Real-time, ultrasensitive monitoring of air toxics by laser photoionization time-of-flight mass spectrometry

Gas phase concentrations of individual polycyclic aromatic hydrocarbons (PAHs) were measured in real time in combustion products from a co-flow diffusion flame using laser photoionization (LP) time-of-flight mass spectrometry (TOF/MS). In particular, a naphthalene detection sensitivity of 4 parts per billion (ppb) was demonstrated. The use of calibration mixtures with argon indicated the feasibility of naphthalene detection at about 45 parts per trillion (ppt) at a signal-to-noise (S/N) ratio of 20. This suggests the possibility of low-ppt level detection at a S/N of 1. The novelty of the system is the use of a heated sampling probe and a continuously purged, heated-pulse valve that was positioned close to the ionization zone, thereby allowing the generation of photoions in the high-density region of the sample jet, where concentrations of PAH are high. Because the system developed allows for the real time detection of select species, it represents a useful tool in continuous emissions monitoring (CEM) for environmental compliance as well as direct process control.     

Determination of Ozone in Outdoor and Indoor Environments Using Nitrite-Impregnated Passive Samplers Followed by Ion Chromatography

Abstract

An improved ion chromatographic (IC) method has been developed for the separation of nitrate in filter extracts in the presence of high concentrations of nitrite. This analytical method was successfully used for an indirect measurement of ozone (O₃) in outdoor and indoor air, following its collection using a nitrite-impregnated passive sampler. The limit of detection and the limit of quantification, using the modified IC method, were 6 μg l^-1 (3σ) and 20 μg l^-1 (10σ), respectively. Improved detection limits and low baseline noise were obtained with the use of eluent generator and high-capacity ion exchange column. The optimized method was used for assessing O₃ concentration in both indoor and outdoor environments of 28 child care centers (CCCs) located in different parts of Singapore. The O₃ concentrations ranged from 0.1 to 11.95 parts per billion (ppb) in indoor and from 3.2 to 21.7 ppb in outdoor environments during the study period. It was found that, among the CCCs investigated in this study, air-conditioned CCCs and those located in close proximity to traffic emissions had significantly lower O₃ concentrations indoors.     

Ambient measurements of 2,2,4-trimethyl, 1,3-pentanediol monoisobutyrate in Southern California

2,2,4-trimethyl, 1,3-pentanediol monoisobutyrate (TPM) is a widely used solvent found in water-based coatings. Ambient measurements of TPM are reported here for the first time. Although this compound has been previously measured in indoor air, this study illustrates successful detection and quantification of TPM in ambient air at three locations in Southern California: Pico Rivera, Azusa, and Riverside. TPM was detected in every sample collected, with concentrations ranging from 0.7 to 49.5 parts per trillion (ppt). Collections took place during summer 2009, fall 2009, winter 2009/2010, and spring 2010, for 5–7 days during each season. The highest mean concentrations were observed during the summer months for each city, when coating activities are typically at their highest.

Implications 2,2,4-Trimethyl, 1,3-pentanediol monoisobutyrate (TPM) is a widely used solvent found in water-based coatings. Ambient measurements of TPM are reported here for the first time. The highest mean concentrations were observed during the summer months for each city, when coating activities are typically at their highest. Unreacted TPM constitutes approximately 0.01% of the total nonmethane hydrocarbon (NMHC) concentrations in the Los Angeles air basin and given its slow reactivity rate in forming ozone, this would be an approximate upper limit for the fraction of ozone that it is responsible for forming.     

Continuous Emissions Monitoring Using Spark-Induced Breakdown Spectroscopy

ABSTRACT

A new technology for monitoring airborne heavy metals on aerosols and particulates based on spark-induced breakdown spectroscopy (SIBS) was evaluated at a joint U.S. Environmental Protection Agency (EPA)/U.S. Department of Energy test at the rotary kiln incinerator simulator (RKIS) facility at EPA/Research Triangle Park, NC, in September 1997. The instrument was configured to measure lead and chromium in a simulated combustion flue gas in real time and in situ at target levels of 15 and 75 u, g/dry standard cubic meters. Actual metal concentrations were measured during the tests using EPA Reference Method (RM) 29.

The SIBS technology detected both lead and chromium at the low- and high-level concentrations. Additionally, the hardware performed without failure for more than 100 hr of operation and acquired data for 100% of the RM tests. The chromium data were well correlated with concentration increases resulting from duct operations and pressure fluctuations that are known to entrain dust.     

Investigation of the Treatability of the Primary Indoor Volatile Organic Compounds on Activated Carbon Fiber Cloths at Typical Indoor Concentrations

Abstract

Volatile organic compounds (VOCs) are a major concern for indoor air pollution because of the impacts on human health. In recent years, interest has increased in the development and design of activated carbon filters for removing VOCs from indoor air. Although extensive information is available on sources, concentrations, and types of indoor VOCs, there is little or no information on the performance of indoor air adsorption systems for removing low concentrations of primary VOCs. Filter designs need to consider various factors such as empty bed contact time, humidity effects, competitive adsorption, and feed concentration variations, whereas adsorption capacities of the indoor VOCs at the indoor concentration levels are important parameters for filter design. A preliminary assessment of the feasibility of using adsorption filters to remove low concentrations of primary VOCs can be performed. This work relates the information (including VOC classes in indoor air, the typical indoor concentrations, and the adsorption isotherms) with the design of a particular adsorbent/adsorbates system. As groundwork for filter design and development, this study selects the primary VOCs in indoor air of residences, schools, and offices in different geographical areas (North America, Europe, and Asia) on the basis of occurrence, concentrations, and health effects. Activated carbon fiber cloths (ACFCs) are chosen as the adsorbents of interest. It is demonstrated that the isotherm of a VOC (e.g., toluene on the ACFC) at typical indoor concentrations—parts per billion by volume (ppbv) level—is different than the isotherm at parts per million by volume (ppmv) levels reported in the publications. The isotherms at the typical indoor concentrations for the selected primary VOCs are estimated using the Dubinin–Radushkevitch equation. The maximum specific throughput for an indoor VOC removal system to remove benzene is calculated as a worst-case scenario. It is shown that VOC adsorption capacity is an important indicator of a filter’s lifetime and needs to be studied at the appropriate concentration range. Future work requires better understanding of the realistic VOC concentrations and isotherms in indoor environments to efficiently utilize adsorbents.     

Swine wastewater treatment in a two stage sequencing batch reactor using real‐time control

Abstract

A laboratory scale two‐stage sequencing batch reactor (TSSBR) was used to study the effectiveness of pH as a real‐time control parameter in swine wastewater treatment. A Ringlace media was inserted into the A/O (Anoxic/Oxic) reactor for bacteria immobilization. The TSSBR was subjected to three levels of organic loading. The pH and ORP (Oxidation Reduction Potential) patterns obtained were consistent with distinct features, enabling the real‐time control strategy to effectively set a flexible aeration time pending on influent concentration, hence resulting in flexible cycle time and HRT (Hydraulic Retention Time) for the system. The real‐time process ensured a removal efficiency of over 99% and 95%, respectively, for ammonia and TOC (Total Organic Carbon). For NO₃ ^‐‐N and PO₄ ^‐3, the run with influent TOC = 4,000 mg/L yielded the most efficient removal of 61% and 95%, respectively. Test results suggest that pH can be a viable tool for on‐line real‐time control of a biological treatment process.     

In Situ Determination of the Rate of Unassisted Degradation of Saturated-Zone Hydrocarbon Contamination

Abstract

A method to measure the in situ degradation rate of dissolved hydrocarbon contamination has been developed and applied at two locations at a field site. The method uses the rates of downward diffusion of oxygen and upward diffusion of carbon dioxide through the unsaturated zone, as calculated from vertical soil-gas concentration gradients, combined with stoichiometry to obtain two degradation rates in hydrocarbon mass per water table surface area per time. Values of 0.385 gram per m² per day and 0.52 gram per m² per day (based upon oxygen data) and 0.056 gram per m² per day and 0.12 gram per m² per day (based upon carbon dioxide data) were calculated at a field site with dissolved fuel contamination. This result of lower values from ground-air carbon dioxide concentrations is consistent with a significant fraction of the carbon dioxide produced being lost to the aqueous phase. Based upon a single-stage equilibrium phase-transfer model, gas/water volume ratios of 0.02 and 0.2 for the capillary fringe were calculated. Groundwater carbon dioxide fugacities and soil-gas carbon dioxide concentrations were used at the two locations and a third to determine whether the source of elevated soil carbon dioxide concentrations were unsaturated-zone hydrocarbon degradation or a saturated-zone process. This technique has potential applicability in setting risk-based remedial criteria and in allowing inclusion of the contribution of in situ degradation in remedial design. This can result in major remedial cost savings.     

Abbauverhalten von triadimefon und seinem metaboliten triadimenol in einer weizenmonokultur

Summary

In a 4‐year study, the behaviour of the residues of triadimefon and its metabolite triadimenol in different plant parts of winter wheat and in soil was investigated. The fungicide Bayleton DF (triadimefon + captafol) was applied at the beginning of earing. Triadimefon residues were quickly degraded in the great majority of the examined samples (more than 90% within the first 2 weeks after application in all aerial parts of the plant). Triadimenol residues were considerably more persistent. No residues either of triadimefon or triadimenol were found in grain at harvest time (detection limit 0.01 mg/kg).     

Predicting Extents of Mercury Oxidation in Coal-Derived Flue Gases

Abstract

The proposed mercury (Hg) oxidation mechanism consists of a 168-step gas phase mechanism that accounts for interaction among all important flue gas species and a heterogeneous oxidation mechanism on unburned carbon (UBC) particles, similar to established chemistry for dioxin production under comparable conditions. The mechanism was incorporated into a gas cleaning system simulator to predict the proportions of elemental and oxidized Hg species in the flue gases, given relevant coal properties (C/H/O/N/S/Cl/Hg), flue gas composition (O₂, H₂O, HCl), emissions (NO_X, SO_X, CO), the recovery of fly ash, fly ash loss-on-ignition (LOI), and a thermal history. Predictions are validated without parameter adjustments against datasets from lab-scale and from pilot-scale coal furnaces at 1 and 29 MW_t. Collectively, the evaluations cover 16 coals representing ranks from sub-bituminous through high-volatile bituminous, including cases with Cl₂ and CaCl₂ injection. The predictions are, therefore, validated over virtually the entire domain of Cl-species concentrations and UBC levels of commercial interest. Additional predictions identify the most important operating conditions in the furnace and gas cleaning system, including stoichiometric ratio, NO_X, LOI, and residence time, as well as the most important coal properties, including coal-Cl.     

Carbonyl Sulfide Removal with Compost and Wood Chip Biofilters,and in the Presence of Hydrogen Sulfide

Abstract

Carbonyl sulfide (COS) is an odor-causing compound and hazardous air pollutant emitted frequently from wastewater treatment facilities and chemical and primary metals industries. This study examined the effectiveness of biofiltration in removing COS. Specific objectives were to compare COS removal efficiency for various biofilter media; to determine whether hydrogen sulfide (H₂S), which is frequently produced along with COS under anaerobic conditions, adversely impacts COS removal; and to determine the maximum elimination capacity of COS for use in biofilter design. Three laboratory-scale polyvinyl chlo-ride biofilter columns were filled with up to 28 in. of biofilter media (aged compost, fresh compost, wood chips, or a compost/wood chip mixture). Inlet COS ranged from 5 to 46 parts per million (ppm) (0.10–9.0 g/m³fihr). Compost and the compost/wood chip mixture produced higher COS removal efficiencies than wood chips alone. The compost and compost/wood chip mixture had a shorter stabilization times compared with wood chips alone. Fresh versus aged compost did not impact COS removal efficiency. The presence of H₂S did not adversely impact COS removal for the concentration ratios tested. The maximum elimination capacity is at least 9 g/m³·hr for COS with compost media.     

Environmental Issues—Persistent Problems and Emerging Challenges

Abstract

A field study was performed to evaluate indoor air concentrations and vapor intrusion (VI) of tetrachloroethylene (PCE) and other chlorinated solvents at a commercial retail site in Dallas, TX. The building is approximately 40 yr old and once housed a dry cleaning operation. Results from an initial site characterization were used to select sampling locations for the VI study. The general approach for evaluating VI was to collect time-integrated canister samples for off-site U.S. Environmental Protection Agency Method TO-15 analyses. PCE and other chlorinated solvents were measured in shallow soil gas, subslab soil-gas, indoor air, and ambient air. The subslab soil gas exhibited relatively high values: PCE ≤2,600,000 parts per billion by volume (ppbv) and trichloroethylene ≤170 ppbv. The attenuation factor, the ratio of indoor air and subslab soil-gas concentrations, was unusually low: approximately 5 x 10^-6 based on the maximum subslab soil-gas concentration of PCE and 1.4 x 10^-5 based on average values.     

Metal Oxides Remove Hydrogen Sulfide from Landfill Gas Produced from Waste Mixed with Plaster Board under Wet Conditions

Abstract

Hydrogen sulfide (H₂S) is a major odorant in landfills. We have studied H₂S production from landfill residual waste with and without sulfur-containing plaster board, including the influence of the water content in the waste. The laboratory experiments were conducted in 30-L polyethylene containers with a controlled water level. We also studied how different materials removed H₂S in reactive layers on top of the waste. The organic waste produced H₂S in concentrations of up to 40 parts per million (ppm) over a period of 80 days. When plaster board was added, the H₂S concentration increased to 800 ppm after a lag period of approximately 40 days with a high water level, and to approximately 100 ppm after 50 days with a low water level. The methane (CH₄) concentration in the initial experiment was between 5 and 70% after 80 days. The CH₄ concentration in the second experiment increased to nearly 70% in the container with a high water level, slowly declining to approximately 60% between days 20 and 60. The CH₄ concentrations during the experiments resembled normal landfill concentrations. Metallic filter materials were very efficient in removing H₂S, whereas organic filter materials showed poor H₂S removal.     

Influence of additives in the end‐use mixes of tebufenozide on deposition,adhesion and persistence in spruce foliage

Abstract

A commercial flowable formulation of tebufenozide, RH‐5992 2F [N'‐t‐butyl‐N'‐(3,5‐dimethylbenzoyl)‐N‐(4‐ethylbenzoyl) hydrazine], was diluted with water, water and canola oil, and water and the methyl ester of canola oil, to provide six end‐use mixes with concentrations of 35 and 70 g of active ingredient (Al) litre^‐1. The mixes were applied at 70 and 140 g Al ha^‐1 over white spruce [Picea glauca (Moench) Voss] seedlings in a laboratory spray chamber and foliar concentrations of tebufenozide were determined over a 60‐d period. At intervals of time post‐spray, seedlings were sprayed with monosized droplets of Sunspray®11N as rainfall, and the amount of tebufenozide knocked off from foliage was determined. The potential energy of adhesion (PEA) of the Al particles on the foliage increased with time and varied according to the type of end‐use mix, its viscosity and the dosage sprayed.

The end‐use mixes were applied over white spruce trees under field conditions and persistence of tebufenozide was investigated. DT₅₀ values were influenced by the type of mix and dosage sprayed. Oil‐containing mixes and higher dosages increased the PEA of tebufenozide particles.     

Consultant Guide/1987

ABSTRACT

This study considers the characteristics of ground-level ozone (O₃) in five Korean cities over a time period of 6-8 years. The focus of this study is daily maximum 1-hr and 8-hr concentrations. For all the study cities in the period examined, the mean and most of the percentiles (5, 10, 25, 50, 75, 90, and 95) for the daily maximum 1-hr and 8hr concentrations showed increasing trends, although not all trends were statistically significant. The daily maximum 1-hr and 8-hr concentrations slowly increased during late winter, and peaks were attained during the summer season (from May to September). All the selected cities exhibited a high degree of correlation between their daily maximum 8-hr and 1-hr concentrations. The daily maximum 8-hr concentrations, which were climatologi-cally equivalent to the Korean 1 hr/100 parts per billion (ppb) standard, were higher than the current 8 hr/60 ppb by a difference of 8-16 ppb. Compared with other cities in Korea, Seoul recorded a substantially higher frequency of days and hours with concentrations above 1 hr/100 ppb, and a higher frequency of days with concentrations above 8 hr/60 ppb and 8 hr/80 ppb. Seoul also recorded a substantially higher frequency of hours with concentrations above 1 hr/100 ppb than days with concentrations above 1 hr/100 ppb, implying that on some days severe exceedances persisted for more than one hour per day. During multiple-day episodes a North Pacific High dominated Korea, which is quite typical in Korea during the summer season.     

Ozone Decay Rates in Residences

ABSTRACT

In urban and suburban settings, indoor ozone exposures can represent a significant fraction of an individual's total exposure. The decay rate, one of the factors determining indoor ozone concentrations, is inadequately understood in residences. Decay rates were calculated by introducing outdoor air containing 80-160 parts per billion ozone into 43 residences and monitoring the reduction in indoor concentration as a function of time. The mean decay rate measured in the living rooms of 43 Southern California homes was 2.80 + 1.30 hr^-1, with an average ozone deposition velocity of 0.049 + 0.017 cm/sec. The experimental protocol was evaluated for precision by repeating measurements in one residence on five different days, collecting 44 same-day replicate measurements, and by simultaneous measurements at two locations in six homes. Measured decay rates were significantly correlated with house type and the number of bedrooms. The observed decay rates were higher in multiple-family homes and homes with fewer than three bedrooms. Homes with higher surface-area-to-volume ratios had higher decay rates. The ratio of indoor-to-outdoor ozone concentrations in homes not using air conditioning and open windows was 68 + 18%, while the ratio of indoor-to-outdoor ozone was less than 10% for the homes with air conditioning in use.     

Biofiltration of Cyclic Air Emissions of [H9251]-Pinene at Low and High Frequencies

Abstract

Biofiltration of periodically fluctuating concentrations of an α-pinene-laden waste gas was investigated to treat both high-frequency and low-frequency fluctuations. The effects of periodic concentration fluctuations on biofilter performance were measured. Controlled variables of periodic operation included cycle period and amplitude. The cycle period ranged from 10 min to 6 days, with the inlet α-pinene concentration fluctuating between 0 and 100 parts per million volume. At high-frequency concentration cycling (i.e., on the order of minutes), both cyclic and constant concentration biofilters maintained similar long-term performance with an average removal efficiency of 77% at an averaged loading rate of 29 g α-pinene/m³ bed/hr. A first approximation suggests kinetics that are time-independent, indicating that steady-state data can be used to predict transient behavior at this time scale. Cyclic biofilter operation with a cycle period of 24 hr (with equal on/off time) was achievable for biofilters without a significant loss in performance. At longer time scales, cyclic biofilter performance decreased at the restart of the ON cycle. The recovery time to previous levels of performance increased with increasing cycle period; the recovery time was less than 1 hr for a cycle period of 24 hr and between 6 and 8 hr for a cycle period of 6 days.     

Summary of efficacy evaluations using aerially applied Gypchek® against gypsy moth in the U.S.A.

Abstract

Gypchek^®, the gypsy moth (Lymantria dispar L.) nucleopolyhedrosis virus product, is manufactured by the United States Department of Agriculture (USDA) Forest Service, and Animal and Plant Health Inspection Service under controlled conditions in a laboratory strain of gypsy moth larvae. Gypchek was registered with the U.S. Environmental Protection Agency in 1978 as a general use pesticide to control gypsy moth. This product has been the subject of intense research and development targeted toward maximizing efficacy while minimizing the cost of production and application. The current Gypchek tank mix is applied at 1.25 × 10¹²occlusion bodies (OB's) per hectare for each of two applications (3‐days apart) at 18.7 litres/ha per application.     

Development of a High-Speed Ultraviolet Spectrometer for Remote Sensing of Mobile Source Nitric Oxide Emissions

ABSTRACT

The University of Denver (DU) has developed a new remote sensor for the measurement of mobile source nitric oxide (NO). This system is integrated with an existing infrared remote sensor and is capable of measuring carbon monoxide and hydrocarbons in addition to NO, at a rate of more than 1000 vehicles/hr. The detection limit on a low-emitting vehicle under typical measurement conditions is 24 parts per million NO (3σ). Measurements from this instrument correlated well in a side-by-side comparison with the previous NO remote sensor developed at DU, and we have used this study to confirm a suspected interference by aromatic hydrocarbons in the older instrument. The results of an extended field experiment using the new instrument, conducted in fall 1997, are also presented. The NO emissions of the fleet measured in this study (averaging 15.0 g NO/gal) exhibit a skewed distribution typical of mobile sources. This paper also describes the relationship between NO emissions and model year and NO emissions and vehicle acceleration, as measured by the new remote sensor.     

Effect of Monosodium Methanarsonate Application on Cuticle Wax Content of Cocklebur and Cotton Plants

Leaf cuticle waxes were extracted from monosodium methanearsonate (MSMA)-resistant (R) and -susceptible (S) common cocklebur (Xanthium strumarium L.) and cotton (Gossypium hirsutum L.) plants at 0, 3, 5, and 7 days after treatment (DAT) following 1× and 2× MSMA applications. Wax constituents were analyzed by gas chromatography (GC) with flame ionization detection and compared to alkane and alcohol standards of carbon lengths varying from C21 to C30. Differences in waxes were calculated and reported as change per ng mm^2–1. Tricosane (C23) was found to increase following MSMA applications. All other alkanes decreased by 7 DAT, with some showing a linear effect over time in the R-cocklebur. Alcohol constituents were also observed to decrease by 7 DAT. Total arsenic in the extracted wax fraction was determined, with greatest quantities detected in the R-cocklebur. Wax changes are not believed to play a role in cotton tolerance, since changes in cuticle concentrations were minimal. Cocklebur resistance to MSMA is not due to cuticle constituents; the wax changes are a secondary effect in response to herbicide application.     

Assessment of a regulatory model's performance relative to large spatial heterogeneity in observed ozone in Houston,Texas

In Houston, some of the highest measured 8-hr ozone (O₃) peaks are characterized by sudden increases in observed concentrations of at least 40 ppb in 1 hr, or 60 ppb in 2 hr. Measurements show that these large hourly changes appear at only a few monitors and span a narrow geographic area, suggesting a spatially heterogeneous field of O₃ concentrations. This study assessed whether a regulatory air quality model (AQM) can simulate this observed behavior. The AQM did not reproduce the magnitude or location of some of the highest observed hourly O₃ changes, and it also failed to capture the limited spatial extent. On days with measured large hourly changes in O₃ concentrations, the AQM predicted high O₃ over large regions of Houston, resulting in overpredictions at several monitors. This analysis shows that the model can make high O₃, but on these days the predicted spatial field suggests that the model had a different cause. Some observed large hourly changes in O₃ concentrations have been linked to random releases of industrial volatile organic compounds (VOCs). In the AQM emission inventory, there are several emission events when an industrial point source increases VOC emissions in excess of 10,000 mol/hr. One instance increased predicted downwind O₃ concentrations up to 25 ppb. These results show that the modeling system is responsive to a large VOC release, but the timing and location of the release, and meteorological conditions, are critical requirements. Attainment of the O₃ standard requires the use of observational data and AQM predictions. If the large observed hourly changes are indicative of a separate cause of high O₃, then the model may not include that cause, which might result in regulators enacting control strategies that could be ineffective.

Implications To show the attainment of the O₃ standard, the U.S. Environmental Protection Agency (EPA) requires the use of observations and model predictions under the assumption that simulations are capable of reproducing observed phenomena. The regulatory model is unable to reproduce observed behavior measured in the observational database. If the large observed hourly changes were indicative of a separate cause of high O₃, then the model would not include that cause. Inaccurate model predictions may prompt air quality regulators to enact control strategies that are effective in the modeling system, but prove ineffective in the real world.