This document summarizes a presentation given to the Kentucky Chemical Demilitarization Citizens’ Advisory Commission and Chemical Destruction Community Advisory Board Secondary Waste Working Group. The presentation addressed the technical challenge of cyanide formation during the energetics neutralization process for destroying rocket warheads and the approach taken to safely treat cyanide. It was explained that enhancing auxiliary systems to the Energetics Neutralization Reactors would increase operating temperatures to destroy cyanide without changing the baseline destruction schedule or processes. The presentation also addressed worker safety programs and exposure limits.
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Cyanide Mitigationand Worker Protection April 28, 2014
1. Cyanide mitigation
and 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 Brubaker
ACWA Site Manager
Doug Omichinski
Systems Contractor Project Manager
Roger Thompson, CIH, CSP
Systems Contractor Safety & Health Manager
Charlie Satterwhite, CIH
Systems Contractor Senior Industrial Hygienist
Dr. John Barton
Systems Contractor Chief Scientist
Neil Frenzl
Systems Contractor Resident Engineering Manager
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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
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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.
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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 BGCAPP
EBH 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).
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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
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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
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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
12
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).
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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
Questions & Responses (cont.)
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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 were
non-detect at detection limit ~ 0.7 mg/m3
– Exposure concentrations would be less
than these values
Questions & Responses (cont.)
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Energetics hydrolysate testing.
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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
Questions & Responses (cont.)
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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
Questions & Responses (cont.)
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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
Questions & Responses (cont.)
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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
Questions & Responses (cont.)
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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
Questions & Responses (cont.)
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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 employment
for 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 Building
warrant additional measures to control exposure
Hazards will be addressed through a comprehensive workplace
Hazard Communication Plan, through existing engineering controls,
and through administrative controls
Questions & Responses (cont.)
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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
Questions & Responses (cont.)
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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
Questions & Responses (cont.)
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