Validation of atmospheric VOC measurements by proton-transfer-reaction mass spectrometry using a gas-chromatographic preseparation method

Proton-transfer-reaction mass spectrometry (PTR-MS) has emerged as a useful tool to study volatile organic compounds (VOCs) in the atmosphere. In PTR-MS, proton-transfer reactions with H30+ ions are used to ionize and measure VOCs in air with a high sensitivity and fast time response. Only the masses of the ionized VOCs and their fragments, if any, are determined, and these product ions are not unique indicators of VOC identities. Here, a combination of gas chromatography and PTR-MS (GC-PTR-MS) is used to validate the measurements by PTR-MS of a number of common atmospheric VOCs. We have analyzed 75 VOCs contained in standard mixtures by GC-PTR-MS, which allowed detected masses to be unambiguously related to a specific compound. The calibration factors for PTR-MS and GC-PTR-MS were compared and showed that the loss of VOCs in the sample acquisition and GC system is small. GC-PTR-MS analyses of 56 air samples from an urban site were used to address the specificity of PTR-MS in complex air masses. It is demonstrated that the ions associated with methanol, acetonitrile, acetaldehyde, acetone, benzene, toluene, and higher aromatic VOCs are free from significant interference. A quantitative intercomparison between PTR-MS and GC-PTR-MS measurements of the aforementioned VOCs was performed and shows that they are accurately measured by PTR-MS.     

Full-scale chamber investigation and simulation of air freshener emissions in the presence of ozone

Volatile organic compound (VOC) emissions from one electrical plug-in type of pine-scented air freshener and their reactions with O3 were investigated in the U.S. Environmental Protection Agency indoor air research large chamber facility. Ozone was generated from a device marketed as an ozone generator air cleaner. Ozone and oxides of nitrogen concentrations and chamber conditions such as temperature, relative humidity, pressure, and air exchange rate were controlled and/or monitored. VOC emissions and some of the reaction products were identified and quantified. Source emission models were developed to predict the time/concentration profiles of the major VOCs (limonene, alpha-pinene, beta-pinene, 3-carene, camphene, benzyl propionate, benzyl alcohol, bornyl acetate, isobornyl acetate, and benzaldehyde) emitted bythe air freshener. Gas-phase reactions of VOCs from the air freshener with O3 were simulated by a photochemical kinetics simulation system using VOC reaction mechanisms and rate constants adopted from the literature. The concentration-time predictions were in good agreement with the data for O3 and VOCs emitted from the air freshener and with some of the primary reaction products. Systematic differences between the predictions and the experimental results were found for some species. Poor understanding of secondary reactions and heterogeneous chemistry in the chamber is the likely cause of these differences. The method has the potential to provide data to predict the impact of O3/VOC interactions on indoor air quality.     

Source apportionment of ambient volatile organic compounds in Beijing

The ambient air quality standard for ozone is frequently exceeded in Beijing in summer and autumn. Source apportionments of volatile organic compounds (VOCs), which are precursors of ground-level ozone formation, can be helpful to the further study of tropospheric ozone formation. In this study, ambient concentrations of VOCs were continuously measured with a time resolution of 30 min in August 2005 in Beijing. By using positive matrix factorization (PMF), eight sources for the selected VOC species were extracted. Gasoline-related emissions (the combination of gasoline exhaust and gas vapor), petrochemicals, and liquefied petroleum gas (LPG) contributed 52, 20, and 11%, respectively, to total ambient VOCs. VOC emissions from natural gas (5%), painting (5%), diesel vehicles (3%), and biogenic emissions (2%) were also identified. The gasoline-related, petrochemical, and biogenic sources were estimated to be the major contributors to ozone formation potentials in Beijing.     

Reactivity-based VOC control for solvent products: more efficient ozone reduction strategies

It has been almost 40 years since scientists and regulators began to publicly recognize that volatile organic compounds (VOCs) differ in their potential to form ozone. Since 1977, our understanding of the mechanisms by which VOCs contribute to ozone formation has grown substantially. An assessment of the science indicates that we now have sufficient understanding to develop and implement a more efficient approach to VOC control policy that will promote smarter, more cost-effective VOC controls. Furthermore, the U.S. Environmental Protection Agency's recently published Interim Guidance on Control of Volatile Organic Compounds in Ozone State Implementation Plans "encourages States to consider recent scientific information on the photochemical reactivity of volatile organic compounds (VOC) in the development of State implementation plans (SIPs)." As has been demonstrated by the California Air Resources Board's Aerosol Coatings Rule and the recent experience in Houston addressing high-reactivity VOCs, reactivity-based regulations may be more effective and efficient than mass-based rules in many applications. It is time for regulators, industry, and other stakeholders to work togetherto accelerate efforts to bring about a new paradigm in VOC control, in which the focus is on the ozone-forming potential of VOC emissions, rather than the mass of VOCs emitted.     

Intercomparison of volatile organic carbon measurement techniques and data at La Porte during the TexAQS2000 Air Quality Study

The Texas Air Quality Study 2000 (TexAQS2000) investigated the photochemical production of ozone and the chemistry of related precursors and reaction products in the vicinity of Houston, TX. The colocation of four instruments for the measurement of volatile organic carbon compounds (VOCs) allowed a unique opportunity for the intercomparison of the different in-situ measuring techniques. The instruments included three gas chromatographs, each with a different type of detector, and a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS) with each system designed to measure a different suite of VOCs. Correlation plots and correlation statistics are presented for species measured by more than one of these instruments. The GC instruments were all in agreement to within 10-20% (slope) with coefficients of variation (r2) of > or = 0.85. The PTR-MS agreement with other instruments was more dependent on species with some very good agreements (r2 values of approximately 0.95 for some aromatics), but isoprene, acetaldehyde and propene were substantially less highly correlated (0.55 < r2 < 0.80). At least part of these differences were undoubtedly due to the timing of sample acquisition in an environment in which VOC levels changed very rapidly on both quantitative and temporal scales.     

Real-Time Detection of Volatiles Released During Meat Spoilage: a Case Study of Modified Atmosphere-Packaged Chicken Breast Fillets Inoculated with <Emphasis Type="Italic">Br. thermosphacta</Emphasis>

The microbial spoilage of meat is accompanied by the release of volatile organic compounds (VOCs), many of which are odorous. These compounds give spoiled meat its characteristic pungent, sour, sulphury odour that provides consumers with an indication that the meat is unpalatable. Characterising meat spoilage based on volatile markers is of interest to the food industry in view of developing food freshness indicators (FFIs) to maintain food quality and reduce food waste. Conventional analytical methods for detecting VOCs developing during food spoilage involve intermittent sampling that delivers only snapshots of the release processes and thereby only limited information on the kinetics of their production and release. Proton-transfer-reaction mass spectrometry (PTR-MS) is an on-line technique that enables the detection of VOCs in real-time, thereby offering the possibility to follow the release of VOCs with a high time resolution. An analytical method using PTR-MS was developed to enable the continuous detection of VOCs released from chicken breast fillets inoculated with Brochothrix thermosphacta and stored under modified atmosphere (30 % CO₂, 70 % O₂) at 4 °C for 1 week. The meat spoilage VOCs detected by PTR-MS displayed different temporal dynamics of production and release, depending on the extent of spoilage. This paper describes the development of an analytical set-up for real-time detection of volatile spoilage markers using PTR-MS. This case study using inoculated chicken breast fillets demonstrates the applicability of this method to characterise individual VOC release patterns, which is of potential utility in the development of FFIs for the consumer market.     

Short communication: Identifying challenges and opportunities for improved nutrient management through the USDA's Dairy Agroecosystem Working Group

Nutrient management on US dairy farms must balance an array of priorities, some of which conflict. To illustrate nutrient management challenges and opportunities across the US dairy industry, the USDA Agricultural Research Service Dairy Agroecosystems Working Group (DAWG) modeled 8 confinement and 2 grazing operations in the 7 largest US dairy-producing states using the Integrated Farm System Model (IFSM). Opportunities existed across all of the dairies studied to increase on-farm feed production and lower purchased feed bills, most notably on large dairies (>1,000 cows) with the highest herd densities. Purchased feed accounted for 18 to 44% of large dairies' total operating costs compared with 7 to 14% on small dairies (<300 milk cows) due to lower stocking rates. For dairies with larger land bases, in addition to a reduction in environmental impact, financial incentives exist to promote prudent nutrient management practices by substituting manure nutrients or legume nutrients for purchased fertilizers. Environmental priorities varied regionally and were principally tied to facility management for dry-lot dairies of the semi-arid western United States (ammonia-N emissions), to manure handling and application for humid midwestern and eastern US dairies (nitrate-N leaching and P runoff), and pasture management for dairies with significant grazing components (nitrous oxide emissions). Many of the nutrient management challenges identified by DAWG are beyond slight modifications in management and require coordinated solutions to ensure an environmentally and economically sustainable US dairy industry.     

Treatment of volatile organic compounds from polyurethane and epoxy manufacture by a trickle-bed air biofilter

The objective of this study was to evaluate the performance of a trickle-bed air biofilter (TBAB) for the removal of volatile organic compound (VOC) produced during polyurethane (PU) and epoxy manufacture. The major VOCs emitted are ethyl acetate (EA) for PU and EA and xylene for epoxy production. For the treatment of VOCs emitted during PU production, the employed coal carbon appears to be efficient as a VOC concentration buffer in the biofiltration of waste gases. Based on the results of EA and total hydrocarbon (THC) removal, it was concluded that the TBAB is suitable for controlling VOC emission during PU manufacture. For the treatment of VOCs emitted during epoxy production, it was found that the performance of the TBAB is relatively poor due to the lack of VOC sources. However, this problem could be easily solved by mixing the VOCs emitted during PU and epoxy manufacture.     

Ozone-initiated particle formation, particle aging, and precursors in a laser printer

An increasing number of researchers have hypothesized that ozone may be involved in the particle formation processes that occur during printing, however no studies have investigated this further. In the current study, this hypothesis was tested in a chamber study by adding supplemental ozone to the chamber after a print job without measurable ozone emissions. Subsequent particle number concentration and size distribution measurements showed that new particles were formed minutes after the addition of ozone. The results demonstrated that ozone did react with printer-generated volatile organic compounds (VOCs) to form secondary organic aerosols (SOAs). The hypothesis was further confirmed by the observation of correlations among VOCs, ozone, and particles concentrations during a print job with measurable ozone emissions. The potential particle precursors were identified by a number of furnace tests, which suggested that squalene and styrene were the most likely SOA precursors with respect to ozone. Overall, this study significantly improved scientific understanding of the formation mechanisms of printer-generated particles, and highlighted the possible SOA formation potential of unsaturated nonterpene organic compounds by ozone-initiated reactions in the indoor environment.     

Assessment of management and basic beef quality assurance practices on Idaho dairies

In 2004 a mail-in survey was conducted to establish a baseline level of awareness and knowledge related to dairy beef quality assurance (BQA) issues in Idaho. A 30-question survey was mailed to every (n = 736) registered Idaho dairy. Two-hundred seventy-three (37%) dairies participated and were categorized as small (n <201 cows; 53.5%), medium-sized (n = 201 to 1,000 cows; 27.1%) or large (n >1,000 cows; 19.4%). The majority of respondents were dairy owners (83%). Eighty-nine percent of respondents indicated they followed BQA recommendations for animal care. The neck region in cows was used by 68% of respondents for i.m. injections and by 80% for s.c. injections. In calves, the values were 61 and 78%, respectively. Seventy-four percent of respondents indicated they had been trained for injections. Training methods cited included veterinarians (19.8%), dairy owners (16.8%), experience (9.9%), and BQA events or schools (4.5%). The importance of BQA in the dairy industry was rated 2.6 on a 5-point scale (0 = low; 4 = high). Participants rated the effect of dairy animals on the beef industry at 2.5. Plastic ear tags were the preferred method of animal identification, with 100% of large dairies, 97.3% of medium-sized dairies, and 84% of small dairies citing their use. Less than 10% used electronic identification for their animals. Almost half (48%) of large and medium-sized (49%) dairies and 32% of small dairies supported a national animal identification program. A mandatory identification program was supported by 41, 69, and 59% for small, medium-sized, and large dairies, respectively. The percentage of dairies keeping records was similar between small (93%), medium-sized (99%), and large (100%) dairies. Most small dairies (58%) used some form of paper records, whereas most medium-sized (85%) and large (100%) dairies used computers for record keeping. The preferred method to market cull cows by Idaho dairies was the auction market (64%), followed by order buyers (17%), direct to the packer (17%), private treaty sales (16%), and forward contracts (1%). To market calves, dairies used private treaty sales (52%), auction markets (42%), order buyers (14%), and forward contracts (1%). The results of this study will be used by University of Idaho Extension faculty in the design, development, and delivery of dairy BQA program information and materials.     

Survey of Beef Quality Assurance on California dairies

In October 2011, a mail and online survey of California dairy personnel was conducted to assess producer familiarity with and support of the Dairy Animal Care and Quality Assurance (DACQA) program. The DACQA program addresses cattle of all ages (birth to culling) and standard practices that affect the use of dairy cattle for beef. The survey was mailed to a random sample of 1,071 California dairies (65%) stratified by county, proportional to the number of dairies in each respective county. Data from the 158 responses received (15%) showed that 90% of culled cows on California dairies were sold for beef. However, personnel on more than one-half of California dairies (56%) had no knowledge of how their herd cull cows ranked in terms of beef quality measures (body condition score, US Department of Agriculture carcass grade, and hot carcass weight). Survey results showed that a considerable proportion of California dairy personnel were aware of recommended injection practices including a preference for subcutaneous injections (45%). A drug inventory was maintained on approximately 50% of the state's dairies. Management at these dairies was twice as likely to test for drug residues compared with dairies that did not maintain a drug inventory. More information about the DACQA program was requested by more than half of California dairies.     

Sensitivity analysis of ozone formation and transport for a central California air pollution episode

We developed a first- and second-order sensitivity analysis approach with the decoupled direct method to examine spatial and temporal variations of ozone-limiting reagents and the importance of local vs upwind emission sources in the San Joaquin Valley of central California for a 5 day ozone episode (Jul 29th to Aug 3rd, 2000). Despite considerable spatial variations, nitrogen oxides (NO(x)) emission reductions are overall more effective than volatile organic compound (VOC) control for attaining the 8 h ozone standard in this region for this episode, in contrast to the VOC control that works better for attaining the prior 1 h ozone standard. Interbasin source contributions of NO(x) emissions are limited to the northern part of the SJV, while anthropogenic VOC (AVOC) emissions, especially those emitted at night, influence ozone formation in the SJV further downwind. Among model input parameters studied here, uncertainties in emissions of NO(x) and AVOC, and the rate coefficient of the OH + NO2 termination reaction, have the greatest effect on first-order ozone responses to changes in NO(x) emissions. Uncertainties in biogenic VOC emissions only have a modest effect because they are generally not collocated with anthropogenic sources in this region.     

VOC and particulate emissions from commercial cigarettes: analysis of 2,5-DMF as an ETS tracer

Emissions of particulate matter (PM) and a broad suite of target volatile organic compounds (VOCs) in total, main-stream (MS) and side-stream (SS) smoke emissions are measured for six types of commercial cigarettes. The suitability of 2,5-dimethyl furan (DMF) as a tracer for environmental tobacco smoke (ETS) is investigated using laboratory results and a field study of 47 residences. Over 30 VOCs were characterized in cigarette smoke, including several that have not been reported previously. "regular tar", "low tar", menthol, and nonmenthol cigarettes showed only minor differences in PM and VOC emissions. When total emissions are considered, PM emissions averaged 18 +/- 2 mg cigarette(-1) and VOC emissions averaged 3644 +/- 160 mg cigarette(-1). DMF appears to satisfy all requirements for a tracer, namely, uniqueness, detectability, similar emission factors across tobacco products (211 +/- 16 microg cigarette(-1)), consistent proportions to other ETS compounds, and behavior similar to other ETS components in relevant environments. On the basis of field study results, DMF more reliably indicated smoking status than occupant-completed questionnaires, and cigarette smoking was responsible for significant fractions of benzene (50%), styrene (49%), and other VOCs in the smoker's homes.     

Halogenated volatile organic compounds from the use of chlorine-bleach-containing household products

Sodium hypochlorite (NaOCl) and many organic chemicals contained in household cleaning products may react to generate halogenated volatile organic compounds (VOCs). Halogenated VOC emissions from eight different chlorine bleach containing household products (pure and diluted) were investigated by headspace experiments. Chloroform and carbon tetrachloride were the leading compounds along with several halogenated compounds in the headspace of chlorine bleach products. One of the most surprising results was the presence of carbon tetrachloride (a probable human carcinogen and a powerful greenhouse gas that was banned for household use by the U.S. Food and Drug Administration) in very high concentrations (up to 101 mg m(-3)). By mixing surfactants or soap with NaOCl, it was shown that the formation of carbon tetrachloride and several other halogenated VOCs is possible. In addition to quantitatively determined halogenated VOCs (n = 15), several nitrogen-containing (n = 4), chlorinated (n = 10), oxygenated compounds (n = 22), and hydrocarbons (n = 14) were identified in the headspace of bleach products. Among these, 1,1-dichlorobutane and 2-chloro-2-nitropropane were the most abundant chlorinated VOCs, whereas trichloronitromethane and hexachloroethane were the most frequently detected ones. Indoor air halogenated VOC concentrations resulting from the use of four selected household products were also measured before, during, and 30 min after bathroom, kitchen, and floor cleaning applications. Chloroform (2.9-24.6 microg m(-3)) and carbon tetrachloride (0.25-459 microg m(-3)) concentrations significantly increased during the use of bleach containing products. During/ before concentration ratios ranged between 8 and 52 (25 +/- 14, average +/- SD) for chloroform and 1-1170 (146 +/- 367, average +/- SD) for carbon tetrachloride, respectively. These results indicated that the bleach use can be important in terms of inhalation exposure to carbon tetrachloride, chloroform and several other halogenated VOCs.     

Management practices and reported antimicrobial usage on conventional and organic dairy farms

The primary objective was to compare reported antimicrobial usage between conventional and organic dairy farms. A secondary objective was to contrast selected management characteristics of conventional and organic dairy herds. A questionnaire was administered on site to selected dairy farmers located in Michigan, Minnesota, New York, and Wisconsin. Organic herds (n = 32) were smaller and produced less milk than conventional herds (n = 99). Lactating cows in organic dairies were more likely to be housed in tie stalls, whereas most conventional dairies housed cows in free stalls and milked in a parlor. Total mixed rations and purchased feeds were used on more conventional dairy farms compared with organic dairy farms. Conventional dairy producers were more likely to use advice from veterinarians for recommendations of treatment, and organic dairy producers were more likely to rely on advice from other farmers. Based on recall of antibiotic usage in the previous 60 d, 5.1, 84.9, 9.1, and 0.9% of farmers with conventional herds reported treatment of none, 1 to 10%, 11 to 25%, and >25% of milk cows, respectively. Most organic farmers (90.6%) reported no antibiotic treatments of milk cows, whereas 9.4% reported treating 1 to 10% of milk cows. Ceftiofur was the most commonly reported antibiotic for both farm types. Milk replacer containing antibiotics was reportedly used on 49.5% of conventional herds but only on one organic herd (3.1%). Antibiotics were used in heifer calves on 74.7% of conventional herds versus 21.9% of organic herds. Antibiotics to treat mastitis were used on 79.8% of conventional herds but on none of the organic herds. Most organic farms were in compliance with standards in advance of implementation of regulations.     

Prevalence of lameness and leg lesions of lactating dairy cows housed in southern Brazil: Effects of housing systems

Within the last few decades, the North American and European dairy industries have been collecting information about lameness and leg injury prevalence on dairy farms and have tried to develop solutions to mitigate these ailments. Few published articles report the prevalence of lameness and leg lesions in areas outside of those 2 regions, or how alternative housing systems, such as compost-bedded packs, affect the prevalence of these maladies. The objectives of this study were to compare the prevalence of lameness and leg lesions on confined dairies that used freestall, compost-bedded packs, or a combination of these 2 systems in Brazil. Data were collected in the autumn and winter of 2016 from 50 dairy farms located in Paraná state, including 12 compost-bedded pack dairies (CB), 23 freestall dairies (FS), and 15 freestall dairies that used compost-bedded packs for vulnerable cows (FS+C). A visit to the farm consisted of a management questionnaire, an inspection of the housing areas as well as the milking parlor, and an evaluation of all lactating cows as they exited the parlor for lameness (score 1–5), hygiene (score 0–2), body condition score (score 1–5), and hock and knee lesions (score 0–1). Median 1-way chi-squared test was used to compare production systems. We found no difference between farm types in management practices related to hoof health management or average daily milk production per cow [31 (29–33.9) kg/d; median (quartile 1–3)], percentage of Holstein cattle in the herd [100% (90–100%)], conception rate [35.8% (30.2–38%)], or pregnancy rate [15% (13.7–18%)]. The CB farms were smaller [85 (49.5–146.5) milking cows] than both the FS [270 (178–327.5) milking cows] and FS+C farms [360 (150–541.5) milking cows). The overall prevalence of severe lameness (score 4 and 5) across all farms was 21.2% (15.2–28.5%) but was lower on the CB farms [14.2% (8.45–15.5%)] in comparison to the FS [22.2% (16.8–26.7%)] and the FS+C farms [22.2% (17.4–32.8%)]. Less than 1% of all cows scored on CB farms were observed with swollen or wounded knees (or both), which was lower than either the FS or FS+C farms [7.4% (3.6–11.9%) and 6.4% (2.6–11.8%) of all cows scored, respectively]. The same pattern was found for hock lesions, where the farm-level prevalence within the 3 different housing types was 0.5% (0–0.9%), 9.9% (0.8–15.3%), and 5.7% (2.6–10.9%) for CB, FS, and FS+C farms, respectively. No differences between farm systems were observed for hygiene or body condition score. On average, 2.7% (0.8–10.9%) of lactating cows had a soiled side, 15.4% (2.1–37.4%) had dirty legs and 1.7% (0–9.3%) had dirty udders. The average herd-level body condition score across farms was 2.9 (2.9–3), with 0.86% of the all cows scored having a body condition score <2.5. These results indicate that lameness prevalence on confined dairies in Brazil is high and highlight the need for remedial changes in environmental design and management practices. We found that CB farms in this region had reduced lameness and lesions in relation to FS or FS+C dairies.     

Mobile source and livestock feed contributions to regional ozone formation in Central California

A three-dimensional air quality model with 8 km horizontal resolution was applied to estimate the summertime ozone (O(3)) production from mobile sources and fermented livestock feed in California's San Joaquin Valley (SJV) during years 2000, 2005, 2010, 2015, and 2020. Previous studies have estimated that animal feed emissions of volatile organic compounds (VOCs) have greater O(3) formation potential than mobile-source VOC emissions when averaging across the entire SJV. The higher spatial resolution in the current study shows that the proximity of oxides of nitrogen (NO(x)) and VOC emissions from mobile sources enhances their O(3) formation potential. Livestock feed VOC emissions contributed 3-4 ppb of peak O(3) (8-h average) in Tulare County and 1-2 ppb throughout the remainder of the SJV during the CCOS 2000 July-August episode. In total, livestock feed contributed ~3.5 tons of the ground level peak O(3) (8 h average) in the SJV region, and mobile VOC contributed ~12 tons in this episode. O(3) production from mobile sources is declining over time in response to emissions control plans that call for cleaner fuels and engines with advanced emissions controls. Projecting forward to the year 2020, mobile-source VOC emissions are predicted to produce ~3 tons of the ground level peak O(3)(8-h average) and livestock feed VOC emissions are predicted to contribute ~2.5 tons making these sources nearly equivalent.     

Dietary cation-anion difference effects on performance and acid-base status of lactating dairy cows: a meta-analysis

A meta-analysis was conducted to examine potential empirical relationships between dietary cation-anion difference (DCAD) (Na + K - Cl) and the response of lactating dairy cows. The database was developed from 12 studies published between 1984 and 1997 that included a total of 17 trials, 69 dietary treatments, and 230 cows. Results indicated that DCAD affected performance of lactating dairy cows. Maximum milk yield and feed intake were reached when DCAD was 34 and 40 meq/100 g of feed dry matter, respectively. Blood pH and HCO3 concentrations increased with DCAD, indicating an improved acid-base balance of lactating dairy cows. Changes in urinary pH and urinary excretion of Na, K, and Cl were consistent with varying DCAD, thus dietary acidity or alkalinity. The effects of DCAD were likely mediated via modification of acid-base status in the cows.     

Gaseous and particulate emissions from prescribed burning in Georgia

Prescribed burning is a significant source of fine particulate matter (PM2.5) in the southeastern United States. However, limited data exist on the emission characteristics from this source. Various organic and inorganic compounds both in the gas and particle phase were measured in the emissions of prescribed burnings conducted at two pine-dominated forest areas in Georgia. The measurements of volatile organic compounds (VOCs) and PM2.5 allowed the determination of emission factors for the flaming and smoldering stages of prescribed burnings. The VOC emission factors from smoldering were distinctly higher than those from flaming except for ethene, ethyne, and organic nitrate compounds. VOC emission factors show that emissions of certain aromatic compounds and terpenes such as alpha and beta-pinenes, which are important precursors for secondary organic aerosol (SOA), are much higher from active prescribed burnings than from fireplace wood and laboratory open burning studies. Levoglucosan is the major particulate organic compound (POC) emitted for all these studies, though its emission relative to total organic carbon (mg/g OC) differs significantly. Furthermore, cholesterol, an important fingerprint for meat cooking, was observed only in our in situ study indicating a significant release from the soil and soil organisms during open burning. Source apportionment of ambient primary fine particulate OC measured at two urban receptor locations 20-25 km downwind yields 74 +/- 11% during and immediately after the burns using our new in situ profile. In comparison with the previous source profile from laboratory simulations, however, this OC contribution is on average 27 +/- 5% lower.     

Relationships between fertility and postpartum changes in body condition and body weight in lactating dairy cows

The relationship between energy status and fertility in dairy cattle was retrospectively analyzed by comparing fertility with body condition score (BCS) near artificial insemination (AI; experiment 1), early postpartum changes in BCS (experiment 2), and postpartum changes in body weight (BW; experiment 3). To reduce the effect of cyclicity status, all cows were synchronized with Double-Ovsynch protocol before timed AI. In experiment 1, BCS of lactating dairy cows (n = 1,103) was evaluated near AI. Most cows (93%) were cycling at initiation of the breeding Ovsynch protocol (first GnRH injection). A lower percentage pregnant to AI (P/AI) was found in cows with lower (≤2.50) versus higher (≥2.75) BCS (40.4 vs. 49.2%). In experiment 2, lactating dairy cows on 2 commercial dairies (n = 1,887) were divided by BCS change from calving until the third week postpartum. Overall, P/AI at 70-d pregnancy diagnosis differed dramatically by BCS change and was least for cows that lost BCS, intermediate for cows that maintained BCS, and greatest for cows that gained BCS [22.8% (180/789), 36.0% (243/675), and 78.3% (331/423), respectively]. Surprisingly, a difference existed between farms with BCS change dramatically affecting P/AI on one farm and no effect on the other farm. In experiment 3, lactating dairy cows (n = 71) had BW measured weekly from the first to ninth week postpartum and then had superovulation induced using a modified Double-Ovsynch protocol. Cows were divided into quartiles (Q) by percentage of BW change (Q1 = least change; Q4 = most change) from calving until the third week postpartum. No effect was detected of quartile on number of ovulations, total embryos collected, or percentage of oocytes that were fertilized; however, the percentage of fertilized oocytes that were transferable embryos was greater for cows in Q1, Q2, and Q3 than Q4 (83.8, 75.2, 82.6, and 53.2%, respectively). In addition, percentage of degenerated embryos was least for cows in Q1, Q2, and Q3 and greatest for Q4 (9.6, 14.5, 12.6, and 35.2% respectively). In conclusion, for cows synchronized with a Double-Ovsynch protocol, an effect of low BCS (≤2.50) near AI on fertility was detected, but change in BCS during the first 3 wk postpartum had a more profound effect on P/AI to first timed AI. This effect could be partially explained by the reduction in embryo quality and increase in degenerate embryos by d 7 after AI in cows that lost more BW from the first to third week postpartum.