Waste Isolation Pilot Plant Flammable Gas Analysis (Rev. 1.2)

This document describes and implements the process to establish the concentration of flammable gas/volatile organic compounds (VOCs), hydrogen, and methane in a waste container intended for shipment in the Transuranic Package Transporter-II (TRUPACT-II) or HalfPACT packagings. An aliquot of headspace gas (HSG) is sampled from a waste container and analyzed using one analytical unit which is a gas chromatograph (GC) with two detectors, a mass spectrometer (MS) and a thermal conductivity detector (TCD). The sample introduced to the GC is split and part goes to MS and the other part goes to TCD. The MS analyzes sample for volatile organic compounds (VOC) and the TCD analyzes for hydrogen and methane. The requirements and technical bases for allowable flammable gas/VOC concentrations are described in the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC).

This document describes and implements the process to establish the concentration of flammable gas/volatile organic compounds (VOCs), hydrogen, and methane in a waste container intended for shipment in the Transuranic Package Transporter-II (TRUPACT-II) or HalfPACT packagings. An aliquot of headspace gas (HSG) is sampled from a waste container and analyzed using one analytical unit which is a gas chromatograph (GC) with two detectors, a mass spectrometer (MS) and a thermal conductivity detector (TCD). The sample introduced to the GC is split and part goes to MS and the other part goes to TCD. The MS analyzes sample for volatile organic compounds (VOC) and the TCD analyzes for hydrogen and methane. The requirements and technical bases for allowable flammable gas/VOC concentrations are described in the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC).

This document describes and implements the process to establish the concentration of flammable gas/volatile organic compounds (VOCs), hydrogen, and methane in a waste container intended for shipment in the Transuranic Package Transporter-II (TRUPACT-II) or HalfPACT packagings. An aliquot of headspace gas (HSG) is sampled from a waste container and analyzed using one analytical unit which is a gas chromatograph (GC) with two detectors, a mass spectrometer (MS) and a thermal conductivity detector (TCD). The sample introduced to the GC is split and part goes to MS and the other part goes to TCD. The MS analyzes sample for volatile organic compounds (VOC) and the TCD analyzes for hydrogen and methane. The requirements and technical bases for allowable flammable gas/VOC concentrations are described in the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC).

This document describes and implements the process to establish the concentration of flammable gas/volatile organic compounds (VOCs), hydrogen, and methane in a waste container intended for shipment in the Transuranic Package Transporter-II (TRUPACT-II) or HalfPACT packagings. An aliquot of headspace gas (HSG) is sampled from a waste container and analyzed using one analytical unit which is a gas chromatograph (GC) with two detectors, a mass spectrometer (MS) and a thermal conductivity detector (TCD). The sample introduced to the GC is split and part goes to MS and the other part goes to TCD. The MS analyzes sample for volatile organic compounds (VOC) and the TCD analyzes for hydrogen and methane. The requirements and technical bases for allowable flammable gas/VOC concentrations are described in the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC).

This document describes and implements the process to establish the concentration of flammable gas/volatile organic compounds (VOCs), hydrogen, and methane in a waste container intended for shipment in the Transuranic Package Transporter-II (TRUPACT-II) or HalfPACT packagings. An aliquot of headspace gas (HSG) is sampled from a waste container and analyzed using one analytical unit which is a gas chromatograph (GC) with two detectors, a mass spectrometer (MS) and a thermal conductivity detector (TCD). The sample introduced to the GC is split and part goes to MS and the other part goes to TCD. The MS analyzes sample for volatile organic compounds (VOC) and the TCD analyzes for hydrogen and methane. The requirements and technical bases for allowable flammable gas/VOC concentrations are described in the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC).

This document describes and implements the process to establish the concentration of flammable gas/volatile organic compounds (VOCs), hydrogen, and methane in a waste container intended for shipment in the Transuranic Package Transporter-II (TRUPACT-II) or HalfPACT packagings. An aliquot of headspace gas (HSG) is sampled from a waste container and analyzed using one analytical unit which is a gas chromatograph (GC) with two detectors, a mass spectrometer (MS) and a thermal conductivity detector (TCD). The sample introduced to the GC is split and part goes to MS and the other part goes to TCD. The MS analyzes sample for volatile organic compounds (VOC) and the TCD analyzes for hydrogen and methane. The requirements and technical bases for allowable flammable gas/VOC concentrations are described in the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC).

This document describes and implements the process to determine the concentration of flammable gas/volatile organic compounds (VOCs), hydrogen, and methane in a waste container intended for shipment in the Transuranic Package Transporter-II (TRUPACT-II), HalfPACT, or RH-TRU 72-B packagings. An aliquot of headspace gas (HSG) is sampled from a waste container and analyzed using a gas chromatograph (GC) with two detectors: a mass spectrometer (MS), and a thermal conductivity detector (TCD). The sample analyzed in the GC is split and half is sent to the MS for volatile organic compound (VOC) analysis while the other half is sent to the TCD for hydrogen and methane analysis. The requirements and technical bases for allowable flammable gas/VOC concentrations are described in the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC) and the Remote-Handled Transuranic Waste Authorized Methods for Payload Control (RHTRAMPAC).

This document describes and implements the process to determine the concentration of flammable gas/volatile organic compounds (VOCs), hydrogen, and methane in a waste container intended for shipment in the Transuranic Package Transporter-II (TRUPACT-II), HalfPACT, TRUPACT-III, or RH-TRU72-B packagings. An aliquot of headspace gas (HSG) is sampled from a waste container and analyzed using a gas chromatograph (GC) with two detectors: a mass spectrometer (MS), and a thermal conductivity detector (TCD). The sample analyzed in the GC is split and half is sent to the MS for volatile organic compound (VOC) analysis while the other half is sent to the TCD for hydrogen and methane analysis.

PurposeVolatile organic compounds (VOCs) are a major source of air pollution, significantly affecting both human health and the environment. These VOCs from wastewater can enter the atmosphere through air–water exchange and pose a great threat to human health, as the quality of our environment has consequences for agriculture, drinking water, pollution, greenhouse effect, and so on. ApproachGas chromatography (GC) is one of many techniques for detecting VOCs. Recent research has explored the integration of various detectors with GC, such as mass spectrometers, flame ionization detectors, ion mobility spectrometers, and thermal conductivity detectors. While GC remains a cornerstone in VOC detection, other techniques are also gaining significant attention. Notably, emerging technologies such as different types of E-nose and acoustic wave sensing devices offer promising results for VOC detection. Additionally, the evolution of data processing for VOCs through statistical and numerical methods, as well as the incorporation of artificial intelligence methodologies with smart sensing devices, further broadens the horizon of VOC detection and quantification. FindingsApart from the well-established GC suite of experimental VOC detection and measurement tools, much progress has recently been made in the development of relatively inexpensive and portable semiconductor metal oxides-, conducting polymers-, and carbon nanomaterials-based E-nose and surface acoustic wave sensing devices for VOC sensing and quantification. Another significant development in wastewater VOC detection and characterization is the adoption of artificial intelligence tools such as machine learning and deep learning that have shown great promise towards automation and ability to deal with large and complex VOC analysis. ValueThis article provides valuable insights into the development of methodologies for monitoring VOCs in wastewater. The review outlines the advantages and limitations of different VOCs detection techniques as well as the challenges associated with VOCs monitoring in wastewater. Our aim is to provide guidance from a methodology perspective for researchers and practitioners working in the field of wastewater management and environmental monitoring, highlighting areas for future research and development. The insights presented will aid in the development of more accurate and efficient VOC monitoring methods for wastewater, thereby helping to protect human health and the environment.

This document presents the technical justification for choosing and using propane as a calibration standard for estimating total flammable volatile organic compounds (VOCs) in an air matrix. A propane-in-nitrogen standard was selected based on a number of criteria: (1) has an analytical response similar to the VOCs of interest, (2) can be made with known accuracy and traceability, (3) is available with good purity, (4) has a matrix similar to the sample matrix, (5) is stable during storage and use, (6) is relatively non-hazardous, and (7) is a recognized standard for similar analytical applications. The Waste Retrieval Project (WRP) desires a fast, reliable, and inexpensive method for screening the flammable VOC content in the vapor-phase headspace of waste containers. Table 1 lists the flammable VOCs of interest to the WRP. The current method used to determine the VOC content of a container is to sample the container's headspace and submit the sample for gas chromatography--mass spectrometry (GC-MS) analysis. The driver for the VOC measurement requirement is safety: potentially flammable atmospheres in the waste containers must be allowed to diffuse prior to processing the container. The proposed flammable VOC screening method is to inject an aliquot of the headspace sample into an argon-doped pulsed-discharge helium ionization detector (Ar-PDHID) contained within a gas chromatograph. No actual chromatography is performed; the sample is transferred directly from a sample loop to the detector through a short, inert transfer line. The peak area resulting from the injected sample is proportional to the flammable VOC content of the sample. However, because the Ar-PDHID has different response factors for different flammable VOCs, a fundamental assumption must be made that the agent used to calibrate the detector is representative of the flammable VOCs of interest that may be in the headspace samples. At worst, we desire that calibration with the selected calibrating agent overestimate the value of the VOCs in a sample. By overestimating the VOC content of a sample, we want to minimize false negatives. A false negative is defined as incorrectly estimating the VOC content of the sample to be below programmatic action limits when, in fact, the sample,exceeds the action limits. The disadvantage of overestimating the flammable VOC content of a sample is that additional cost may be incurred because additional sampling and GC-MS analysis may be required to confirm results over programmatic action limits. Therefore, choosing an appropriate calibration standard for the Ar-PDHID is critical to avoid false negatives and to minimize additional analytical costs.

Polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOCs) mitigation in the pyrolysis process of waste tires using CO2 as a reaction medium

In the conditional no-migration determination (NMD) for the test phase of the Waste Isolation Pilot Plant (WIPP), the US Environmental Protection Agency (EPA) imposed certain conditions on the US Department of Energy (DOE) regarding gas phase volatile organic compound (VOC) concentrations in the void space of transuranic (TRU) waste containers. Specifically, the EPA required the DOE to ensure that each waste container has no layer of confinement that contains flammable mixtures of gases or mixtures of gases that could become flammable when mixed with air. The EPA also required that sampling of the headspace of waste containers outside inner layers of confinement be representative of the entire void space of the container. The EPA stated that all layers of confinement in a container would have to be sampled until DOE can demonstrate to the EPA that sampling of all layers is either unnecessary or can be safely reduced. A test program was conducted at the Idaho National Engineering and Environmental Laboratory (INEEL) to demonstrate that the gas phase VOC concentration in the void space of each layer of confinement in vented drums can be estimated from measured drum headspace using a theoretical transport model and that sampling of each layer of confinement is unnecessary. This report summarizes the studies performed in the INEEL test program and extends them for the purpose of developing a methodology for determining gas phase VOC concentrations in both vented and unvented TRU waste containers. The methodology specifies conditions under which waste drum headspace gases can be said to be representative of drum gases as a whole and describes a method for predicting drum concentrations in situations where the headspace concentration is not representative. The methodology addresses the approach for determining the drum VOC gas content for two purposes: operational period drum handling and operational period no-migration calculations.

In the conditional no-migration determination (NMD) for the test phase of the Waste Isolation Pilot Plant (WIPP), the US Environmental Protection Agency (EPA) imposed certain conditions on the US Department of Energy (DOE) regarding gas phase volatile organic compound (VOC) concentrations in the void space of transuranic (TRU) waste containers. Specifically, the EPA required the DOE to ensure that each waste container has no layer of confinement that contains flammable mixtures of gases or mixtures of gases that could become flammable when mixed with air. The EPA also required that sampling of the headspace of waste containers outside inner layers of confinement be representative of the entire void space of the container. The EPA stated that all layers of confinement in a container would have to be sampled until DOE can demonstrate to the EPA that sampling of all layers is either unnecessary or can be safely reduced. A test program was conducted at the Idaho National Engineering Laboratory (INEL) to demonstrate that the gas phase VOC concentration in the void space of each layer of confinement in vented drums can be estimated from measured drum headspace using a theoretical transport model and that sampling of each layer of confinement is unnecessary. This report summarizes the studies performed in the INEL test program and extends them for the purpose of developing a methodology for determining gas phase VOC concentrations in both vented and unvented TRU waste containers. The methodology specifies conditions under which waste drum headspace gases can be said to be representative of drum gases as a whole and describes a method for predicting drum concentrations in situations where the headspace concentration is not representative. The methodology addresses the approach for determining the drum VOC gas content for two purposes: operational period drum handling and operational period no-migration calculations.

Design parameters, process flows, electro-thermal-fluidic simulations and experimental characterizations of Micro-Electro-Mechanical-Systems (MEMS) suited for gas-chromatographic (GC) applications are presented and thoroughly described in this thesis, whose topic belongs to the research activities the Institute for Microelectronics and Microsystems (IMM)-Bologna is involved since several years, i.e. the development of micro-systems for chemical analysis, based on silicon micro-machining techniques and able to perform analysis of complex gaseous mixtures, especially in the field of environmental monitoring. In this regard, attention has been focused on the development of micro-fabricated devices to be employed in a portable mini-GC system for the analysis of aromatic Volatile Organic Compounds (VOC) like Benzene, Toluene, Ethyl-benzene and Xylene (BTEX), i.e. chemical compounds which can significantly affect environment and human health because of their demonstrated carcinogenicity (benzene) or toxicity (toluene, xylene) even at parts per billion (ppb) concentrations. The most significant results achieved through the laboratory functional characterization of the mini-GC system have been reported, together with in-field analysis results carried out in a station of the Bologna air monitoring network and compared with those provided by a commercial GC system. The development of more advanced prototypes of micro-fabricated devices specifically suited for FAST-GC have been also presented (silicon capillary columns, Ultra-Low-Power (ULP) Metal OXide (MOX) sensor, Thermal Conductivity Detector (TCD)), together with the technological processes for their fabrication. The experimentally demonstrated very high sensitivity of ULP-MOX sensors to VOCs, coupled with the extremely low power consumption, makes the developed ULP-MOX sensor the most performing metal oxide sensor reported up to now in literature, while preliminary test results proved that the developed silicon capillary columns are capable of performances comparable to those of the best fused silica capillary columns. Finally, the development and the validation of a coupled electro-thermal Finite Element Model suited for both steady-state and transient analysis of the micro-devices has been described, and subsequently implemented with a fluidic part to investigate devices behaviour in presence of a gas flowing with certain volumetric flow rates.

This article describes a new gas chromatography-based emissions monitoring system for measuring volatile organic compounds (VOCs) and hazardous air pollutants (HAPs). The system is composed of a dual-column gas chromatograph equipped with thermal conductivity detectors, in which separation is optimized for fast chromatography. The system has the necessary valving for stream selection, which allows automatic calibration of the system at predetermined times and successive measurement of individual VOCs before and after a control device. Nine different VOCs (two of which are HAPs), plus methane (CH4) and carbon dioxide (CO2) are separated and quantified every two minutes. The accuracy and precision of this system has been demonstrated to be greater than 95%. The system employs a mass flow measurement device and also calculates and displays processed emission data, such as control device efficiency and total weight emitted during given time periods. Two such systems have been operational for one year in two separate gravure printing facilities; minimal upkeep is required, about one hour per month. One of these systems, used before and after a carbon adsorber, has been approved by the pertinent local permitting authority.