen

methyl phosphonate

methyl phosphonic acid

sodium hypochlorite

sodium hydroxide

oxygen

phosphorus pentoxide

dithiane

sulfur

chloroform

Chemical Agents

Hydrogen Cyanide


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Health Hazard Assessments

Preliminary Hazard Assessment completed during design phase

Health Hazard Assessments and Job Hazard Analyses identify potential exposure hazards

– Completed to Project System Safety Program Plan standards

– Completed after procedure development initiated

– Completed to appropriate phases of the project (Design, Construction, Systemization, Operations, Closure)

A Construction worker (above) wears personal protective equipment.Systemization workers (below), inspect energized lock-out/tag-out systems.


Hazard tracking and communication

Health Hazard Inventory updated after Health Hazard Assessment

Documents shared with Medical Director and emergency preparedness

Hazards identified during analyses are tracked in Hazard Tracking Log

BGCAPP has formal Hazard Communication Program and Hazardous Waste and Emergency Response Program

Employees are educated and trained for potential exposure to hazards

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Worker Safety and Occupational Medicine Program

Personal Reliability Program

Workers’ activities involving the potential exposure to nerve agents receive a medical examination to document

1. Exhibit no physical, mental, or emotional impairment that may result in a higher vulnerability to nerve agent exposure

2. Are physically/mentally able to wear and use the required protective clothing and equipment

Individual baseline nerve-agent testing and ongoing surveillance dependent on type of work categories

Medical Screening Program

Medical and Industrial Hygiene programs are in place for industrial work activities depending on potential exposures

As part of ongoing Health Hazard Assessment, the extent of potential exposures identified determine which of programs are required for each worker


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The Technical Challenge

Neutralizing rocket warhead explosives poses unique technical challenge at Blue Grass

Cyanide formation expected during energetics neutralization process, trapped in caustic liquid energetics hydrolysate

Cyanide produced during energetics neutralization process isn’t a public risk, but if not treated, could require additional protective measures during future plant operations in some work locations(Supercritical Water Oxidation Process feed preparation)

BGCAPP has focused on engineering controls and treatment of hazards, to provide better protection for workers during operations

Small piece of Composition B in an aluminum pan


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Treatment Approach

Year long collaborative effort among BGCAPP scientists, engineers and corporate subject matter experts

Mission focused on safely and efficiently treating cyanide hazard during energetics neutralization processing

Focus on energetics neutralization process

– Portion of process where cyanide first occurs

– Un-manned, automated process (i.e. no workers)

– Upstream before Supercritical Water Oxidation Process (where cyanide might have posed worker hazard)

Mettler RC1® Calorimeter Reactor at Battelle’s HERLA Used to Simulate BGCAPPEBH and ENR Operations


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A Safe Solution

Enhance auxiliary systems to Energetics Neutralization Reactors (ENRs) to increase operating temperature

– Safely and efficiently destroys cyanide

– Does not change neutralization process

– Does not alter Supercritical Water Oxidation process

– Does not impact weapons destruction baseline schedule

Auxiliary systems enhancements

– Insulating jacket placed around reactors

– Heat exchanger to increase temperatures

– Heat exchanger to cool sampling line

Munitions Demilitarization Building,ENRs (above). A representative heat exchanger (below).


Without Treatment With Higher Temperature Treatment

Liquid(mg/L)

Air/Headspace (mg/m3)

Liquid(mg/L)

Air/Headspace (mg/m3)

Energetics Batch Hydrolyzers

600 non-detect 600 non-detect

Energetics Neutralization Reactors

350 non-detect 15 non-detect

Aluminum Precipitation Reactors

40 > 25 5 < 5

Aluminum Filtration System

20 > 25 < 1 non-detect

Anticipated Cyanide Concentrations

cyanide treatment occurs during this step

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Pilot Plant cyanide levels are below worker safety regulatory standards

National Institute of Occupational Safety & Health assigns short-term maximum limit 15-minute time-weighted average, of 5 mg/m3 for hydrogen cyanide in air

Centers for Disease Control assign an Immediately Dangerous to Life or Health limit of 25 mg/m3 for hydrogen cyanide in air


Questions & responses matrix

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Question Slide Number

Is one holding tank available to receive leaking tank contents? 12

Can HT/HP Treatment of EH be done on large scale without fouling/failures?

13

What does less than 5 mg/m3 mean? 10, 15

What are the effects of chronic low-level exposure to HCN for more than 15 minutes?

16

What are alarm levels and response actions? 17

Can you ‘hood ventilate’ the gas coming off APR and AFS? 18

Can filters be placed in process flow to capture HCN? 19

Will workers be screened prior to assignment to Supercritical Water Oxidation Process Building and will workers be periodically re-evaluated?

4, 5, 6, 20

Will dermal protection be provided? 4, 5, 21

Will workers receive post-work surveillance? 4, 5, 6, 22


Questions & Responses (cont.)

Is one holding tank available to have leaking tank contents transferred to it in the event needed?

Both tanks may be in service simultaneously

Tanks are designed with both spill and overfill prevention controls

Spill containment = content of a tank + regulatory defined rainfall (25-year, 24-hour maximum rainfall) and freeboard

Spill response procedures define actions for rapid response to contain leaks

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Hydrolysate Storage Area (above) construction is nearing completion.The Storage Area is designed and built (below) to environmental regulations.

Hydrolysate Storage Area design, construction and operations regulated by Kentucky Department for Environmental Protection, Environmental Protection Agency and in accordance with the Resource Conservation and Recovery Act (RCRA).


Can High Temperature/High Pressure (HT/HP) Treatment of Energetics Hydrolysate be done on large scale consistently without fouling or failures?

Preliminary evaluation of fouling, corrosion, and downstream impacts performed

– Accumulated sludge-type material on reactor surfaces readily removed using water rinse

– Corrosion studies demonstrated nickel liner resistant over design life

– No impact to downstream processing or Supercritical Water Oxidation process

Evaluation of potential impacts continues:

– Further studies on potential fouling planned


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The project stated that with a thermal treatment process, the building atmospheric concentrations would be reduced to less than 5 mg/m3. What does less than 5 mg/m3 mean? In other words, is it 0 or 4.9 mg/m3?

Bench scale analyses results:

– Filtercake “drying” air was nondetect for HCN at detection limit ~ 0.4 mg/m3

– Equilibrium headspace measurements of both moist and dry filtercake werenon-detect at detection limit ~ 0.7 mg/m3

– Exposure concentrations would be less than these values


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Energetics hydrolysate testing.


Cont: The project stated that with a thermal treatment process, the building atmospheric

concentrations would be reduced to less than 5 mg/m3. What does less than 5 mg/m3 mean? In

other words, is it 0 or 4.9 mg/m3?

Existing design limits potential exposure:

Processes are largely contained:— APRs vent to carbon filters before release to atmosphere with calculated

emission levels much less than 1 short-term exposure limit (STEL) (5 mg/m3)

— AFS feed tanks/filtrate tank vent outside building

— Pressurized air pushes filtrate through filter, dries filtercake, passes to filtrate tank, and vents outside building

— Cyanide offgassing to building may occur drying and/or filtercake temporary storage in collection bins

Building ventilation lowers concentrations of potentially offgassed HCN— SPB equipped with four separate HVAC systems servicing the control area, RO room,

SCWO processing area and relief tank room, and Aluminum Precipitation (AP)/Aluminum Filtration (AF) room (i.e., AP/AF air is isolated from those areas with a higher occupancy rate)

— AP/AF ventilation system - 13,400 cfm and 2 roof exhaust air fans


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What are the effects on humans of chronic low-level exposure (inhalation, ingestion and dermal) to HCN for more than 15 minutes? What level of atmospheric cyanide has no observable effects on workers?

Exposure concentrations expected to be much less than 1 mg/m3

Based on the automation used in the process, exposure durations expected to be much less than 8 hours/day(i.e., maintenance required to change disposable filter media roller (twice/week), drip pan cleaning (weekly), and other activities (weekly or monthly)

BGCAPP will perform a Health Hazard Assessment for the risks and minimize potential worker exposure

– BGCAPP relies on defined occupational exposure limits for HCN

– Mitigations may include engineering controls and administrative controls

– The Health Hazard Assessment establishes what type of personal protective equipment to use and when to use it


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At what level would alarm systems be set? What is the response to an alarm? Don PPE or evacuate? How often and would HCN in the SPB be measured?

The HHA will consider monitoring requirements based on anticipated breathing zone concentrations and monitoring capabilities (i.e., estimated detection limits)

Monitoring will be conducted during start up operations to confirm estimates of breathing zone concentrations

Start-up operations will establish Energetics Neutralization Reactor (ENR) process parameters confirming destruction of cyanide at required levels to mitigate downstream risks

ENR process controls and monitoring results will establish necessity for additional monitoring


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Can you ‘hood ventilate’ the gas coming off APR and AFS?

Aluminum Precipitator Reactor (APR) offgases through carbon filters to Supercritical Water Oxidation (SCWO) Process Building exterior

Aluminum Filtration System (AFS) vents to release points outside of SCWO Process Building

The design incorporates a roof-mounted exhaust fan to draw vapors from the filter cake bins

The Health Hazard Assessment will review the existing design, breathing zone concentrations, and exposure durations to identify the need for additional mitigation measures


18


Can filters be placed somewhere along the process flow to capture HCN prior to it entering the SCWO atmosphere?

Existing SCWO Process Building design minimizes worker exposure:

– The Aluminum Precipitation Reactors (APRs), vent to carbon filters and then outside the building with calculated emission levels much less than 1 short-term-exposure limit (STEL) (5 mg/m3)

– The Aluminum Filtration System (AFS) feed tanks and filtrate tank vent outside building

– The pressurized air used to dry the filtercake passes to the filtrate tank where it is vented outside building

– A roof-mounted exhaust fan draws vapors from filtercake bins to building exterior

The Health Hazard Assessment will identify the need (if any)for additional mitigation measures


19


Will workers by screened prior to assignment to SPB for things like thyroid disorders, neurological disorders, normality of liver/renal functions, smoking, pregnancy and child-bearing age females, and cardiovascular problems? Will physical pre-screens and laboratory baselines for blood/urine be conducted and periodically re-evaluated?

BGCAPP workers undergo medical screening at time of employmentfor specific duty fitness requirements

Screening requirements are determined in accordance with Medical Screening Program

For, HCN, the Health Hazard Assessment will establish whether expected exposure conditions in the SCWO Process Buildingwarrant additional measures to control exposure

Hazards will be addressed through a comprehensive workplace Hazard Communication Plan, through existing engineering controls, and through administrative controls


20


What about dermal protection if HCN is not significantly reduced below 5 mg/m3?

The established operational exposure limits consider contributions from dermal exposure and therefore are considered protective

Expected building air will be less than 1 mg/m3


21


Will workers receive post-work surveillance? If yes, for how many months or years?

The currently expected exposure concentrations/durations do not warrant implementation of post-work surveillance

The Health Hazard Assessment determines whether mitigation measures or medical surveillance is required to address the potential for chronic worker exposure


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Government & Nonprofit

Cyanide Mitigationand Worker Protection April 28, 2014