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Title: Mercury CEM Calibration

Technical Report ·
DOI:https://doi.org/10.2172/993831· OSTI ID:993831

Mercury continuous emissions monitoring systems (CEMS) are being implemented in over 800 coal-fired power plant stacks. The power industry desires to conduct at least a full year of monitoring before the formal monitoring and reporting requirement begins on January 1, 2009. It is important for the industry to have available reliable, turnkey equipment from CEM vendors. Western Research Institute (WRI) is working closely with the Electric Power Research Institute (EPRI), the National Institute of Standards and Technology (NIST), and the Environmental Protection Agency (EPA) to facilitate the development of the experimental criteria for a NIST traceability protocol for dynamic elemental mercury vapor generators. The generators are used to calibrate mercury CEMs at power plant sites. The Clean Air Mercury Rule (CAMR) which was published in the Federal Register on May 18, 2005 requires that calibration be performed with NIST-traceable standards (Federal Register 2007). Traceability procedures will be defined by EPA. An initial draft traceability protocol was issued by EPA in May 2007 for comment. In August 2007, EPA issued an interim traceability protocol for elemental mercury generators (EPA 2007). The protocol is based on the actual analysis of the output of each calibration unit at several concentration levels ranging initially from about 2-40 {micro}g/m{sup 3} elemental mercury, and in the future down to 0.2 {micro}g/m{sup 3}, and this analysis will be directly traceable to analyses by NIST. The document is divided into two separate sections. The first deals with the qualification of generators by the vendors for use in mercury CEM calibration. The second describes the procedure that the vendors must use to certify the generator models that meet the qualification specifications. The NIST traceable certification is performance based, traceable to analysis using isotope dilution inductively coupled plasma/mass spectrometry performed by NIST in Gaithersburg, MD. The outputs of mercury generators are compared to one another using a nesting procedure which allows direct comparison of one generator with another and eliminates analyzer variability effects. The qualification portion of the EPA interim traceability protocol requires the vendors to define generator performance as affected by variables such as pressure, temperature, line voltage, and shipping. WRI is focusing efforts to determine actual generator performance related to the variables defined in the qualification portion of the interim protocol. The protocol will then be further revised by EPA based on what can actually be achieved with the generators. Another focus of the study is to evaluate approaches for field verification of generator performance. Upcoming work includes evaluation of oxidized mercury calibration generators, for which a separate protocol will be prepared by EPA. In addition, the variability of the spectrometers/analyzers under various environmental conditions needs to be defined and understood better. A main objective of the current work is to provide data on the performance and capabilities of elemental mercury generator/calibration systems for the development of realistic NIST traceability protocols for mercury vapor standards for continuous emission CEM calibration. This work is providing a direct contribution to the enablement of continuous emissions monitoring at coal-fired power plants in conformance with the CAMR. EPA Specification 12 states that mercury CEMs must be calibrated with NIST-traceable standards (Federal Register 2005). The initial draft of an elemental mercury generator traceability protocol was circulated by EPA in May 2007 for comment, and an interim protocol was issued in August 2007 (EPA 2007). Initially it was assumed that the calibration and implementation of mercury CEMs would be relatively simple, and implementation would follow the implementation of the Clean Air Interstate Rule (CAIR) SO{sub 2} and NO{sub x} monitoring, and sulfur emissions cap and trade. However, mercury has proven to be significantly more difficult to accurately determine than was originally thought. The purpose of the current phase of this project is to evaluate issues related to the use of dynamic elemental mercury calibrators that are based on mercury vapor headspace above elemental mercury at a particular temperature.

Research Organization:
Univ. of Wyoming, Laramie, WY (United States)
Sponsoring Organization:
USDOE
DOE Contract Number:
FC26-98FT40323
OSTI ID:
993831
Country of Publication:
United States
Language:
English

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