total hydrocarbon monitoring at the agent filtration area

Total Hydrocarbon Monitoring at the Agent Filtration Area (AFA) at PCAPP Using Photoacoustic Spectrometers

Dr. Gary D. Sides and Mr. Walter L. Waybright

Acronyms

ACFM Actual Cubic Feet per Minute AFA Agent Filtration Area

ANR Agent Neutralization Reactor (hydrolyzer) APB Agent Processing Building

CDPHE Colorado Department of Public Health COPC Chemical of Potential Concern

and Environment

DCA 1,2-Dichloroethane ERB Enhanced Reconfiguration Building

HAL High Agent Loading (test) HD Agent mustard

HEPA High Efficiency Particulate Air (filter) HVAC Heating, Ventilation, and Air

Conditioning (system)

IDLH Immediately Dangerous to Life and Health MINICAMS Miniature Automatic Continuous

Air Monitoring System

MPHRA Multiple Pathway Health Risk Assessment MTU Munitions Treatment Unit

MWS Munitions Washout System OTS Off-Gas Treatment System

PAS Photoacoustic Spectrometer PCAPP Pueblo Chemical Agent-Destruction

Pilot Plant

ppm parts per million (by volume) PTD Pilot Test Demonstration

SDU Supplemental Decontamination Unit THC Total Hydrocarbon

VC Vinyl Chloride VOC Volatile Organic Chemical

2

Off-Gassing from Various Systems Vent to the Off-Gas Treatment System (OTS)

3

Systems in Agent Processing

Building (APB) venting to OTS

• Munitions washout systems

• MWS wash water tanks

• Agent/water separators

• Agent hydrolyzers (reactors)

• Agent hydrolysate hold tanks

• Munitions Treatment Units

(MTUs)

• Supplemental

Decontamination Unit (SDU)

• Autoclave

Exhaust from OTS and HVAC Air fromthe APB Pass Through Carbon Filters

4

APB Exhaust

ERB Exhaust

MK-M07-0016

MK-M07-0015

MK-M07-0014

MK-M07-0013

MK-M07-0012

MK-M07-0011

MK-M07-0010

MK-M07-0009

MK-M07-0008

MK-M07-0007

THC Monitoring performed on two on-line AFUs (0011 through 0016) continuously (LSAP CLA#8

and CLA#9b

COPC sampling at stack and at three on-line AFUs (0011 through 0016) during each OTS/AFA

test activity (PTDP Appendix A6; LSAP CLA#8 and CLA#12)

Carbon sampling at Bank 3 and potentially Bank 6 (see DQO) of all AFUs performed minimum of

four times during pilot testing immediately following COPC sampling (Carbon Sampling Strategy;

LSAP CLA #11)

1,2-DCA (VOC) and Hg sampling on 8 on-line AFUs performed during each OTS/AFA test

activity (PTDP Appendix A6, LSAP CLA #10)

General emissions sampling (particulates, sulfur/nitrogen oxides, acid gases, metals, dioxins/

furans) performed at stack (PTDP Appendix A6, LSAP CLA#12

Enhanced Reconfiguration Building

(45,300 ACFM)

Agent Processing Building (APB)

(78,700 ACFM)

Agent Filtration Area (AFA)

APB Exhaust includes

• Exhaust gas from the OTS

• HVAC air “contaminated” due to

—Waste handling activities

—Decontamination activities

—Leaking seals

—Champagning rounds

—Etc.

Eight (8) of ten (10) carbon filter units on-line at all times; Filters 7, 8 and 9 not shown.

Pre-Operational PCAPP Multiple Pathway Health Risk Assessment

5

• Pre-operational chemical emissions estimate completed for PCAPP

• An MPHRA, a screening-level assessment of potential risk of PCAPP operations

on human health, was then completed

• MPHRA results indicated that 1,2-dichloroethane (DCA) and vinyl chloride (VC)

are the non-agent chemicals with the primary impact on potential health risks

• Pre-operational emissions estimates for DCA and VC at the AFA stack were 4.8

and 5.0 lb/day, respectively

• Estimated concentrations for DCA and VC at the AFA stack were much less than

the calculated DCA and VC MPHRA thresholds for a one-in-a-million cancer risk

Pre-Operational Estimates:Chemical Emissions, lb/day Est. Stack Concn, ppm MPHRA Threshold, ppm

1,2-Dichloroethane 4.8 0.13 3.64

Vinyl chloride 5.0 0.21 1.47

Sampling at the Agent Filtration AreaDuring the Pilot Test Demonstration

6

APB Exhaust

ERB Exhaust

MK-M07-0016

MK-M07-0015

MK-M07-0014

MK-M07-0013

MK-M07-0012

MK-M07-0011

MK-M07-0010

MK-M07-0009

MK-M07-0008

MK-M07-0007


and CLA#9b





LSAP CLA #11)





APB Exhaust

ERB Exhaust

MK-M07-0016

MK-M07-0015

MK-M07-0014

MK-M07-0013

MK-M07-0012

MK-M07-0011

MK-M07-0010

MK-M07-0009

MK-M07-0008

MK-M07-0007


and CLA#9b





LSAP CLA #11)





Total Hydrocarbon (THC) Analyzers

COPCs (Summa canisters, TO-15)

Carbon Sampling

(butane working capacity)

Enhanced Reconfiguration Building

(45,300 ACFM)

Agent Processing Building

(78,700 ACFM)

Eight (8) of ten (10) carbon filter units on-line at all times; filters 7, 8 and 9 not shown.

Sampling of concern for the study

described in this presentation

Total Hydrocarbon Monitoring Duringthe Pilot Test Demonstration (PTD)

• Required by the Colorado Department of Public Health and Environment

(CDPHE)

• Real-time THC monitoring intended to supplement manual sampling for

Chemicals of Potential Concern (COPCs) at the Agent Filtration Area

• Goals for THC monitoring during the PTD:

Determine whether real-time THC data

—correlate with COPC sampling data obtained during routine operations and, thus, may be

used as a real-time indicator of process emissions (from systems in the APB)

—correlate with COPC sampling data obtained during process upset conditions and, thus,

may be used as a real-time indicator of upset conditions

—correlate with butane working capacity for AFA carbon and, thus, may be used as an

indicator of remaining carbon activity

7

Reference: PCAPP Position Paper on Total Hydrocarbon Monitoring

During Pilot Test Demonstration, 24852-30H-000-V0003, Rev. 001

Total Hydrocarbon Monitoring During the Pilot Test Demonstration

8

Photoacoustic Spectrometer (PAS)

• Advertised lower detection limits than for

conventional flame-ionization-based THC

analyzers

• Continuously monitor for vinyl chloride (VC)

and 1,2-dichloroethane (DCA)*

• Continuously monitor for total hydrocarbons

(THC, reported as propane; not including VC)

• Reported concentrations compensated for

interferences from water vapor (H2O), carbon

dioxide (CO2) and nitrous oxide (N2O)

INNOVA Model 1412i (LumaSense Technologies, Inc.)

*DCA and VC were expected to constitute 95% of non-HD VOC emissions from systems in the Agent Processing Building.

DCA and VC averaged 97% of non-HD VOCs in 20 HEPA/Bank 1 Summa canister samples collected during 10 different PTD tests.

Operation of the THC Analyzer (PAS)

9

• Based on the measurement of infrared (IR) absorption

• Reports THC, VC and DCA concentrations once every 5 min

—compensated for interferences from H2O, CO2 and N2O

Pre-Operational Performance of theTHC Analyzers 7/22-8/23/16 Baseline

10

Baseline total hydrocarbon (THC), carbon dioxide (CO2), and

nitrous oxide (N2O) concentrations reported were in agreement

with known atmospheric levels of methane (CH4), CO2 and N2O

• THC concentrations (reported as propane)—pooled mean for 4 analyzers: 0.37 ppm

—analyzers 5X less sensitive to methane than to other hydrocarbons

—5 x 0.37 ppm = 1.85 ppm, near atmospheric levels of methane

—pooled standard deviation for 4 analyzers: 0.054 ppm

—baseline mean plus 3 standard deviations: 0.53 ppm (“control limit”)

• CO2 concentrations (baseline lowest levels)—about 420 ppm, near atmospheric levels

• N2O concentrations (baseline lowest levels)—about 0.34 ppm, near atmospheric levels

Pre-Operational Performance of theTHC Analyzers 7/22-8/23/16 Baseline

11

• Water vapor (H2O) concentrations (black trace)

—in the range of 10,000 to 30,000 ppm (about 30 to 95% RH at 25 C)

• Frequent fluctuations in H2O concentrations (black trace) correlated with

—small fluctuations in reported THC concentrations (blue trace)

—periodic false positives for reported DCA concentrations (orange trace)

—no false positives for reported VC concentrations (red trace) but negative baseline

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VC THC DCA H2O

Typical Concentrations Reported During Suspended Operations 11/21/16–1/12/17

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• H2O concentrations about 5,000-9,000 ppm

(low humidity compared to baseline period)

• No “high-frequency” fluctuations in

reported H2O concentrations

• No H2O-correlated false positives for DCA

• VC baseline at about 0.0 ppm

Typical Data Reported DuringMunitions Processing (VC)

13

Typical Data Reported During Munitions Processing (THC, DCA, H2O)

14

Typically, minor changes in THC concentrations No indication of DCA emissions

Does not include VC

Low humidity from mid-Sept 2016

to about April 2017

Example of THC Analyzer Data During Munitions Processing (HEPA/Bank 1)

15

Correlation of munitions processing with reported VC concentrations

Correlation of munitions processing with reported THC concentrations*

*Reported THC

concentrations do

not include VC

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HP Wash Water THC Daily Munitions Count

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VC HP Wash Water Daily Munitions Count

Comparison of THC Analyzer Data andSumma Canister Results (HEPA/Bank 1)

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Date Pilot Test Demonstration (PTD) Test Filter Summa DCA, ppb Summa VC, ppb Analyzer VC, ppb

10/18/16 MWS/MTU Demonstration Test 1 11 34 325 469

16 118 1100 1495

11/01/16 ANR Demonstration Test 1 11 72 164 276

16 79 174 343

11/08/16 ANR Demonstration Test 2 11 73 204 413

16 72 203 390

11/15/16 MWS/MTU Demonstration Test 2 11 * * 1025

16 41 984 1092

11/16/16 OTS/AFA Demonstration Test 1 11 26 662 932

16 28 626 1113

• Obtained during Pilot Test Demonstration tests (5-hr sample periods)

• Dilution factor for COPC (Summa canister) samples typically > 100X

*Not shipped for analysis due to quality failure in the agent screening analysis

Comparison of THC Analyzer Data andSumma Canister Results (HEPA/Bank 1)

17

Date Pilot Test Demonstration (PTD) Test Filter Summa DCA, ppb Summa VC, ppb Analyzer VC, ppb


16 47 1221 1202

02/07/17 MTU Heel Demonstration Test 11 25 418 430

16 30 426 474

02/26/17 HAL Demonstration Test 1 11 78 524 720

16 ND* ND* 763


16 31 892 1141

03/09/17 HAL Demonstration Test 2 11 38 178 278

16 50 236 330

• Tests highlighted in red: simulated process upset conditions

• High Agent Loading (HAL) Demonstration Test 2: one of the two ANR batches

processed during the test had 23% agent by weight versus target of 15%

*Reason for non-detects is unknown.

“Validation” of the Performance of theTHC Analyzer for Vinyl Chloride (VC)

• Comparison to COPC (Summa canister) samples for VC (HEPA/Bank 1)

—average VC concentration over 10 different 5-hr test periods

—good correlation, but THC Analyzer results average 40% higher

—R2 = 0.88 for all VC data; R2 = 0.84 for VC “process upset” data (red)

• VC challenges (2 ppm) in dry and humid air

—reported concentrations within about + 10% of target for up to 9,000 ppm H2O

Correlation with COPC Data (Filters 11 and 16) Dry/Humid/Dry VC Challenges

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H2O

VCR² = 0.8762

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Summa Canister VC, ppmv

Performance of the THC Analyzer for 1,2-Dichloroethane (DCA)

DCA concentrations reported by the THC analyzers are unreliable.

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A, p

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H2O

DCA

• False positives for DCA when water vapor

concentrations greater than about 10,000

ppm and fluctuating

• DCA response suppressed by water vapor

• Means for drying the THC Analyzer sample

stream in real-time are available

• DCA concentrations for “wet” Summa

canister samples typically 25-79 ppb

• Estimated detection limit for DCA for the

THC analyzers: 60 ppb (in dry air)

• Appears to be of little consequence due

DCA emissions << MPHRA threshold value

Dry/Humid/Dry DCA Challenges

THC Analyzers as Indicators of Process Upset Conditions

• Numerous sensors/transducers in the Agent Processing Building provide data indicative of process upset conditions—e.g., flow rates, pressures, temperatures, liquid levels, etc.

• Operators in the Control Room also monitor processes via CCTV —e.g., to detect liquid leaks and spills due to failed seals, champagning rounds, etc.

• MINICAMS units detect process upset conditions that result in significant airborne concentrations of agent HD—even if no sensor/transducer signal being monitored indicates an upset condition

• THC analyzers have the potential to detect, in real time, process upset conditions that result in significant increases in THC and VC process emissions* from systems in the APB—even if no sensor/transducer signal being monitored indicates an upset condition

20

*THC and/or VC process emissions beyond established control limits may be defined as

process upsets even if the underlying causes are not immediately apparent.

THC Data as a Supplement to Other Sensorsin Detecting “Process Upset” Conditions

• Based on review of THC Analyzer data to date, “process upset” conditions for HEPA/Bank 1 locations may exist if —Hourly average vinyl chloride > MPHRA threshold (1.47 ppm) and/or—5-min THC concentration > baseline “control limit” (0.53 ppm)

• Hourly average vinyl chloride concentrations > 1.47 ppm—11 instances during 6 months of munitions processing—6 of the 11 instances during identifiable “off-normal (upset)” conditions

• 5-min THC concentrations (not including VC) > 0.53 ppm

—22 instances during 6 months of munitions processing

—6 of the 22 instances during identifiable “off-normal (upset)” conditions

• Hourly average VC > 1.47 ppm and 5-min THC > 0.53 ppm

—9 instances during 6 months of munitions processing—5 of the 9 instances during identifiable “off-normal (upset)” conditions

21

Bank 3 Carbon Efficiency Butane Working Capacity

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7/5/2016 8/24/2016 10/13/2016 12/2/2016 1/21/2017 3/12/2017

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Filter 7 Filter 8 Filter 9 Filter 10 Filter 11 Filter 12 Filter 13 Filter 14 Filter 15 Filter 16

ASTM D5228 Standard Test Method for

Determination of Butane

Working Capacity of

Activated Carbon

10/25/16 11/17/16 03/14/17

Filter 11

Examples of THC Filtration at Filter 16

23

THCs (HD) filtered effectively by

carbon beds C1-C3 (04/29/17)

THCs (non-HD) not filtered

by carbon beds C1-C3 (02/01/17)

HD MINICAMS (IDLH)MWS Rooms 1 & 2

HD MINICAMS (IDLH)MWS Rooms 1 & 2

Summary

• VC concentrations reported by photoacoustic-based THC analyzers at

PCAPP correlate with munitions processing

• VC concentrations reported by THC analyzers correlate with COPC

sampling data during normal and upset conditions and, thus, may be

used as an indicator of process emissions

• Increases in reported THC and VC concentrations (beyond defined

control limits) may be indicative of process upset conditions

• VC concentration data during munitions processing may be indicative

of remaining carbon activity—additional carbon efficiency data needed

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VC HP Wash Water Daily Munitions Count

total hydrocarbon monitoring at the agent filtration area

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