Performance evaluation of an in situ nitrous acid measurement system and continuous measurement of nitrous acid in an indoor environment

Nitrous acid (HONO) may cause adverse effects to mucous membranes and lung function when people are exposed to higher HONO concentrations than those present in typical indoor residential environments. Therefore, determination of HONO concentration in indoor environments is required to investigate occurrences of high HONO levels. In this work, a high-time-resolution measurement system was utilized to better understand the levels and dynamic behavior of HONO in an indoor environment. The performance of the in situ HONO analyzer applied to this work was evaluated using a 12-hr integrated annular denuder technique under ambient conditions. Both methods for the measurements of HONO were in good agreement, with a regression slope of 0.84, an intercept of 0.09, and correlation coefficient (r2) of 0.67. Indoor HONO and nitrogen oxide concentrations were also observed for approximately 5 days in winter in the living room of an apartment that had a gas range for cooking in the kitchen. Investigation of the relationships among nitric oxide (NO), nitrite (NO2), and HONO concentrations suggests that HONO production during combustion could be the result of direct emission, whereas the heterogeneous NO2 chemistry during the background period and after combustion was the possible pathway of HONO production. Controlled combustion experiments, performed at a burning rate of 50% valve setting, show peak HONO concentrations during the unvented combustion to be approximately 8-10 times higher than background levels depending on the time of day. At a burning rate setting of 50%, the peak concentration of HONO during unvented combustion was found to be 33-37% higher than those from "weak" (airflow = 340 m3/hr) and "strong" (airflow = 540 m3/hr) vented combustions. The decay rate of the HONO concentrations for the unvented combustion conditions was approximately 2-fold higher in the daytime than in the nighttime and significantly less than those of NO and NO2.     

Laboratory evaluation of an aldehyde scrubber system specifically for the detection of acrolein

We demonstrate the use of an aldehyde scrubber system to resolve isobaric aldehyde/alkene interferences in a proton transfer reaction mass spectrometer (PTR-MS) by selectively removing the aldehydes from the gas mixture without loss of quantitative information for the alkene components. The aldehyde scrubber system uses a bisulfite solution, which scrubs carbonyl compounds from the gas stream by forming water-soluble carbonyl bisulfite addition products, and has been evaluated using a synthetic mixture of acrolein and isoprene. Trapping efficiencies of acrolein exceeded 97%, whereas the transmission efficiency of isoprene was better than 92%. Quantification of the PTR-MS response to acrolein was validated through an intercomparison study that included two derivatization methods, dinitrophenylhydrazine (DNPH) and O-(4-cyano-2-ethoxybenzyl)hydroxylamine (CNET), and a spectroscopic method using a quantum cascade laser infrared absorption spectroscopy (QCL) instrument. Finally, using cigarette smoke as a complex matrix, the acrolein content was assessed using the scrubber and compared with direct QCL-based detection.     

A novel low-cost detection method for screening of arsenic in groundwater

In the present work, a novel and simple detection system for As inorganic species contained in groundwater is presented. To reach the required detection limit, the proposed methodology is based on two steps: first is the transport and preconcentration of the inorganic arsenic species using a polymer inclusion membrane (PIM) system and second is the formation of a coloured complex, the  absorbance of which is measured. Different parameters related to the membrane composition and the transport kinetics have been studied, and it was found that membranes made of polyvinyl chloride (PVC) as a polymer, and Aliquat 336 as a carrier, ensured efficient arsenic transport when the carrier content was at least 31 % (w/w). The implementation of the designed PIM in a special device that contained only 5 mL of the stripping solution (0.1 M NaCl) allowed As preconcentration from a 100-mL water sample, thus facilitating its detection with the colorimetric method. The new method developed here was validated, and its analytical figures of merit were determined, i.e. limit of detection of 4.5 μg L^?1 at 820 nm and a relative standard deviation within the range 8–10 %. Finally, the method was successfully applied to the analysis of different water samples from Catalonia region with naturally occurring As.     

Field study of nitrous oxide production with in situ aeration in a closed landfill site

Nitrous oxide (N₂O) has gained considerable attention as a contributor to global warming and depilation of stratospheric ozone layer. Landfill is one of the high emitters of greenhouse gas such as methane and N₂O during the biodegradation of solid waste. Landfill aeration has been attracted increasing attention worldwide for fast, controlled and sustainable conversion of landfills into a biological stabilized condition, however landfill aeration impel N₂O emission with ammonia removal. N₂O originates from the biodegradation, or the combustion of nitrogen-containing solid waste during the microbial process of nitrification and denitrification. During these two processes, formation of N₂O as a by-product from nitrification, or as an intermediate product of denitrification. In this study, air was injected into a closed landfill site and investigated the major N₂O production factors and correlations established between them. The in-situ aeration experiment was carried out by three sets of gas collection pipes along with temperature probes were installed at three different distances of one, two and three meter away from the aeration point; named points A-C, respectively. Each set of pipes consisted of three different pipes at three different depths of 0.0, 0.75 and 1.5 m from the bottom of the cover soil. Landfill gases composition was monitored weekly and gas samples were collected for analysis of nitrous oxide concentrations. It was evaluated that temperatures within the range of 30–40°C with high oxygen content led to higher generation of nitrous oxide with high aeration rate. Lower O₂ content can infuse N₂O production during nitrification and high O₂ inhibit denitrification which would affect N₂O production. The findings provide insights concerning the production potentials of N₂O in an aerated landfill that may help to minimize with appropriate control of the operational parameters and biological reactions of N turnover.

Implications: Investigation of nitrous oxide production potential during in situ aeration in an old landfill site revealed that increased temperatures and oxygen content inside the landfill site are potential factors for nitrous oxide production. Temperatures within the range of optimum nitrification process (30–40°C) induce nitrous oxide formation with high oxygen concentration as a by-product of nitrogen turnover. Decrease of oxygen content during nitrification leads increase of nitrous oxide production, while temperatures above 40°C with moderate and/or low oxygen content inhibit nitrous oxide generation.     

Laboratory testing of a continuous emissions monitor for hydrochloric acid

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, 25ºC, 100ºC, and 200ºC, 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 a function 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 100/200ºC. An HCl absorption line of 1.742 μm 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 μm. 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 25ºC to 200ºC 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.     

A sodium carbonate coated denuder for determination of nitrous acid in the atmosphere

A denuder technique for sampling and analysing nitrous acid at sub ppb levels in air is described. After sampling, the sodium carbonate coated denuder is leached in water, and the NO⁻₂ concentration is determined spectrophotometrically. Field tests show that PAN is partly sorbed and hydrolized to nitrite in the sodium carbonate layer. It seems as HNO₂ also can be formed by heterogeneous reactions between NO and NO₂ at the denuder wall. These sampling artifacts were overcome by sampling with two or three denuders in series. The presence of PAN deteriorates the detection limit, which during optimal conditions is about 0.5 nmole m⁻³ (0.01 ppb). The method is therefore not recommended for measurements in background air, where HNO₂ concentrations normally are low compared to PAN concentrations.     

The need for bioaugmentation after thermal treatment of a TCE-contaminated aquifer: Laboratory experiments

A microcosm study was conducted to evaluate the need for bioaugmentation after a thermal treatment to anaerobically dechlorinate trichloroethene (TCE) to ethene. The microcosms were either: heated to 100 degrees C and slowly cooled to simulate thermal remediation while bioaugmenting when the declining temperature reached 10 degrees C; or kept at ambient groundwater temperatures (10 degrees C) and bioaugmented for comparison. Aquifer samples from three sediment locations within a TCE-polluted source zone were investigated in duplicate microcosms. In biostimulated (5 mM lactate) and heated microcosms, no conversion of TCE was observed in 4 out of 6 microcosms, and in the remaining microcosms the dechlorination of TCE was incomplete to cDCE (cis-dichloroethene). By comparison, complete TCE dechlorination to ethene was observed in 4 out of 6 heated microcosms that were bioaugmented with a highly enriched dechlorinating mixed culture, KB-1, but no electron donor, and also in 4 of 6 microcosms that were augmented with KB-1 and an electron donor (5 mM lactate). These data suggest that electron donor released during heating, was capable of promoting complete dechlorination coincident with bioaugmentation. Heated microcosms demonstrated less methanogenesis than unheated microcosms, even with elevated H2 concentrations and addition of KB-1, which contains methanogens. This suggests that the heating process suppressed the native microbial community, which can decrease competition with the bioaugmented culture and increase the effectiveness of dechlorination following a thermal treatment. Specifically, cDCE removal rates were four to six times higher in heated than unheated bioaugmented microcosms. This study confirms the need for bioaugmentation following a laboratory thermal treatment to obtain complete dechlorination of TCE.     

Laboratory evaluation of zero-valent iron to treat water impacted by acid mine drainage

This study examines the applicability and limitations of granular zero-valent iron for the treatment of water impacted by mine wastes. Rates of acid-neutralization and of metal (Cu, Cd, Ni, Zn, Hg, Al, and Mn) and metalloid (As) uptake were determined in batch systems using simulated mine drainage (initial pH 2.3-4.5; total dissolved solids 14000-16000 mgl(-1)). Metal removal from solution and acid-neutralization occurred simultaneously and were most rapid during the initial 24 h of reaction. Reaction half-lives ranged from 1.50+/-0.09 h for Al to 8.15+/-0.36 h for Zn. Geochemical model results indicate that metal removal is most effective in solutions that are highly undersaturated with respect to pure-metal hydroxides suggesting that adsorption is the initial and most rapid metal uptake mechanism. Continued adsorption onto or co-precipitation with iron corrosion products are secondary metal uptake processes. Sulfate green rust was identified as the primary iron corrosion product, which is shown to be the result of elevated [SO(4)(2-)]/[HCO(3)(-)] ratios in solution. Reversibility studies indicate that zero-valent iron will retain metals after shifts in redox states are imposed, but that remobilization of metals may occur after the acid-neutralization capacity of the material is exhausted.     

Humic acid in ice: Photo-enhanced conversion of nitrogen dioxide into nitrous acid

Laboratory studies on the heterogeneous conversion of nitrogen dioxide into nitrous acid on irradiated ice films containing humic acid are described. It was found that the presence of light in the visible range of the solar spectrum significantly enhances the rate of nitrous acid release from a humic acid doped ice film. This process might contribute to observed HONO production in snow, where the NO₂ is thought to originate from nitrate photolysis. Analysis of the experimental data based on the Langmuir Hinshelwood model framework allowed quantification of the observed dependencies of the nitrous acid production rate on nitrogen dioxide concentration. The observed dependencies on the humic acid concentration as well as on the irradiation intensity were used to estimate light-driven HONO fluxes for environmental snow covers.     

Identification and measurement of nitrous acid in an indoor environment

We report here direct observation by differential optical absorption spectroscopy (DOAS) of the formation of ppb levels of gaseous nitrous acid (MONO) from the reaction of ppm levels of nitrogen dioxide (NO₂) with water vapor, in an indoor environment. The rate of formation of HONO displayed first order kinetics with respect to NO₂ with a rate of (0.25 ±0.04) ppb min⁻¹ per ppm of NO₂ present. Assuming a lifetime of l h with respect to both physical and chemical removal processes for HONO, this leads to an estimated steady state concentration of ~ 15 ppb of HONO per ppm of NO₂ present. This relatively high level of HONO associated with NO₂-air mixtures raises new questions concerning the health implications of elevated NO₂ concentrations in indoor environments e.g. HONO is a respirable nitrite known to convert secondary amines in vitro to carcinogenic nitrosamines.     

原位热处理技术修复重质非水相液体污染场地研究进展

重质非水相液体(DNAPLs)是土壤及地下水中广泛存在的有机污染物,原位热处理技术是目前修复受DNAPLs污染土壤及地下水的最具潜力的技术之一。综述了国内外常用原位热处理技术的基本原理及其影响因素,介绍了相关现场应用实例,并展望了该技术未来的应用前景和发展趋势,以期为中国污染土壤及地下水的原位修复提供有益借鉴。     

Uptake of nitrous acid and nitrogen oxides by nylon surfaces: Implications for nitric acid measurement

The interference in HNO₃ determination due to HNO₂ and NO_x retention on nylon filters has been evaluated in laboratory and field conditions. Nitrous acid is retained on nylon filters with efficiencies varying from 25% at 12ℓ min⁻¹ to 80% at 2ℓ min⁻¹, yielding NO₂⁻ ion. In ambient sampling performed during photochemical smog episodes, NO₂⁻ is oxidized to NO₃⁻ with conversion factors up to 100%, resulting in a positive bias in HNO₃ determination.NO₂ reacts heterogeneously with H₂O on nylon surfaces according to the reaction 2NO₂ + H₂O → HNO₂ + HNO₃ with a removal constant of about 1 × 10⁻⁴ ms⁻¹ at a H₂O concentration of 20,000 ppm. The resulting nitrite and nitrate are independent of the sampling flow rate, while NO₂ concentration, sampling time and exposed nylon surface area play a directly proportional role. Accordingly, the relative interference of NO₂ with respect to HNO₃ determination is almost negligible for nylon filters, usually run at relatively high flow rates, while it may be significant for nylon denuders, which are characterized by larger exposed surfaces and lower operating flow rates.     

Laboratory and field evaluation of a pretreatment system for removing organics from produced water

Co-produced water from the oil and gas industry accounts for a significant waste stream in the United States. This "produced water" is characterized by saline water containing a variety of pollutants, including water soluble and immiscible organics and many inorganic species. To reuse produced water, removal of both the inorganic dissolved solids and organic compounds is necessary. In this research, the effectiveness of a pretreatment system consisting of surfactant modified zeolite (SMZ) adsorption followed by a membrane bioreactor (MBR) was evaluated for simultaneous removal of carboxylates and hazardous substances, such as benzene, toluene, ethylbenzene, and xylenes (BTEX) from saline-produced water. A laboratory-scale MBR, operated at a 9.6-hour hydraulic residence time, degraded 92% of the carboxylates present in synthetic produced water. When BTEX was introduced simultaneously to the MBR system with the carboxylates, the system achieved 80 to 95% removal of BTEX via biodegradation. These results suggest that simultaneous biodegradation of both BTEX and carboxylate constituents found in produced water is possible. A field test conducted at a produced water disposal facility in Farmington, New Mexico confirmed the laboratory-scale results for the MBR and demonstrated enhanced removal of BTEX using a treatment train consisting of SMZ columns followed by the MBR. While most of the BTEX constituents of the produced water adsorbed onto the SMZ adsorption system, approximately 95% of the BTEX that penetrated the SMZ and entered the MBR was biodegraded in the MBR. Removal rates of acetate (influent concentrations of 120 to 170 mg/L) ranged from 91 to 100%, and total organic carbon (influent concentrations as high as 580 mg/L) ranged from 74 to 92%, respectively. Organic removal in the MBR was accomplished at a low biomass concentration of 1 g/L throughout the field trial. While the transmembrane pressure during the laboratory-scale tests was well-controlled, it rose substantially during the field test, where no pH control was implemented. The results suggest that pretreatment with an SMZ/MBR system can provide substantial removal of organic compounds present in produced water, a necessary first step for many water-reuse applications.     

Application of a minicolumn detection method for screening spices for aflatoxin

The minicolumn of Holaday and Lansden was modified by increasing the height of neutral alumina and including a layer of anhydrous sodium sulphate. Using this procedure, aflatoxin was detected in 18 of 125 samples of black pepper, red pepper, ginger and turmeric. A few samples of each spice contained aflatoxin, although red pepper and turmeric showed the highest incidence. Aflatoxin B1 quantities ranged from 10 ug/kg to 120 ug/kg when estimated quantitatively by visual comparison with standards on thin-layer chromatography plates.     

Spectroscopic identification and measurement of gaseous nitrous acid in dilute auto exhaust

We report here the direct spectroscopic detection of gaseous nitrous acid (HONO) in exhaust emissions from certain light duty motor vehicles (LDMV). Co-pollutants such as nitrogen dioxide (NO₂), formaldehyde (HCHO), benzaldehyde (C₆H₅CHO) and sulfur dioxide (SO₂) were also readily determined. Nitric oxide (NO) was measured too, but with reduced accuracy. To avoid possible artifactual formation of HONO on the surfaces of conventional dilution and sampling systems (e.g. Federal and California constant volume sampling systems), an instrument was developed consisting of a multiple reflection cell without walls coupled to a u.v. differential optical absorption spectrometer (DOAS), the entire system being placed in the open air ~ 2 m from the tailpipe of the LDMV. At an optical path of 31.2 m, detection limits (in parts per 10⁹, ppb) were: HONO-12; HCHO-78; C₆H₅CHO-13; NO₂-57; and SO₂-11. With this instrument, HONO levels observed in diluted exhaust ranged from nondetectable (< 12 ppb) for a 1982 California car with an effective 3-way catalyst (and associated low NO_x emissions), to ~ 300 ppb for a heavily used 1974 station wagon having high NO_x emissions and run on leaded gasoline. While the number of LDMV tested was too small for statistical treatment, our results show that the older portion of the total LDMV population (i.e. without current emission control devices) may be a significant primary source of gaseous HONO, a key precursor to photochemical air pollution and an inhalable nitrite.     

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.     

Development of a measuring technique for simultaneous in situ detection of nanoscaled particle size distributions and gas temperatures

Point measurements of time-resolved LII signals have been performed in sooting premixed low pressure flames. Soot particle size distribution and gas temperature in these flames are known from independent measurements. This data is used to validate parameters of an improved LII model, where special emphasis is taken on the accurate modelling of mass and heat transfer rates. Using this model particle size distributions and gas temperatures can be estimated from time-resolved LII signals using non-linear regression. Standard numerical methods are applied. An experimental setup is presented, which allows measuring one-dimensional maps of particle size distribution and gas temperature. The technique is based on the one-dimensional and time-resolved detection of LII signals using a Streak camera.     

Theoretical evaluation of a method for locating gaseous emission hot spots

This paper describes and theoretically evaluates a recently developed method that provides a unique methodology for mapping gaseous emissions from non-point pollutant sources. The horizontal radial plume mapping (HRPM) methodology uses an open-path, path-integrated optical remote sensing (PI-ORS) system in a horizontal plane to directly identify emission hot spots. The radial plume mapping methodology has been well developed, evaluated, and demonstrated. In this paper, the theoretical basis of the HRPM method is explained in the context of the method's reliability and robustness to reconstruct spatially resolved plume maps. Calculation of the condition number of the inversion's kernel matrix showed that this method has minimal error magnification (EM) when the beam geometry is optimized. Minimizing the condition number provides a tool for such optimization of the beam geometry because it indicates minimized EM. Using methane concentration data collected from a landfill with a tunable diode laser absorption spectroscopy (TDLAS) system, it is demonstrated that EM is minimal because the averaged plume map of many reconstructed plume maps is very similar to a plume map generated by the averaged concentration data. It is also shown in the analysis of this dataset that the reconstructions of plume maps are unique for the optimized HRPM beam geometry and independent of the actual algorithm applied.