Laboratory investigation of three distinct emissions monitors for hydrochloric acid.

The measurement of hydrochloric acid (HCl) on a continuous basis in coal-fired plants is expected to become more important if HCl standards become implemented as part of the Federal Mercury and Air Toxics Standards (MATS) standards that are under consideration. For this study, the operational performance of three methods/instruments, including tunable diode laser absorption spectroscopy (TDLAS), cavity ring down spectroscopy (CRDS), and Fourier transform infrared (FTIR) spectroscopy, were evaluated over a range of real-world operating environments. Evaluations were done over an HCl concentration range of 0-25 ppmv and temperatures of 25, 100, and 185 °C. The average differences with respect to temperature were 3.0% for the TDL for values over 2.0 ppmv and 6.9% of all concentrations, 3.3% for the CRDS, and 4.5% for the FTIR. Interference tests for H2O, SO2, and CO, CO2, and NO for a range of concentrations typical of flue gases from coal-fired power plants did not show any strong interferences. The possible exception was an interference from H2O with the FTIR. The instrument average precision over the entire range was 4.4% for the TDL with better precision seen for concentrations levels of 2.0 ppmv and above, 2.5% for the CRDS, and 3.5% for the FTIR. The minimum detection limits were all on the order of 0.25 ppmv, or less, utilizing the TDL values with a 5-m path. Zero drift was found to be 1.48% for the TDL, 0.88% for the CRDS, and 1.28% for the FTIR. IMPLICATIONS: This study provides an evaluation of the operational performance of three methods/instruments, including TDL absorption spectroscopy (TDLAS), cavity ring down spectroscopy (CRDS), and FTIR spectroscopy, for the measurement of hydrochloric acid (HCl) over a range of real-world operating environments. The results showed good instrument accuracy as a function of temperature and no strong interferences for flue gases typical to coal-fired power plants. The results show that these instruments would be viable for the measurement of HCl in coal-fired plants if HCl standards become implemented as part of the Federal Mercury and Air Toxics Standards (MATS) standards that are under consideration.

Laboratory testing of a continuous emissions monitor for hydrochloric acid.

UNLABELLED: Continuous monitoring of exhaust flue gas has become a common practice in power plants in response to Federal Mercury and Air Toxics Standards (MATS) standards. Under the current rules, hydrochloric acid (HCl) is not continuously measured at most plants; however, MATS standards have been proposed for HCl, and tunable diode laser (TDL) absorption spectroscopy is one method that can be used to measure HCl continuously. The focus of this work is on the evaluation and verification of the operation performance of an HCL TDL over a range of real-world operating environments. The testing was conducted at the University of California at Riverside (UCR) spectroscopy evaluation laboratory. Laboratory tests were conducted at three separate temperatures, 25 degrees C, 100 degrees C, and 200 degrees C, and two distinct moisture levels for the enhanced temperatures, 0%, (2 tests) and 4%, over a concentration range from 0 ppmv to 25 ppmv-m at each of the elevated temperatures. The results showed good instrument accuracy as afunction of changing temperature and moisture. Data analysis showed that the average percentage difference between the ammonia concentration and the calibration source was 3.33% for varying moisture from 0% to 4% and 2.69%for varying temperature from 25 to 100/200 degrees C. An HCl absorption line of 1.742 microm was selected for by the manufacturer for this instrument. The Hi Tran database indicated that CO2 is probably the only major interferent, although the CO2 absorption is very weak at that wavelength. Interference tests for NO, CO, SO2, NH3, and CO2 for a range of concentrations typical of flue gasses in coal-fired power plants did not show any interference with TDL HCl measurements at 1.742 microm. For these interference tests, CO2 was tested at a concentration of 11.9% concentration in N2 for these tests. Average precision over the entire range for all 10 tests is 3.12%. IMPLICATIONS: The focus of this study was.an evaluation of the operation performance of a tunable diode laser (TDL) for the measurement of hydrochloric acid (HCl) over a range of real-world operating environments. The results showed good instrument accuracy as a function of changing temperature from 25 degrees C to 200 degrees C and moisture from 0% to 4%. Such as an instrument could be used for continuous monitoring of exhaust flue gas in power plants once the Federal Mercury and Air Toxics Standards (MATS) standards have been fully implemented.

Impact of engine lubricant properties on regulated gaseous emissions of 2000-2001 model-year gasoline vehicles.

The impact of the sulfur (S) content in lubricating oil was evaluated for four ultra-low-emission vehicles and two super-ultra-low-emission vehicles, all with low mileage. The S content in the lube oils ranged from 0.01 to 0.76%, while the S content of the gasoline was fixed at 0.2 ppmw. Vehicles were configured with aged catalysts and tested over the Federal Test Procedure, at idle and at 50-mph cruise conditions. In all testing modes, variations in the S level of the lubricant did not significantly affect the regulated gas-phase tailpipe emissions. In addition to the regulated gas-phase emissions, a key element of the research was measuring the engine-out sulfur dioxide (SO2) in near-real-time. This research used a new methodology based on a differential optical absorption spectrometer (DOAS) to measure SO2 from the lubricants used in this study. With the DOAS, the contribution of SO2 emissions for the highest-S lubricant was found to range from less than 1 to 6 ppm on a gasoline S equivalent basis over the range of vehicles and test cycles used. The development and operation of the DOAS is discussed in this paper.

Investigation of NH3 emissions from new technology vehicles as a function of vehicle operating conditions.

The objective of this study was to measure ammonia (NH3) emissions from modern technology vehicles since information is scarce aboutthis importantsource of particulate matter (PM) precursors. Test variables included the emission level to which the vehicle was certified, the vehicle operating conditions, and catalyst age. Eight vehicles with low-emission vehicle (LEV) to super-ultralow-emission vehicle (SULEV) certification levels were tested over the Federal Test Procedure (FTP75), a US06 cycle, a hot running 505, a New York City Cycle (NYCC), and a specially designed Modal Emissions Cycle (MEC01v7) using both as-received and bench-aged catalysts. NH3 emissions in the raw exhaust were measured by tunable diode laser (TDL) absorption spectroscopy. The results show that NH3 emissions depend on driving mode and are primarily generated during acceleration events. More specifically, high NH3 emissions were found for high vehicle specific power (VSP) events and rich operating conditions. For some vehicles, NH3 emissions formed immediately after catalyst light-off during a cold start.

A passive flux denuder for evaluating emissions of ammonia at a dairy farm.

Passive samplers have been shown to be an inexpensive alternative to direct sampling. Diffusion denuders have been developed to measure the concentration of species such as ammonia (NH3), which is in equilibrium with particulate ammonium nitrate. Conventional denuder sampling has required active sampling that inherently requires air pumps and, therefore, electrical power. To estimate emissions of NH3 from a fugitive source would require an array of active samplers and meteorological measurements to estimate the flux. A recently developed fabric denuder was configured in an open tube to passively sample NH3 flux. Passive and active samplers were collocated at a dairy farm at the California State University, Fresno, Agricultural Research Facility. During this comparison study, NH3 flux measurements were made at the dairy farm lagoon before and after the lagoon underwent acidification. Comparisons were made of the flux measurements obtained directly from the passive flux denuder and those calculated from an active filter pack sampler and wind velocity. The results show significant correlation between the two methods, although a correction factor needed to be applied to directly compare the two techniques. This passive sampling approach significantly reduces the cost and complexity of sampling and has the potential to economically develop a larger inventory base for ambient NH3 emissions.