Long-term evaluation of activated carbon as an adsorbent for biogas desulfurization

ABSTRACT

In this study, granular activated carbon (GAC) was used as an adsorbent for biogas desulfurization. Biogas containing 932–2,350 ppm of H₂S was collected from an anaerobic digester to treat the wastewater from a dairy farm with about 200 cows. An adsorption test was performed by introducing the biogas to a column that was packed with approximately 50 L of commercial GAC. The operation ceased if the effluent gas had an H₂S concentration of over 100 ppm. The GAC was replaced by a given weight of new GAC in a subsequent test. According to the results, for H₂S concentrations in the range of 932–1,560 ppm (average±SD = 1,260 ± 256 ppm), 1 kg of the GAC yielded biogas treatment capacities of 568 ± 112 m³ and H₂S adsorption capacities of 979 ± 235 g. For the higher influent H₂S concentrations of 2,110 ± 219 ppm, the biogas treatment and H₂S-adsorption capacities decreased to 229 ± 18 m³ and 668 ± 47 g, respectively. An estimation indicated a requisite cost of US$16.5 for the purification of 1,000 m³ of biogas containing 2,110 ppm of H₂S. This cost is approximately 5% of US$330, the value of 1,000 m³ of biogas.     

Effect of Advanced Oxidants Generated Via Ultraviolet Light on a Sequentially Loaded and Regenerated Granular Activated Carbon Biofilter

Abstract

The objective of this research was to investigate a sequentially loaded and regenerated granular activated carbon (GAC) biofilter system and to determine whether regenerative ozonation/advanced oxidation could improve the removal and biodegradation of a volatile organic compound from a contaminated airstream. Bench-scale reactors were constructed to operate in a manner analogous to a commercially available system manufactured by Terr-Aqua Environmental Systems (only with longer contact time). The GAC system consisted of two GAC biofilter beds that operated in a cyclical manner. On a given day, the first GAC bed adsorbed methyl isobutyl ketone from a simulated waste airstream, while the second bed underwent regeneration; then on the next day, the second bed was in the adsorption mode while the first was regenerated.

Three bench-scale systems were used to compare the performance under three operating conditions: (1) ozone/ associated oxidant regeneration of a GAC biofilter system that was seeded with microorganisms from a field site, (2) a humid air regeneration of a seeded GAC biofilter, and (3) a humid air regeneration of an unseeded GAC biofilter. For the advanced oxidant regenerated GAC biofilter, a maximum removal efficiency of >95% was achieved with an empty bed contact time of 148 sec and an influent concentration of 125 ppm methyl isobutyl ketone, and 90–95% was achieved at 148-sec empty bed contact time and a 1150-ppm influent.     

Biotrickling Filtration of Nitric Oxide

ABSTRACT

A biotrickling filter with blast-furnace slag packings (sizes = 20-40 mm and specific surface area = 120 m²/m³) was utilized to treat NO in an air stream. The operational stability, as well as the effects of gas empty-bed retention time (EBRT) and nutrient addition on the removal ability of NO, were tested. Approximately six weeks were required for the development of a biofilm for NO degradation, and a two-week organic carbon deficiency resulted in the detachment of biofilms from the packing surfaces. A steady removal rate of 80% was attained at specified influent NO concentrations of 892 to 1237 ppm and an EBRT of 118 sec. The effluent NO concentration diminished exponentially with enlarging EBRT, with influent NO concentrations of 203-898 ppm, and EBRTs of 25 to 118 sec. Nutrient addition is essential for efficient removal of the influent NO. Mass ratios of C: P: N = 7: 1: 30 and NaHCO₃: NO-N = 6.3 could be used for practical applications.     

Effect of advanced oxidants generated via ultraviolet light on a sequentially loaded and regenerated granular activated carbon biofilter

The objective of this research was to investigate a sequentially loaded and regenerated granular activated carbon (GAC) biofilter system and to determine whether regenerative ozonation/advanced oxidation could improve the removal and biodegradation of a volatile organic compound from a contaminated airstream. Bench-scale reactors were constructed to operate in a manner analogous to a commercially available system manufactured by Terr-Aqua Environmental Systems (only with longer contact time). The GAC system consisted of two GAC biofilter beds that operated in a cyclical manner. On a given day, the first GAC bed adsorbed methyl isobutyl ketone from a simulated waste airstream, while the second bed underwent regeneration; then on the next day, the second bed was in the adsorption mode while the first was regenerated. Three bench-scale systems were used to compare the performance under three operating conditions: (1) ozone/ associated oxidant regeneration of a GAC biofilter system that was seeded with microorganisms from a field site, (2) a humid air regeneration of a seeded GAC biofilter, and (3) a humid air regeneration of an unseeded GAC biofilter. For the advanced oxidant regenerated GAC biofilter, a maximum removal efficiency of >95% was achieved with an empty bed contact time of 148 sec and an influent concentration of 125 ppm methyl isobutyl ketone, and 90-95% was achieved at 148-sec empty bed contact time and a 1150-ppm influent.     

Effect of Water and Carbon Dioxide in Chemiluminescent Measurement of Oxides of Nitrogen

ABSTRACT

This paper reports results of studies using a biotrickling filter with blast-furnace slag packings (sizes = 2–4 cm and specific surface area = 120 m²/m³) for treatment of ethylether in air stream. Effects of volumetric loading, superficial gas velocity, empty bed gas retention time, recirculation liquid flow rate, and biofilm renewal on the ethylether removal efficiency and elimination capacity were tested. Results indicate that ethylether removal efficiencies of more than 95% were obtained with an empty bed retention time (EBRT) of 113 sec and loadings of lower than 70 g/m³/hr. At an EBRT of 57 sec, removal efficiencies of more than 90% could only be obtained with loadings of lower than 35 g/m³/hr. The maximum elimination capacities were 71 and 45 g/m³/hr for EBRT = 113 and 57 sec, respectively. The maximum ethylether elimination capacities were 71 and 96 g/m³/hr, respectively, before and after the renewal at EBRT = 113 sec. With an EBRT of 113 sec and a loading of lower than 38 g/m³/hr, the removal efficiency was nearly independent of the superficial liquid recirculation velocity in the range of 3.6 to 9.6 m³/m²/hr. From data regression, simplified mass-transfer limited, and reaction- and mass-transfer limited models correlating the contaminant concentration and the packing height were proposed and verified. The former model is applicable for cases of low influent contaminant concentrations or loadings, and the latter is applicable for cases of higher ones. Finally, CO₂ conversion efficiencies of approximately 90% for the influent ethylether were obtained. The value is comparable to data reported from other related studies.     

The role of precursor gases and meteorology on temporal evolution of O3 at a tropical location in northeast India

South Asia, particularly the Indo-Gangetic Plains and foothills of the Himalayas, has been found to be a major source of pollutant gases and particles affecting the regional as well as the global climate. Inventories of greenhouse gases for the South Asian region, particularly the sub-Himalayan region, have been inadequate. Hence, measurements of the gases are important from effective characterization of the gases and their climate effects. The diurnal, seasonal, and annual variation of surface level O₃ measured for the first time in northeast India at Dibrugarh (27.4° N, 94.9° E, 111 m amsl), a sub-Himalayan location in the Brahmaputra basin, from November 2009 to May 2013 is presented. The effect of the precursor gases NO _x and CO measured simultaneously during January 2012–May 2013 and the prevailing meteorology on the growth and decay of O₃ has been studied. The O₃ concentration starts to increase gradually after sunrise attaining a peak level around 1500 hours LT and then decreases from evening till sunrise next day. The highest and lowest monthly maximum concentration of O₃ is observed in March (42.9?±?10.3 ppb) and July (17.3?±?7.0 ppb), respectively. The peak in O₃ concentration is preceded by the peaks in NO _x and CO concentrations which maximize during the period November to March with peak values of 25.2?±?21.0 ppb and 1.0?±?0.4 ppm, respectively, in January. Significant nonlinear correlation is observed between O₃ and NO, NO₂, and CO. National Atmospheric and Oceanic Administration Hybrid Single-Particle Lagrangian Integrated Trajectory back-trajectory and concentration weighted trajectory analysis carried out to delineate the possible airmass trajectory and to identify the potential source region of NO _x and O₃ concentrations show that in post-monsoon and winter, majority of the trajectories are confined locally while in pre-monsoon and monsoon, these are originated at the Indo-Gangetic plains, Bangladesh, and Bay of Bengal.     

Formation of indoor nitrous acid (HONO) by light-induced NO<Subscript>2</Subscript> heterogeneous reactions with white wall paint

Gaseous nitrogen dioxide (NO₂) represents an oxidant that is present in relatively high concentrations in various indoor settings. Remarkably increased NO₂ levels up to 1.5 ppm are associated with homes using gas stoves. The heterogeneous reactions of NO₂ with adsorbed water on surfaces lead to the generation of nitrous acid (HONO). Here, we present a HONO source induced by heterogeneous reactions of NO₂ with selected indoor paint surfaces in the presence of light (300 nm?<?λ?<?400 nm). We demonstrate that the formation of HONO is much more pronounced at elevated relative humidity. In the presence of light (5.5 W m^?2), an increase of HONO production rate of up to 8.6?·?10⁹ molecules cm^?2 s^?1 was observed at [NO₂]?=?60 ppb and 50 % relative humidity (RH). At higher light intensity of 10.6 (W m^?2), the HONO production rate increased to 2.1?·?10¹⁰ molecules cm^?2 s^?1. A high NO₂ to HONO conversion yield of up to 84 % was observed. This result strongly suggests that a light-driven process of indoor HONO production is operational. This work highlights the potential of paint surfaces to generate HONO within indoor environments by light-induced NO₂ heterogeneous reactions.     

Biotrickling filtration of nitric oxide

A biotrickling filter with blast-furnace slag packings (sizes = 20-40 mm and specific surface area = 120 m2/m3) was utilized to treat NO in an air stream. The operational stability, as well as the effects of gas empty-bed retention time (EBRT) and nutrient addition on the removal ability of NO, were tested. Approximately six weeks were required for the development of a biofilm for NO degradation, and a two-week organic carbon deficiency resulted in the detachment of biofilms from the packing surfaces. A steady removal rate of 80% was attained at specified influent NO concentrations of 892 to 1237 ppm and an EBRT of 118 sec. The effluent NO concentration diminished exponentially with enlarging EBRT, with influent NO concentrations of 203-898 ppm, and EBRTs of 25 to 118 sec. Nutrient addition is essential for efficient removal of the influent NO. Mass ratios of C: P: N = 7: 1: 30 and NaHCO3: NO-N = 6.3 could be used for practical applications.     

Analysis of air quality in Dire Dawa,Ethiopia

Ambient air quality was monitored and analyzed to develop air quality index and its implications for livability and climate change in Dire Dawa, Ethiopia. Using survey research design, 16 georeferenced locations, representing different land uses, were randomly selected and assessed for sulfur dioxide (SO₂), nitrogen dioxide (NO₂), carbon dioxide (CO₂), carbon monoxide (CO),volatile organic compounds (VOCs), and meteorological parameters (temperature and relative humidity). The study found mean concentrations across all land uses for SO₂ of 0.37 ± 0.08 ppm, NO₂ of 0.13 ± 0.17 ppm, CO₂ of 465.65 ± 28.63 ppm, CO of 3.35 ± 2.04 ppm, and VOCs of 1850.67 ± 402 ppm. An air quality index indicated that ambient air quality for SO₂ was very poor, NO₂ ranged from moderate to very poor, whereas CO rating was moderate. Significant positive correlations existed between temperature and NO₂, CO₂, and CO and between humidity and VOCs. Significant relationships were also recorded between CO₂ and NO₂ and between CO and CO₂. Poor urban planning, inadequate pollution control measure, and weak capacity to monitor air quality have implications for energy usage, air quality, and local meteorological parameters, with subsequent feedback into global climate change. Implementation of programs to monitor and control emissions in order to reduce air pollution will provide health, economic, and environmental benefits to the city.

Implications: The need to develop and implement emission control programs to reduce air pollution in Dire Dawa City is urgent. This will provide enormous economic, health, and environmental benefits. It is expected that economic effects of air quality improvement will offset the expenditures for pollution control. Also, strategies that focus on air quality and climate change present a unique opportunity to engage different stakeholders in providing inclusive and sustainable development agenda for Dire Dawa.     

Phosphorus removal in a sulfur–limestone autotrophic denitrification (SLAD) biofilter

The sulfur–limestone autotrophic denitrification (SLAD) biofilter was able to remove phosphorous from wastewater during autotrophic denitrification. Parameters influencing autotrophic denitrification in the SLAD biofilter, such as hydraulic retention time (HRT), influent nitrate (NO₃ ^?), and influent PO₄ ^3? concentrations, had significant effects on P removal. P removal was well correlated with total oxidized nitrogen (TON) removed in the SLAD biofilter; the more TON removed, the more efficient P removal was achieved. When treating the synthetic wastewater containing NO₃ ^?-N of 30 mg L^?1 and PO₄ ^3?-P of 15 mg L^?1, the SLAD biofilter removed phosphorus of 45 % when the HRT was 6 h, in addition with TN removal of nearly 100 %. The optimal phosphorus removal in the SLAD biofilter was around 60 %. For the synthetic wastewater containing a PO₄ ^3?-P concentration of 15 mg L^?1, the main mechanism of phosphorus removal was the formation of calcium phosphate precipitates.     

Regenerative Thermal Oxidation of Airborne N,N-Dimethylformamide and Its Associated Nitrogen Oxides Formation Characteristics

Abstract

In this study, a two-bed electrically heated regenerative thermal oxidizer (RTO) was used to test the thermal destruction and oxides of nitrogen (NO_x) formation characteristics in burning airstreams that contain either N, N-dimethylformamide or dimethylformamide (DMF) mixed with methyl ethyl ketone (MEK). The RTO contained two 0.152 m × 0.14 m × 1 m (L × W times] H) beds, both packed with gravel particles with an average diameter of approximately 0.0111 m and a height of up to 1 m with a void fraction of 0.42 in the packed section. The thermal recovery efficiency (TRE) and the gas pressure drop over the beds were also studied. Experimental results reveal that, with a valve shifting time (t _s) of 1.5 min, a superficial gas velocity (U _g) of 0.39 m/sec (evaluated at an influent air temperature of around 30 °C) and preset maximum destruction temperatures (T _S) of 750–950 °C, no NO_x was present in the effluent gas from the RTO when it was loaded with DMF-free air. When only DMF was present in the influent air, the average destruction efficiencies exceeded 96%, and increased with the influent DMF concentration from 300 to 750 mg/N?m³. The “NO_x-N formation/DMF-N destruction” mass ratios were in the range 0.76–1.05, and decreased as the influent DMF concentration increased within the experimental range. When both DMF and MEK were present in the influent gas, the NO_x formation ratio was almost the same and the DMF destruction efficiency increased with the influent MEK/DMF ratio from 150/300 to 4500/300 (mg/mg) and in the preset temperature range. The NO_x formation ratios were in the range 0.75–0.96. The TRE decreased as U _g increased but was invariant with T _s. The Ergun equation was found to suffice in the estimation of the pressure drop when the gas flowed over the packing beds.     

Biotrickling filtration of airborne styrene: A comparison of filtration media

This study compares the performances of fern and plastic chips as packing media for the biofiltration of a styrene-laden waste gas stream emitted in a plant for the manufacture of plastic door plates. Fern chips (with a specific surface area of 1090 m² m^?3) and plastic chips (with a specific surface area of 610 m² m^?3) were packed into a pilot-scale biotrickling filter with a total medium volume of 50 L for the performance test. Field waste gas with styrene concentrations in the range of 161–2390 mg Am^?3 at 28–30 °C) was introduced to the bed and a fixed empty-bed retention time (EBRT) of 21 sec, a volumetric gas flow rate of 8.57 m³ hr^?1, and superficial gas velocity of 53.6 m hr^?1 were maintained throughout the experimental period. Nutrients containing metal salts, nitrogen, phosphorus, and milk were supplemented to the filters for maintaining the microbial activities. Results reveal that the biotrickling filter developed in this study had the highest styrene monomer (SM) elimination capacities (170 g m^?3 hr^?1 for fern-chip packing and 300 g m^?3 hr^?1 for plastic-chip packing) among those cited in the literature. The plastic medium is a favorable substitute for endangered fern chips. The thermal-setting nature of plastic chips limits their recycle and reuse as raw materials, and the study provides an opportunity for the utilization of the materials.

Implications: Biotreatment of contaminants in air streams offers an inexpensive and efficient alternative to conventional technologies. Biofiltration has a great potential for the degradation of gas-borne styrene and total hydrocarbon (THC) removal efficiency of around 80%. The objective of this research was to compare the performances of fern chips and a kind of plastic chips as packing media for biofiltration of the styrene-laden waste gas stream emitted from cutting operations of stripes of premixed unsaturated polyester (UP) and styrene paste before hot-pressing operations for making plastic door plates. From a practical point of view, the plastic medium can be a good substitute medium for fern chips, which has been declared as a protected plant. This study provides an experimentally verified model for the design and operation of such biotreatment systems.     

The Adsorptive Capacity of Vapor-Phase Mercury Chloride onto Powdered Activated Carbon Derived from Waste Tires

Abstract

Injection of powdered activated carbon (PAC) upstream of particulate removal devices (such as electrostatic precipitator and baghouses) has been used effectively to remove hazardous air pollutants, particularly mercury-containing pollutants, emitted from combustors and incinerators. Compared with commercial PACs (CPACs), an alternative PAC derived from waste tires (WPAC) was prepared for this study. The equilibrium adsorptive capacity of mercury chloride (HgCl₂) vapor onto the WPAC was further evaluated with a self-designed bench-scale adsorption column system. The adsorption temperatures investigated in the adsorption column were controlled at 25 and 150 °C. The superficial velocity and residence time of the flow were 0.01 m/sec and 4 sec, respectively. The adsorption column tests were run under nitrogen gas flow. Experimental results showed that WPAC with higher Brunauer–Emmett–Teller (BET) surface area could adsorb more HgCl₂ at room temperature. The equilibrium adsorptive capacity of HgCl₂ for WPAC measured in this study was 1.49 × 10^?1 mg HgCl₂/g PAC at 25 °C with an initial HgCl₂ concentration of 25 μg/m³. With the increase of adsorption temperature ≤150 °C, the equilibrium adsorptive capacity of HgCl₂ for WPAC was decreased to 1.×34 10^?1 mg HgCl₂/g PA≤C. Furthermore,WPAC with higher sulfur contents could adsorb even more HgCl₂ because of the reactions between sulfur and Hg²⁺ at 150 °C. It was demonstrated that the mechanisms for adsorbing HgCl₂ onto WPAC were physical adsorption and chemisorption at 25 and 150 °C, respectively. Experimental results also indicated that the apparent overall driving force model appeared to have the good correlation with correlation coefficients (r) >0.998 for HgCl₂ adsorption at 25 and 150 °C. Moreover, the equilibrium adsorptive capacity of HgCl₂ for virgin WPAC was similar to that for CPAC at 25 °C, whereas it was slightly higher for sulfurized WPAC than for CPAC at 150 °C.     

Treatment of ethylether in air stream by a biotrickling filter packed with slags.

This paper reports results of studies using a biotrickling filter with blast-furnace slag packings (sizes = 2-4 cm and specific surface area = 120 m2/m3) for treatment of ethylether in air stream. Effects of volumetric loading, superficial gas velocity, empty bed gas retention time, recirculation liquid flow rate, and biofilm renewal on the ethylether removal efficiency and elimination capacity were tested. Results indicate that ethylether removal efficieincies of more than 95% were obtained with an empty bed retention time (EBRT) of 113 sec and loadings of lower than 70 g/m3/hr. At an EBRT of 57 sec, removal efficiencies of more than 90% could only be obtained with loadings of lower than 35 g/m3/hr. The maximum elimination capacities were 71 and 45 g/m3/hr for EBRT = 113 and 57 sec, respectively. The maximum ethylether elimination capacities were 71 and 96 g/m3/hr, respectively, before and after the renewal at EBRT = 113 sec. With an EBRT of 113 sec and a loading of lower than 38 g/m3/hr, the removal efficiency was nearly independent of the superficial liquid recirculation velocity in the range of 3.6 to 9.6 m3/m2/hr. From data regression, simplified masstransfer limited, and reaction- and mass-transfer limited models correlating the contaminant concentration and the packing height were proposed and verified. The former model is applicable for cases of low influent contaminant concentrations or loadings, and the latter is applicable for cases of higher ones. Finally, CO2 conversion efficiencies of approximately 90% for the influent ethylether were obtained. The value is comparable to data reported from other related studies.     

Modeling landfill gas potential and potential energy recovery from Thohoyandou landfill site,South Africa

ABSTRACT

The increase in solid waste generation has been a major contributor to the amount of Greenhouse gases (GHGs) present in the atmosphere. To some extent, a great chunk of these GHGs in the atmosphere is from landfill. This study assesses two theoretical models (LandGEM and Afvalzorg models) to estimate the amount of landfill gas (LFG) emitted from Thohoyandou landfill site. Also, the LFGcost Web model was used to estimate the cost and benefits of the implementation of an LFG utilization technology. The Thohoyandou landfill started operations in the year 2005 and it is proposed to reach its peak at approximately in the year 2026. The LandGEM calculates the mass of landfill gas emission using methane generation capacity, mass of deposited waste, methane generation constant and methane generation rate. Meanwhile, the Afvalzorg model determines the LFG emissions using the Methane correction factor, yearly waste mass disposal, waste composition, Degradation Organic Carbon, methane generation rate constant, LFG recovery efficiency. The study findings indicate that the methane (CH₄) and carbon dioxide (CO₂) emitted from the landfill estimated from LandGEM will peak in the year 2026 with values of 3517 Mg/year and 9649 Mg/year, respectively. Results from the Afvalzorg model show that CH₄ emission will peak in the year 2026 (3336 Mg/year). The LandGEM model showed that the total LFG, CH₄ and CO₂ emitted from the landfill between 2005 and 2040 are 293239.3 Mg/year, 78325.7 Mg/year and 214908.6 Mg/year, respectively. The simulation from the Afvalzorg model found that the CH₄ emitted from the years 2005– 2040 is 74302 Mg/year. The implementation of an LFG utilization technology was economically feasible from consideration of the sales of electricity generated and Certified Emission Reductions (CER) (carbon credits).     

Methane biofiltration in the presence of ethanol vapor under steady and transient state conditions: an experimental study

Methane (CH₄) removal in the presence of ethanol vapors was performed by a stone-based bed and a hybrid packing biofilter in parallel. In the absence of ethanol, a methane removal efficiency of 55 ± 1% was obtained for both biofilters under similar CH₄ inlet load (IL) of 13 ± 0.5 g_CH4 m^?3 h^?1 and an empty bed residence time (EBRT) of 6 min. The results proved the key role of the bottom section in both biofilters for simultaneous removal of CH₄ and ethanol. Ethanol vapor was completely eliminated in the bottom sections for an ethanol IL variation between 1 and 11 g_ethanol m^?3 h^?1. Ethanol absorption and accumulation in the biofilm phase as well as ethanol conversion to CO₂ contributed to ethanol removal efficiency of 100%. In the presence of ethanol vapor, CO₂ productions in the bottom section increased almost fourfold in both biofilters. The ethanol concentration in the leachate of the biofilter exceeding 2200 g_ethanol m^?3 _leachate in both biofilters demonstrated the excess accumulation of ethanol in the biofilm phase. The biofilters responded quickly to an ethanol shock load followed by a starvation with 20% decrease of their performance. The return to normal operations in both biofilters after the transient conditions took less than 5 days. Unlike the hybrid packing biofilter, excess pressure drop (up to 1.9 cmH₂O m^?1) was an important concern for the stone bed biofilter. The biomass accumulation in the bottom section of the stone bed biofilter contributed to 80% of the total pressure drop. However, the 14-day starvation reduced the pressure drop to 0.25 cmH₂O m^?1.     

Sensitivity of Native Desert Vegetation To SO2 and to SO2 and NO2 Combined

Interest in air pollution injury to native vegetation has been generated with the construction and planned construction of large coal-fired power plants near the coal reserves in the southwest desert areas of the United States. Since information on the effects of SO₂ on these native species was not available in the literature, fumigation studies were conducted with portable chambers placed over native species in the field with SO₂ and SO₂ + NO₂. Pollutant concentrations were measured and controlled with instruments located in a mobile laboratory. Each fumigation was of two hours duration and the concentration ranged from 0.5 to 11 ppm SO₂ and from 0.1 to 5 ppm NO₂. Concentrations of SO₂ above 2 ppm were required to cause injury to all but a few of the 87 species studied. Many of the native desert species proved to be highly resistant to injury from these gases.     

Effect of ozonation on the biodegradability of atrazine in GAC columns

Abstract

The biodegradation of atrazine as influenced by preozonation was studied in biological GAC columns. Metabolism of isopropyl‐¹⁴C atrazine produced more ¹⁴CO₂ than ring‐UL‐¹⁴C atrazine, indicating dealkylation was more rapid than ring cleavage. Preozonation increased mineralization of ring‐UL‐¹⁴C atrazine and, consequently, enhanced the performance of the GAC columns. Sixty‐two percent of the influent atrazine was converted to ¹⁴CO₂ in columns that received ozonated atrazine and ozonated surface water, while 50% of the influent atrazine was converted to ¹⁴CO₂ in columns that received untreated atrazine and ozonated surface water, and only 38% of the influent atrazine was converted to ¹⁴CO₂ in columns with untreated influent.     

Potential interferences in photolytic nitrogen dioxide converters for ambient air monitoring: Evaluation of a prototype

ABSTRACT

Mixing ratios of the criteria air contaminant nitrogen dioxide (NO₂) are commonly quantified by reduction to nitric oxide (NO) using a photolytic converter followed by NO-O₃ chemiluminescence (CL). In this work, the performance of a photolytic NO₂ converter prototype originally designed for continuous emission monitoring and emitting light at 395 nm was evaluated. Mixing ratios of NO₂ and NO_x (= NO + NO₂) entering and exiting the converter were monitored by blue diode laser cavity ring-down spectroscopy (CRDS). The NO₂ photolysis frequency was determined by measuring the rate of conversion to NO as a function of converter residence time and found to be 4.2 s^?1. A maximum 96% conversion of NO₂ to NO over a large dynamic range was achieved at a residence time of (1.5 ± 0.3) s, independent of relative humidity. Interferences from odd nitrogen (NO_y) species such as peroxyacyl nitrates (PAN; RC(O)O₂NO₂), alkyl nitrates (AN; RONO₂), nitrous acid (HONO), and nitric acid (HNO₃) were evaluated by operating the prototype converter outside its optimum operating range (i.e., at higher pressure and longer residence time) for easier quantification of interferences. Four mechanisms that generate artifacts and interferences were identified as follows: direct photolysis, foremost of HONO at a rate constant of 6% that of NO₂; thermal decomposition, primarily of PAN; surface promoted photochemistry; and secondary chemistry in the connecting tubing. These interferences are likely present to a certain degree in all photolytic converters currently in use but are rarely evaluated or reported. Recommendations for improved performance of photolytic converters include operating at lower cell pressure and higher flow rates, thermal management that ideally results in a match of photolysis cell temperature with ambient conditions, and minimization of connecting tubing length. When properly implemented, these interferences can be made negligibly small when measuring NO₂ in ambient air.

Implications: A new near-UV photolytic converter for measurement of the criteria pollutant nitrogen dioxide (NO₂) in ambient air by CL was characterized. Four mechanisms that generate interferences were identified and investigated experimentally: direct photolysis of HONO which occurred at a rate constant 6% that of NO₂, thermal decomposition of PAN and N₂O₅, surface promoted chemistry involving HNO₃, and secondary chemistry involving NO in the tubing connecting the converter and CL analyzer. These interferences are predicted to occur in all NO₂ P-CL systems but can be avoided by appropriate thermal management and operating at high flow rates.     

Manganese-cerium oxide (MnOx-CeO2) catalysts supported by titanium-bearing blast furnace slag for selective catalytic reduction of nitric oxide with ammonia at low temperature

A series of manganese-cerium oxide (MnO_x-CeO₂) catalysts supported by Ti-bearing blast furnace slag were prepared by wet impregnation and used for low-temperature selective catalytic reduction (SCR) of NO with NH₃. The slag-based catalyst exhibited high nitrogen oxide removal (deNO_x) activity and wide effective temperature range. Under the condition of NO = 500 ppm, NH₃ = 500 ppm, O₂ = 7–8 vol%, and total flow rate = 1600 mL/min, the Mn-Ce/Slag catalyst exhibited a NO conversion higher than 95% in the range of 180–260 °C. The activity of Mn/Slag catalysts was greatly enhanced with the addition of CeO₂. The results indicated that Ti-bearing blast furnace slag had suitable phase composition as good support of SCR catalyst.

Implications: Ti-bearing blast furnace slag is a kind of industrial waste in China. Much slag was underused and piling up, which could cause many environmental issues, such as enormous waste of titanium and groundwater and soil contamination by heavy metals in leachates. The utilization of slag as the support of SCR catalyst will not only make use of solid waste but also cut down the NO_x emitted from power plant.