Lingshuang Cai

Evaluation of wood chip-based biofilters to reduce odor, hydrogen sulfide, and ammonia from swine barn ventilation air.

Abstract A pilot-scale biofilter was developed in which two types of wood chips (western cedar [WC] and 2-in. hardwood [HW]) were examined to treat odor emissions from a deep-pit swine finishing facility in central Iowa. The biofilters were operated continuously for 13 weeks at different airflow rates resulting in variable empty bed residence times (EBRTs) from 1.6 to 7.3 sec. The effects of three media moisture levels were also evaluated. A dynamic forced-choice olfactometer was used to evaluate odor concentrations from both the control (inlet) plenum and biofilter treatments (outlet). Hydrogen sulfide (H2S) and ammonia (NH3) concentrations were also measured from these olfactometry samples. Solid-phase microextraction (SPME) polydimethylsiloxane (PDMS)/divinylbenzene (DVB) 65-µm fibers were used to extract volatile organic compounds from both the control plenum and biofilter treatments. Analyses of separated odors were carried out using a gas chromatography-mass spectrometry-olfactometry (GC-MS-O) system. Static sample results indicated that both types of chips achieved significant reductions in odor (average 70.1 and 82.3% for HW and WC, respectively), H2S (average 81.8 and 88.6% for HW and WC, respectively) and NH3 (average 43.4 and 74% for HW and WC, respectively) concentrations. GC-MS-O aromagram results showed both treatments reached high odor reduction efficiency (average 99.4 and 99.8% for HW and WC, respectively). The results also showed that maintaining proper moisture content and a minimum EBRT are critical to the success of wood chip-based biofilters.

Performance evaluation of a wood-chip based biofilter using solid-phase microextraction and gas chromatography–mass spectroscopy–olfactometry

A pilot-scale mobile biofilter was developed where two types of wood chips (western cedar and 2 in. hardwood) were examined to treat odor emissions from a deep-pit swine finishing facility in central Iowa. The biofilters were operated continuously for 13 weeks at different air flow rates resulting in a variable empty bed residence time (EBRT) from 1.6 to 7.3 s. During this test period, solid-phase microextraction (SPME) PDMS/DVB 65 microm fibers were used to extract volatile organic compounds (VOCs) from both the control plenum and biofilter treatments. Analyses of VOCs were carried out using a multidimentional gas chromatography-mass spectrometry-olfactometry (MDGC-MS-O) system. Results indicated that both types of chips achieved significant reductions in p-cresol, phenol, indole and skatole which represent some of the most odorous and odor-defining compounds known for swine facilities. The results also showed that maintaining proper moisture content is critical to the success of wood-chip based biofilters and that this factor is more important than media depth and residence time.

Characterization of livestock odors using steel plates, solid-phase microextraction, and multidimensional gas chromatography-mass spectrometry-olfactometry.

Abstract Livestock operations are associated with emissions of odor, gases, and particulate matter (PM). Livestock odor characterization is one of the most challenging analytical tasks. This is because odor-causing gases are often present at very low concentrations in a complex matrix of less important or irrelevant gases. The objective of this project was to develop a set of characteristic reference odors from a swine barn in Iowa and, in the process, identify compounds causing characteristic swine odor. Odor samples were collected using a novel sampling methodology consisting of clean steel plates exposed inside and around the swine barn for ≤1 week. Steel plates were then transported to the laboratory and stored in clean jars. Head-space solid-phase microextraction was used to extract characteristic odorants collected on the plates. All of the analyses were conducted on a gas chromatography-mass spectrometry-olfactometry system where the human nose is used as a detector simultaneously with chemical analysis via mass spectrometry. Multidimensional chromatography was used to isolate and identify chemicals with high-characteristic swine odor. The effects of sampling time, distance from a source, and the presence of PM on the abundance of specific gases, odor intensity, and odor character were tested. Steel plates were effectively able to collect key volatile compounds and odorants. The abundance of specific gases and odor was amplified when plates collected PM. The results of this research indicate that PM is major carrier of odor and several key swine odorants. Three odor panelists were consistent in identifying p-cresol as closely resembling characteristic swine odor, as well as attributing to p-cresol the largest odor response out of the samples. Further research is warranted to determine how the control of PM emissions from swine housing could affect odor emissions.

Odor and Odorous Chemical Emissions from Animal Buildings: Part 6. Odor Activity Value

There is a growing concern with air and odor emissions from agricultural facilities. A supplementary research project was conducted to complement the U.S. National Air Emissions Monitoring Study (NAEMS). The overall goal of the project was to establish odor and chemical emission factors for animal feeding operations. The study was conducted over a 17-month period at two freestall dairies, one swine sow farm, and one swine finisher facility. Samples from a representative exhaust airstream at each barn were collected in 10 L Tedlar bags and analyzed by trained human panelists using dynamic triangular forced-choice olfactometry. Samples were simultaneously analyzed for 20 odorous compounds (acetic acid, propanoic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, hexanoic acid, heptanoic acid, guaiacol, phenol, 4-methylphenol, 4-ethylphenol, 2-aminoacetophenone, indole, skatole, dimethyl disulfide, diethyl disulfide, dimethyl trisulfide, hydrogen sulfide, and ammonia). In this article, which is part 6 of a six-part series summarizing results of the project, we investigate the correlations between odor concentrations and odor activity value (OAV), defined as the concentration of a single compound divided by the odor threshold for that compound. The specific objectives were to determine which compounds contributed most to the overall odor emanating from swine and dairy buildings, and develop equations for predicting odor concentration based on compound OAVs. Single-compound odor thresholds (SCOT) were statistically summarized and analyzed, and OAVs were calculated for all compounds. Odor concentrations were regressed against OAV values using multivariate regression techniques. Both swine sites had four common compounds with the highest OAVs (ranked high to low: hydrogen sulfide, 4-methylphenol, butyric acid, isovaleric acid). The dairy sites had these same four compounds in common in the top five, and in addition diethyl disulfide was ranked second at one dairy site, while ammonia was ranked third at the other dairy site. Summed OAVs were not a good predictor of odor concentration (R2 = 0.16 to 0.52), underestimating actual odor concentrations by 2 to 3 times. Based on the OAV and regression analyses, we conclude that hydrogen sulfide, 4-methylphenol, isovaleric acid, ammonia, and diethyl disulfide are the most likely contributors to swine odor, while hydrogen sulfide, 4-methyl phenol, butyric acid, and isovaleric acid are the most likely contributors to dairy odors.

Improving the Biodegradation of Organic Pollutants with Ozonation during Biological Wastewater Treatment

Pre-ozonation is often used to enhance the biodegradability of recalcitrant compounds prior to biological treatment of wastewater. A usual shortcoming of such an approach is wasting ozone on other compounds that are already biodegradable. This research followed a groundbreaking approach of degrading a recalcitrant substance with ozone during biological treatment. Two parallel bench-top activated sludge processes were fed a synthetic wastewater containing typical biodegradable substances and also methylene blue at 5 mg/L. Ozone was applied continuously and directly into one of the activated sludge units at 17 mg/L based on inflow rate. The methylene blue was removed by 95% in the ozonated process compared with just 40% removal in the non-ozonated control. The removal in the activated sludge without ozonation was demonstrated to be mainly due to biosorption. The ozone oxidation reaction by-products were analyzed using GC-MS on volatile substances collected in the headspace above ozonated samples of methylene blue and most found to be biodegradable. These by-products are expected to be degraded and assimilated in the same process unit together with the other biodegradables in the feed stream by the activated sludge process. The reaction rate with organic substances depleted the dissolved ozone at such a rate that the inactivation of the treatment bacteria (and protozoa) was minimal, mostly affecting the filamentous bacteria. A concern that ozone, as a powerful disinfectant, could inhibit or kill the beneficial bacteria in the activated sludge process was proven to be incorrect.

Chemical-Sensory Characterization of Dairy Manure Odor Using Headspace Solid-Phase Microextraction and Multidimensional Gas Chromatography Mass Spectrometry-Olfactometry

Abstract Livestock operations are associated with emissions of odor, gases, and particulate matter. The majority of previous livestock odor studies focused on swine operations whereas relatively few relate to dairy cattle. Identifying the compounds responsible for the primary odor impact is a demanding analytical challenge because many critical odor components are frequently present at very low concentrations within a complex matrix of numerous insignificant volatiles. The objective of this study was to describe a chemical-sensory profile of dairy manure odor using headspace solid-phase microextraction (HS-SPME) and multidimensional gas chromatography-mass spectrometry-olfactometry (MDGC-MS-O). Two analytical approaches were used: (1) HS-SPME time-series extractions (from seconds up to 20 hr) followed by gas chromatography-mass spectrometry-olfactometry (GC-MS-O) analyses, and (2) relatively short HS-SPME extractions (30 min) followed by MDGC-MS-O analyses on selected chromatogram heart-cuts. Dairy manure was collected at research dairy farms in the United States and Israel. Volatile organic compounds (VOCs) resolved from multiple analyses included sulfur-containing compounds, volatile fatty acids, ketones, esters, and phenol/indole derivatives. A total of 86 potential odorants were identified. Of them, 17 compounds were detected by the human nose only. A greater number of VOCs and odorous compounds were detected, as well as higher mass loading, on solid-phase microextraction (SPME) fibers observed for longer extractions with SPME. However, besides sulfur-containing compounds, other selected compounds showed no apparent competition and displacement on the SPME fiber. The use of MDGC-MS-O increased chromatographic resolution even at relatively short extractions and revealed 22 additional odorants in one of the regions of the chromatogram. The two analytical approaches were found to be parallel to some extent whereas MDGC-MS-O can also be considered as a complementary approach by resolving more detailed chemical-sensory odor profiles.

Ozonation within an Activated Sludge System for Azo Dye Removal by Partial Oxidation and Biodegradation

Pre-ozonation is often uneconomical for typical wastewaters with varied mixtures of organic compounds as more biodegradables than non-biodegradables are oxidized, all requiring ozone. The concept developed in this paper is ozonation within an activated sludge system to oxidize recalcitrant substances to more degradable forms and byproducts and to immediately assimilate or biodegrade these within the biological system. The focus was on a novel method of combining ozonation and biological treatment in one integrated unit without adversely affecting the bacterial population responsible for the biological degradation. An azo dye, spiked into the wastewater feed was used to study removal of a recalcitrant compound in a biological system.

Odor and Odorous Chemical Emissions from Animal Buildings: Part 4—Correlations Between Sensory and Chemical Measurements

This study supplemented the National Air Emissions Monitoring Study (NAEMS) with one year of comprehensive measurements of odor emission at five swine and four dairy buildings. The measurements included both standard human sensory measurements using dynamic forced-choice olfactometry and chemical analysis of the odorous compounds using gas chromatography-mass spectrometry. In this article, multilinear regressions between odor and gas concentrations (a total of 20 compounds including H2S, NH3, and VOCs) were investigated. Regressions between odor and gas emission rates were also tested. It was found that gas concentrations, rather than emission rates, should be used to develop multilinear regression models. For the dairy sites, H2S, NH3, acetic acid, propanoic acid, 2-methyl propanoic, and pentanoic acids were observed to be the compounds with the most significant effect on sensory odor. For the swine sites, in addition to these gases, higher molecular weight compounds such as phenol, 4-methyl phenol, 4-ethyl phenol, and 1H-indole were also observed to be significant predictors of sensory odor. When all VOCs were excluded from the model, significant correlations between odor and H2S and NH3 concentrations were still observed. Although these coefficients of determination were lower when only H2S and NH3 were used, they can be used to predict odor variability by up to 83% when VOC data are unavailable.

Analysis of trace contaminants in hot gas streams using time-weighted average solid-phase microextraction: Proof of concept

Time-weighted average (TWA) passive sampling using solid-phase microextraction (SPME) and gas chromatography was investigated as a new method of collecting, identifying and quantifying contaminants in process gas streams. Unlike previous TWA-SPME techniques using the retracted fiber configuration (fiber within needle) to monitor ambient conditions or relatively stagnant gases, this method was developed for fast-moving process gas streams at temperatures approaching 300 °C. The goal was to develop a consistent and reliable method of analyzing low concentrations of contaminants in hot gas streams without performing time-consuming exhaustive extraction with a slipstream. This work in particular aims to quantify trace tar compounds found in a syngas stream generated from biomass gasification. This paper evaluates the concept of retracted SPME at high temperatures by testing the three essential requirements for TWA passive sampling: (1) zero-sink assumption, (2) consistent and reliable response by the sampling device to changing concentrations, and (3) equal concentrations in the bulk gas stream relative to the face of the fiber syringe opening. Results indicated the method can accurately predict gas stream concentrations at elevated temperatures. Evidence was also discovered to validate the existence of a second boundary layer within the fiber during the adsorption/absorption process. This limits the technique to operating within reasonable mass loadings and loading rates, established by appropriate sampling depths and times for concentrations of interest. A limit of quantification for the benzene model tar system was estimated at 0.02 g m(-3) (8 ppm) with a limit of detection of 0.5 mg m(-3) (200 ppb). Using the appropriate conditions, the technique was applied to a pilot-scale fluidized-bed gasifier to verify its feasibility. Results from this test were in good agreement with literature and prior pilot plant operation, indicating the new method can measure low concentrations of tar in gasification streams.

Odor and odorous chemical emissions from animal buildings: Part 2. odor emissions

This study was an add-on project to the National Air Emissions Monitoring Study (NAEMS) and focused on comprehensive measurement of odor emissions considering variations in seasons, animal types, and olfactometry laboratories. Odor emissions from four of 14 NAEMS sites with nine barns/rooms (two dairy barns at the WI5B and IN5B sites, two pig finishing rooms at IN3B, and two sow gestation barns and a farrowing room at the IA4B site) were measured during four 13-week cycles. Odor emissions were reported per barn area (OU h-1 m-2), head (OU h-1 head-1), and animal unit (OU h-1 AU-1). The highest overall odor emission rates were measured in summer (1.2 × 105 OU h-1 m-2, 3.5 × 105 OU h-1 head-1, and 6.2 × 105 OU h-1 AU-1), and the lowest rates were measured in winter (2.5 × 104 OU h-1 m-2, 9.1 × 104 OU h-1 head-1, and 1.5 × 105 OU h-1 AU-1). The highest ambient odor concentrations and barn odor emissions were measured from the sow gestation barns of the IA4B site, which had unusually high H2S concentrations. The most intense odor and the least pleasant odor were also measured at this site. The overall odor emission rates of the pig finishing rooms at IN3B were lower than the emission rates of the IA4B sow gestation barns. The lowest overall barn odor emission rates were measured at the IN5B dairy barns. However, the lowest ambient odor concentrations were measured at the ventilation inlets of the WI5B dairy barns.