Determination of α-Dicarbonyl compounds in traditional Chinese herbal medicines.

α-DCs (α-dicarbonyls) have been proven to be closely related to aging and the onset and development of many chronic diseases. The wide presence of this kind of components in various foods and beverages has been unambiguously determined, but their occurrence in various phytomedicines remains in obscurity. In this study, we established and evaluated an HPLC-UV method and used it to measure the contents of four α-DCs including 3-deoxyglucosone (3-DG), glyoxal (GO), methylglyoxal (MGO), and diacetyl (DA) in 35 Chinese herbs after they have been derivatized with 4-nitro-1,2-phenylenediamine. The results uncover that 3-DG is the major component among the α-DCs, being detectable in all the selected herbs in concentrations ranging from 22.80 µg/g in the seeds of Alpinia katsumadai to 7032.75 µg/g in the fruit of Siraitia grosuenorii. The contents of the other three compounds are much lower than those of 3-DG, with GO being up to 22.65 µg/g, MGO being up to 55.50 µg/g, and DA to 18.75 µg/g, respectively. The data show as well the contents of the total four α-DCs in the herbs are generally in a comparable level to those in various foods, implying that herb medicines may have potential risks on human heath in view of the α-DCs.

A network pharmacology integrated pharmacokinetics strategy to investigate the pharmacological mechanism of absorbed components from crude and processed Zingiberis Rhizoma on deficiency-cold and hemorrhagic syndrome.

ETHNOPHARMACOLOGICAL RELEVANCE: Zingiberis Rhizoma (ZR) and Zingiberis Rhizoma Carbonisata (ZRC), as two forms of ginger-based herbal drugs used in China for at least 2000 years, have been recorded in Chinese Pharmacopoeia and applied for specific indications in traditional Chinese medicine (TCM). AIM OF THE STUDY: The present study aimed to explore the underlying therapeutic and processing mechanism of the absorbed components of ZR and ZRC on deficiency-cold and hemorrhagic syndrome (DCHS) using network pharmacological technique combined with pharmacokinetics strategy. MATERIALS AND METHODS: In this study, a rapid and sensitive approach was conceived to simultaneously determine the seven components (zingiberone, 6-gingerol, 8-gingerol, 6-shogaol, 6-paradol, diacetyl-6-gingerol and 10-gingerol) in rat serum by HPLC-DAD-MS. The network pharmacological technique was employed to evaluate the effect of the absorbed components of ZR and ZRC on DCHS. Also, the vitro experiments were carried out to validate the functions of the seven compounds on coagulation and other major haematological effects. RESULTS: The values of intra-assay and inter-assay precision were determined to be less than 7.44%, with an accuracy value ranging from 83.64% to 107.99%. Analysis of rat plasma revealed that the extraction recoveries and matrix effects of the seven analytes were >85.76%. The method for validation following oral administration of ZR and ZRC to rats was proved to be a success in the pharmacokinetic study of the seven ingredients. Pharmacokinetics showed that ZR processing could enhance the absorption and utilization of 6-shogaol, 6-paradol and diacetyl-6-gingerol, meanwhile reduce the absorption of 6-gingerol, 8-gingerol, and 10-gingerol. Through the pathway enrichment analysis, it was found that the significant biological process of ZR and ZRC on DCHS was primarily associated with complement, coagulation cascades and platelet activation pathways. The vitro experiments indicated that zingiberone, 6-paradol and diacetyl-6-gingerol had a hemostatic effect by upregulating the expression of one or more targets such as TNF-α, FⅩa, FⅫ, FⅧ, ICAM-1, vWF and ITGB3. While 6-gingerol, 6-shogaol, 8-gingerol and 10-gingerol played a critical role in promoting blood circulation by increasing the expression of TM and/or PORC, and/or reducing the expression of ITGB3. CONCLUSION: In brief, network pharmacological technique in combination with pharmacokinetics strategy provided an applicable method for pharmacological mechanism study of ZR and ZRC, which, also, could be used as reference for quality control of the two drugs. In a broader sense, this combined strategy might even be valuable in uncovering the therapeutic and processing mechanism of Chinese herbs on a systematic level.

Impacts of risk assessment data, assumptions, and methods: Considering the evidence for diacetyl and 2,3-pentanedione.

The articles published as part of the Frontiers in Public Health research topic, "Investigating exposures and respiratory health in coffee workers" present research findings that better characterize exposures to diacetyl and 2,3-pentanedione and inform our understanding of the health risks posed by these exposures. Although various research groups and organizations have conducted risk assessments to derive occupational exposure limits (OELs) for diacetyl, differences in the data used and assumptions made in these efforts have resulted in a wide range of recommended OELs designed to protect human health. The primary drivers of these differences include the decision to use data from human or animal studies in conducting a quantitative risk assessment, and the application of uncertainty factors (UF) to derive an OEL. This Perspectives paper will discuss the practical implications of these decisions, and present additional commentary on the potential role that the recent investigation of human exposures to relatively low concentrations of α-diketones, specifically diacetyl and 2,3-pentanedione, may play in supporting qualitative or quantitative human health risk assessments.

Phytochemical analysis of Artemisia kopetdaghensis: Sesquiterpene lactones with proapoptotic activity against prostate cancer cells.

Phytochemical investigation of the aerial parts of Artemisia kopetdaghensis resulted in the isolation and characterization of three undescribed eudesmane-type sesquiterpene lactones, persianolide A, 4-epi-persianolide A, and 3α,4-epoxypersianolide A, together with three previously described eudesmane-type sesquiterpene lactones, 11-epi-artapshin, 1ß,8α-dihydroxy-11α,13-dihydrobalchanin, and 1ß-hydroxy-11-epi-colartin. The abundantly obtained 11-epi-artapshin was oxidized to undescribed 11α,13-dihydroeudesma-12,6α-olide-1,8-dione and 8ß-hydroxy-11α,13-dihydroeudesma-12,6α-olide-1-one and acetylated to the undescribed 1,8-O-diacetyl-11α,13-dihydroeudesma-12,6α-olide. Structures were elucidated based on extensive spectral data analyses, including 1D and 2D NMR and HRESIMS. The absolute configuration was determined using calculated and experimental ECD spectral data. Compounds were subsequently subjected to the MTT assay to evaluate their cytotoxicity against prostate cancer cells (DU-145 and LNCaP). Related factors associated with the sequence of apoptosis were tested by ELISA, western blotting, and biochemical assay. Results suggested that 11-epi-artapshin hinders the growth of DU-145 cells through mitochondria-mediated apoptosis initiated by stimulation of ROS build-up, ΔΨm depletion, regulation of the Bax/Bcl-2 ratio, and activation of caspase 3, respectively.

Determinants of Task-Based Exposures to Alpha-Diketones in Coffee Roasting and Packaging Facilities Using a Bayesian Model Averaging Approach.

Coffee production workers can be exposed to inhalational hazards including alpha-diketones such as diacetyl and 2,3-pentanedione. Exposure to diacetyl is associated with the development of occupational lung disease, including obliterative bronchiolitis, a rare and irreversible lung disease. We aimed to identify determinants contributing to task-based exposures to diacetyl and 2,3-pentanedione at 17 U.S. coffee production facilities. We collected 606 personal short-term task-based samples including roasting (n = 189), grinding (n = 74), packaging (n = 203), quality control (QC, n = 44), flavoring (n = 15), and miscellaneous production/café tasks (n = 81), and analyzed for diacetyl and 2,3-pentanedione in accordance with the modified OSHA Method 1013/1016. We also collected instantaneous activity-based (n = 296) and source (n = 312) samples using evacuated canisters. Information on sample-level and process-level determinants relating to production scale, sources of alpha-diketones, and engineering controls was collected. Bayesian mixed-effect regression models accounting for censored data were fit for overall data (all tasks) and specific tasks. Notable determinants identified in univariate analyses were used to fit all plausible models in multiple regression analysis which were summarized using a Bayesian model averaging method. Grinding, flavoring, packaging, and production tasks with ground coffee were associated with the highest short-term and instantaneous-activity exposures for both analytes. Highest instantaneous-sources of diacetyl and 2,3-pentanedione included ground coffee, flavored coffee, liquid flavorings, and off-gassing coffee bins or packages. Determinants contributing to higher exposures to both analytes in all task models included sum of all open storage sources and average percent of coffee production as ground coffee. Additionally, flavoring ground coffee and flavoring during survey contributed to notably higher exposures for both analytes in most, but not all task groups. Alternatively, general exhaust ventilation contributed to lower exposures in all but two models. Additionally, among facilities that flavored, local exhaust ventilation during flavoring processes contributed to lower 2,3-pentanedione exposures during grinding and packaging tasks. Coffee production facilities can consider implementing additional exposure controls for processes, sources, and task-based determinants associated with higher exposures to diacetyl and 2,3-pentanedione, such as isolating, enclosing, and directly exhausting grinders, flavoring mixers, and open storage of off-gassing whole bean and ground coffee, to reduce exposures and minimize risks for lung disease among workers.

Case Study: Efficacy of Engineering Controls in Mitigating Diacetyl and 2,3-Pentanedione Emissions During Coffee Grinding.

Exposure to elevated levels of diacetyl in flavoring and microwave popcorn production has been associated with respiratory impairment among workers including from a severe lung disease known as obliterative bronchiolitis. Laboratory studies demonstrate damage to the respiratory tract in rodents exposed to either diacetyl or the related alpha-diketone 2,3-pentanedione. Respiratory tract damage includes the development of obliterative bronchiolitis-like changes in the lungs of rats repeatedly inhaling either diacetyl or 2,3-pentanedione. In one flavored coffee processing facility, current workers who spent time in higher diacetyl and 2,3-pentanedione areas had lower lung function values, while five former flavoring room workers were diagnosed with obliterative bronchiolitis. In that and other coffee roasting and packaging facilities, grinding roasted coffee beans has been identified as contributing to elevated levels of diacetyl and 2,3-pentanedione. To reduce worker exposures, employers can take various actions to control exposures according to the hierarchy of controls. Because elimination or substitution is not applicable to coffee production facilities not using flavorings, use of engineering controls to control exposures at their source is especially important. This work demonstrates the use of temporary ventilated enclosures around grinding equipment in a single coffee roasting and packaging facility to mitigate diacetyl and 2,3-pentanedione emissions from grinding equipment to the main production space. Concentrations of diacetyl and 2,3-pentanedione were measured in various locations throughout the main production space as well as inside and outside of ventilated enclosures to evaluate the effect of the enclosures on exposures. Diacetyl and 2,3-pentanedione concentrations outside one grinder enclosure decreased by 95 and 92%, respectively, despite ground coffee production increasing by 12%, after the enclosure was installed. Outside a second enclosure, diacetyl and 2,3-pentanedione concentrations both decreased 84%, greater than the 33% decrease in ground coffee production after installation. Temporary ventilated enclosures used as engineering control measures in this study effectively reduced emissions of diacetyl and 2,3-pentanedione at the source in this facility. These findings motivated management to explore options with a grinding equipment manufacturer to permanently ventilate their grinders to reduce emissions of diacetyl and 2,3-pentanedione.

Model Predictions of Occupational Exposures to Diacetyl and 2,3-Pentanedione Emitted From Roasted Whole Bean and Ground Coffee: Influence of Roast Level and Physical Form on Specific Emission Rates.

Roasted coffee emits hazardous volatile organic compounds including diacetyl and 2,3-pentanedione. Workers in non-flavored coffee roasting and packaging facilities might inhale diacetyl and 2,3-pentanedione from roasted coffee above occupational exposure limits depending on their work activities and proximity to the source of emissions. Objectives of this laboratory study were to: (1) investigate factors affecting specific emission rates (SERs) of diacetyl and 2,3-pentanedione from freshly roasted coffee, (2) explore the effect of time on SERs of coffee stored in sealed bags for 10-days, and (3) predict exposures to workers in hypothetical workplace scenarios. Two roast levels (light and dark) and three physical forms (whole bean, coarse ground, and fine ground) were investigated. Particle size for whole bean and ground coffee were analyzed using geometric mean of Feret diameter. Emitted chemicals were collected on thermal desorption tubes and quantified using mass spectrometry analysis. SERs developed here coupled with information from previous field surveys provided model input to estimate worker exposures during various activities using a probabilistic, near-field/far-field model. For freshly roasted coffee, mean SER of diacetyl and 2,3-pentantedione increased with decreasing particle size of the physical form (whole bean < coarse ground < fine ground) but was not consistent with roast levels. SERs from freshly roasted coffee increased with roast level for diacetyl but did not change for 2,3-pentanedione. Mean SERs were greatest for diacetyl at 3.60 mg kg-1 h-1 for dark, fine ground and for 2,3-pentanedione at 3.88 mg kg-1 h-1 for light, fine ground. For storage, SERs of whole bean remained constant while SERs of dark roast ground coffee decreased and light roast ground coffee increased. Modeling demonstrated that near-field exposures depend on proximity to the source, duration of exposure, and air velocities in the near-field further supporting previously reported chemical air measurements in coffee roasting and packaging facilities. Control of source emissions using local exhaust ventilation especially around grinding activities as well as modification of work practices could be used to reduce exposures in this workforce.

Measurement of Diacetyl and Related Compounds in Coffee Roasteries and Breweries.

α-Diketones such as diacetyl (2,3-butanedione) and 2,3-pentanedione are generated during the roasting and fermentation of foods and are also used as flavoring compounds. Exposure to these compounds has been associated with obliterative bronchiolitis in workers. We report indoor air concentrations of diacetyl and 2,3-pentanedione, as well as acetoin (3-hydroxy-2-butanone), in several small coffee roasteries and breweries using standard integrated air sampling sorbent tubes followed by gas chromatography tandem mass spectrometry as well as the first use of on-site continuous real-time proton-transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS). Diacetyl and 2,3-pentanedione were detected in most of the sorbent samples at concentrations between 0.02 and 8 ppbv, and in general were higher in coffee roasteries compared with breweries. Three integrated air samples, all from the barista area at one facility, exceeded the NIOSH recommended exposure limit (REL) of 5 ppbv for diacetyl. 2,3-Pentanedione concentrations in these three samples were greater than 50% of its REL, but did not exceed it. Acetoin, a precursor to diacetyl, was also detected at concentrations between 0.03 and 5 ppbv in most sorbent tube samples, with concentrations generally higher in breweries. PTR-ToF-MS measurements exhibited similar trends and provided continuous real-time volatile organic compound data that showed episodic excursions with peak concentrations of diacetyl and 2,3-pentanedione between 15 and 20 ppbv. Examination of the time series data identified specific activities associated with peak diketone emissions, including transfer of freshly roasted coffee beans to the cooling tray, or the opening of a brew kettle. Additional indoor air quality parameters including CO2, NO2, and PM2.5 were also assessed on-site. Airway inflammation was assessed in 19 workers before and after each work shift using online measurements of fractional exhaled nitric oxide (FENO). The pre-shift mean FENO was 3.7 (95% confidence interval: -3.6, 11.0) ppbv higher and the post-shift FENO was 7.1 (-1.9, 16.1) ppbv higher for workers at coffee roasteries compared with breweries. The cross-shift change in FENO was 3.4 (-2.8, 9.6) ppbv higher for workers at coffee roasteries compared with breweries. However, none of these differences were statistically significant, and the cross-shift change in FENO was not statistically different from zero for either group of workers. The findings from this pilot study demonstrate that α-diketones and related compounds are present in the indoor air of both breweries and coffee roasteries and may exceed health protective guidelines in coffee roasteries. Additional studies are required to fully characterize worker exposures in these settings and to identify specific work activities and processes associated with high exposures. Engineering controls, including targeted exhaust ventilation and the use of low-cost sensors, are recommended as an approach to protect workers from exposure to hazardous levels of α-diketones.

A Strategy for Field Evaluations of Exposures and Respiratory Health of Workers at Small- to Medium-Sized Coffee Facilities.

Coffee production is a global industry with roasteries throughout the world. Workers in this industry are exposed to complex mixtures of gases, dusts, and vapors including carbon monoxide, carbon dioxide, coffee dust, allergens, alpha-diketones, and other volatile organic compounds (VOCs). Adverse respiratory health outcomes such as respiratory symptoms, reduced pulmonary function, asthma, and obliterative bronchiolitis can occur among exposed workers. In response to health hazard evaluations requests received from 17 small- to medium-sized coffee facilities across the United States, the National Institute for Occupational Safety and Health conducted investigations during 2016-2017 to understand the burden of respiratory abnormalities, exposure characteristics, relationships between exposures and respiratory effects, and opportunities for exposure mitigation. Full-shift, task-based, and instantaneous personal and area air samples for diacetyl, 2,3-pentanedione and other VOCs were collected, and engineering controls were evaluated. Medical evaluations included questionnaire, spirometry, impulse oscillometry, and fractional exhaled nitric oxide. Exposure and health assessments were conducted using standardized tools and approaches, which enabled pooling data for aggregate analysis. The pooled data provided a larger population to better address the requestors' concern of the effect of exposure to alpha-diketones on the respiratory heath of coffee workers. This paper describes the rationale for the exposure and health assessment strategy, the approach used to achieve the study objectives, and its advantages and limitations.

Case Report: Flavoring-Related Lung Disease in a Coffee Roasting and Packaging Facility Worker With Unique Lung Histopathology Compared With Previously Described Cases of Obliterative Bronchiolitis.

Occupational exposure to diacetyl, a butter flavor chemical, can result in obliterative bronchiolitis. Obliterative bronchiolitis is characterized by exertional dyspnea, fixed airflow obstruction, and histopathologic constrictive bronchiolitis, with bronchiolar wall fibrosis leading to luminal narrowing and obliteration. We describe a case of advanced lung disease with histopathology distinct from obliterative bronchiolitis in a 37-year-old male coffee worker following prolonged exposure to high levels of diacetyl and the related compound 2,3-pentanedione, who had no other medical, avocational, or occupational history that could account for his illness. He began working at a coffee facility in the flavoring room and grinding area in 2009. Four years later he moved to the packaging area but continued to flavor and grind coffee at least 1 full day per week. He reported chest tightness and mucous membrane irritation when working in the flavoring room and grinding area in 2010. Beginning in 2014, he developed dyspnea, intermittent cough, and a reduced sense of smell without a work-related pattern. In 2016, spirometry revealed a moderate mixed pattern that did not improve with bronchodilator. Thoracoscopic lung biopsy results demonstrated focal mild cellular bronchiolitis and pleuritis, and focal peribronchiolar giant cells/granulomas, but no evidence of constrictive bronchiolitis. Full-shift personal air-samples collected in the flavoring and grinding areas during 2016 measured diacetyl concentrations up to 84-fold higher than the recommended exposure limit. Medical evaluations indicate this worker developed work-related, airway-centric lung disease, most likely attributable to inhalational exposure to flavorings, with biopsy findings not usual for obliterative bronchiolitis. Clinicians should be aware that lung pathology could vary considerably in workers with suspected flavoring-related lung disease.

Characterization of Naturally Occurring Alpha-Diketone Emissions and Exposures at a Coffee Roasting Facility and Associated Retail Café.

BACKGROUND: Alpha-diketones such as diacetyl and 2,3-pentanedione have been used as artificial flavorings in a variety of industries and are produced naturally when food products such as coffee beans are roasted. Exposure to these compounds has been associated with bronchiolitis obliterans, a rare and severe respiratory disease. In the current paper, we (i) evaluate which steps in the coffee production process are associated with the highest alpha-diketone emissions at a small craft coffee roaster and associated café, (ii) determine the extent to which direct-reading measurements of CO, CO2, and total volatile organic compounds (VOCs) can serve as lower-cost surrogate indicators for diacetyl concentrations, and (iii) conduct a limited emissions study to quantify the effect that the process variable of roast type has on diacetyl emissions from grinding beans. METHODS: Exposure and area concentration data for diacetyl and 2,3-pentanedione were collected over 4 days of sampling at a single coffee roaster and associated café. Additional measurements of café patrons' exposure to diacetyl were collected in seven other craft roastery/cafes in Seattle, WA. For the emissions experiments, integrated area air samples for diacetyl were collected using sorbent tubes over 30-min intervals for each roast type with the sorbent tubes positioned next to a grinder placed in an exposure chamber. Sorbent tubes were analyzed for alpha-diketones using gas chromatography-mass spectrometry. A photoionization detector (PID) was also used to measure continuous total VOC concentrations at the coffee roastery, and during each grinding experiment. RESULTS: Diacetyl concentrations in five of the seven personal samples from the craft roastery were above the United States National Institute of Occupational Safety and Health (NIOSH) Recommended Exposure Limit (REL) of 5 ppb as an 8-h time-weighted average (TWA)-and one of the seven personal samples exceeded the NIOSH REL for 2,3-pentanedione-9.3 ppb as an 8-h TWA. Median diacetyl and 2,3-pentanedione emissions were highest at the bagging machine followed by the grinder, roaster, barista, and background areas. The arithmetic mean diacetyl concentrations from the seven personal samples collected from café patrons was 3.96 ppb, suggesting that diacetyl exposure poses a negligible health risk to café patrons. Correlations between diacetyl and total VOCs, CO, and CO2 showed that diacetyl was well correlated with total VOCs, but poorly correlated with CO and CO2. Based on our limited emissions study, French roast was associated with the highest mass emission factor of diacetyl. CONCLUSIONS: Results from the exposure assessment study indicated that coffee production workers at this facility had elevated exposures to diacetyl and 2,3-pentanedione compared to recommended guidelines, whereas baristas and café patrons received lower exposures. Area sampling showed that the areas with the highest alpha-diketone emissions were the grinder and the bagging machine, which are both areas associated with tasks involving ground roasted coffee. Future research could focus on designing and evaluating effective engineering controls, in the form of local exhaust ventilation, with the goal of reducing alpha diketone exposures, as well as conducting similar studies at other small-scale craft coffee roasters and cafés to better understand the variability in these emissions and exposures within these types of facilities.

Analysis of α-dicarbonyl compounds in coffee (Coffea arabica) prepared under various roasting and brewing methods.

This study investigated the correlations of α-dicarbonyl compounds (α-DCs), including glyoxal (GO), methylglyoxal (MGO) and diacetyl (DA), formed in coffee prepared under various roasting and brewing methods. The levels of α-DCs in Brazilian coffee beans (Coffea arabica) ranged from 28.3 to 178 µg/mL. Concentration ranges of GO, MGO and DA were 1.31-6.57, 25.5-159 and 1.50-12.9 µg/mL, respectively. The level of α-DCs increased with high roasting temperature, long roasting time, small coffee bean particles, mineral water and espresso brewing. In correlation analysis, the roasting temperature-time showed strong negative correlations with α-DCs in espresso (-0.886) and cold-brew coffee (-0.957). In espresso coffee, there was a strong negative correlation between the α-DCs and coffee bean particle size (-0.918).

Exposures and Emissions in Coffee Roasting Facilities and Cafés: Diacetyl, 2,3-Pentanedione, and Other Volatile Organic Compounds.

Roasted coffee and many coffee flavorings emit volatile organic compounds (VOCs) including diacetyl and 2,3-pentanedione. Exposures to VOCs during roasting, packaging, grinding, and flavoring coffee can negatively impact the respiratory health of workers. Inhalational exposures to diacetyl and 2,3-pentanedione can cause obliterative bronchiolitis. This study summarizes exposures to and emissions of VOCs in 17 coffee roasting and packaging facilities that included 10 cafés. We collected 415 personal and 760 area full-shift, and 606 personal task-based air samples for diacetyl, 2,3-pentanedione, 2,3-hexanedione, and acetoin using silica gel tubes. We also collected 296 instantaneous activity and 312 instantaneous source air measurements for 18 VOCs using evacuated canisters. The highest personal full-shift exposure in part per billion (ppb) to diacetyl [geometric mean (GM) 21 ppb; 95th percentile (P95) 79 ppb] and 2,3-pentanedione (GM 15 ppb; P95 52 ppb) were measured for production workers in flavored coffee production areas. These workers also had the highest percentage of measurements above the NIOSH Recommended Exposure Limit (REL) for diacetyl (95%) and 2,3-pentanedione (77%). Personal exposures to diacetyl (GM 0.9 ppb; P95 6.0 ppb) and 2,3-pentanedione (GM 0.7 ppb; P95 4.4 ppb) were the lowest for non-production workers of facilities that did not flavor coffee. Job groups with the highest personal full-shift exposures to diacetyl and 2,3-pentanedione were flavoring workers (GM 34 and 38 ppb), packaging workers (GM 27 and 19 ppb) and grinder operator (GM 26 and 22 ppb), respectively, in flavored coffee facilities, and packaging workers (GM 8.0 and 4.4 ppb) and production workers (GM 6.3 and 4.6 ppb) in non-flavored coffee facilities. Baristas in cafés had mean full-shift exposures below the RELs (GM 4.1 ppb diacetyl; GM 4.6 ppb 2,3-pentanedione). The tasks, activities, and sources associated with flavoring in flavored coffee facilities and grinding in non-flavored coffee facilities, had some of the highest GM and P95 estimates for both diacetyl and 2,3-pentanedione. Controlling emissions at grinding machines and flavoring areas and isolating higher exposure areas (e.g., flavoring, grinding, and packaging areas) from the main production space and from administrative or non-production spaces is essential for maintaining exposure control.

The Burden of Respiratory Abnormalities Among Workers at Coffee Roasting and Packaging Facilities.

Introduction: Respiratory hazards in the coffee roasting and packaging industry can include asthmagens such as green coffee bean and other dust and alpha-diketones such as diacetyl and 2,3-pentanedione that can occur naturally from roasting coffee or artificially from addition of flavoring to coffee. We sought to describe the burden of respiratory abnormalities among workers at 17 coffee roasting and packaging facilities. Methods: We completed medical surveys at 17 coffee roasting and packaging facilities that included interviewer-administered questionnaires and pulmonary function testing. We summarized work-related symptoms, diagnoses, and spirometry testing results among all participants. We compared health outcomes between participants who worked near flavoring and who did not. Results: Participants most commonly reported nose and eye symptoms, and wheeze, with a work-related pattern for some. Symptoms and pulmonary function tests were consistent with work-related asthma in some participants. About 5% of workers had abnormal spirometry and most improved after bronchodilator. Health outcomes were similar between employees who worked near flavoring and who did not, except employees who worked near flavoring reported more chronic bronchitis and ever receiving a diagnosis of asthma than those who did not work near flavoring. Conclusion: The symptoms and patterns likely represent overlapping health effects of different respiratory hazards, including green coffee bean and other dust that can contribute to work-related asthma, and diacetyl and 2,3-pentanedione that can contribute to obliterative bronchiolitis. Healthcare providers and occupational health and safety practitioners should be aware that workers at coffee roasting and packaging facilities are potentially at risk for occupational lung diseases.

Melanoidins from Coffee, Cocoa, and Bread Are Able to Scavenge α-Dicarbonyl Compounds under Simulated Physiological Conditions.

Free amino residues react with α-dicarbonyl compounds (DCs) contributing to the formation of advanced glycation end products (AGEs). Phenolic compounds can scavenge DCs, thus controlling the dietary carbonyl load. This study showed that high-molecular weight cocoa melanoidins (HMW-COM), HMW bread melanoidins (HMW-BM), and especially HMW coffee melanoidins (HMW-CM) are effective DC scavengers. HMW-CM (1 mg/mL) scavenged more than 40% DCs within 2 h under simulated physiological conditions, suggesting some physiological relevance. Partial acid hydrolysis of HMW-CM decreased the dicarbonyl trapping capacity, demonstrating that the ability to react with glyoxal, methylglyoxal (MGO), and diacetyl was mainly because of polyphenols bound to macromolecules. Caffeic acid (CA) and 3-caffeoylquinic acid showed a DC-scavenging kinetic profile similar to that of HMW-CM, while mass spectrometry data confirmed that hydroxyalkylation and aromatic substitution reactions led to the formation of a stable adduct between CA and MGO. These findings corroborated the idea that antioxidant-rich indigestible materials could limit carbonyl stress and AGE formation across the gastrointestinal tract.

Measurement of Diacetyl and 2,3-Pentanedione in the Coffee Industry Using Thermal Desorption Tubes and Gas Chromatography-Mass Spectrometry.

Diacetyl is a potentially harmful chemical that is used as an artificial flavouring in the food industry and may also be generated during processing of some natural products including coffee. In Europe, an 8-h time weighted average occupational exposure limit (TWA-OEL) of 20 ppb has been adopted for diacetyl, together with a short-term exposure limit (STEL) of 100 ppb. A new measurement method involving sampling on thermal desorption tubes and analysis by gas chromatography-mass spectrometry has been used to investigate potential exposure to diacetyl, and the related compound 2,3-pentanedione, at eight companies involved in the coffee industry including large- and small-scale manufacturers and coffee shops. A total of 124 static and personal samples were collected. In the majority of personal samples airborne concentrations of diacetyl were <5 ppb, with those at coffee shops generally <1 ppb. However, diacetyl concentrations in ~40% of the long-term personal samples, mainly originating from one site, were found to be in excess of the newly adopted European TWA-OEL of 20 ppb. Diacetyl concentrations up to 400 ppb were detected on the static samples, with the highest values occurring during grinding of roasted coffee beans. 2,3-Pentanedione was also detected in most of the samples at airborne concentrations around half of those for diacetyl. A significant number of other volatile organic compounds (VOCs) were also detected at sub-ppm concentrations, including acetoin, aliphatic carboxylic acids, aldehydes, ketones and esters, methylfuran, furfural and furfuryl-based alcohols and ketones, and nitrogen containing compounds, such as pyridines and pyrazines. In laboratory tests, diacetyl emissions generated during heating of whole beans were found to be significantly lower than those from heating the same beans after grinding. Diacetyl emissions from both ground and whole beans were also found to be significantly dependent on temperature.

Determination of glyoxal, methylglyoxal, and diacetyl in red ginseng products using dispersive liquid-liquid microextraction coupled with GC-MS.

A simple and rapid dispersive liquid-liquid microextraction method coupled with gas chromatography and mass spectrometry was applied for the determination of glyoxal as quinoxaline, methylglyoxal as 2-methylquinoxaline, and diacetyl as 2,3-dimethylquinoxaline in red ginseng products. The performance of the proposed method was evaluated under optimum extraction conditions (extraction solvent: chloroform 100 µL, disperser solvent: methanol 200 µL, derivatizing agent concentration: 5 g/L, reaction time: 1 h, and no addition of salt). The limit of detection and limit of quantitation were 1.30 and 4.33 µg/L for glyoxal, 1.86 and 6.20 µg/L for methylglyoxal, and 1.45 and 4.82 µg/L for diacetyl. The intra- and interday relative standard deviations were <4.95 and 5.80%, respectively. The relative recoveries were 92.4-103.9% in red ginseng concentrate and 99.4-110.7% in juice samples. Red ginseng concentrates were found to contain 191-4274 µg/kg of glyoxal, 1336-4798 µg/kg of methylglyoxal, and 0-830 µg/kg of diacetyl, whereas for red ginseng juices, the respective concentrations were 72-865, 69-3613, and 6-344 µg/L.

Mrakia gelida in brewing process: An innovative production of low alcohol beer using a psychrophilic yeast strain.

Due to the increasing consumer demand, the production of low alcoholic and non alcoholic beer is the new goal of the present brewing producers. Although the beer with reduced alcohol content is currently obtained by physical methods, the use of non-Saccharomyces yeast, with low fermentations capacities, may represent an interesting biological approach. In this study the ethanol content and the volatile profile of a beer obtained using the basidiomycetous psychrophilic yeast strain Mrakia gelida DBVPG 5952 was compared with that produced by a commercial starter for low alcohol beers, Saccharomycodes ludwigii WSL17. The two beers were characterized by a low alcohol content (1.40% and 1.32% v/v) and by a low diacetyl production (5.04 and 5.20 µg/L). However, the organoleptic characteristics of the beer obtained using M. gelida are more appreciated by the panelists, in comparison to the analogous produced with the commercial strain of S. ludwigii.

Effect of Furan Fatty Acids and 3-Methyl-2,4-nonanedione on Light-Induced Off-Odor in Soybean Oil.

Soybean oil is one of the most widely consumed vegetable oils. However, under photooxidative conditions, this oil develops a beany and green off-odor through a mechanism that has not yet been elucidated. Upon photooxidation, 3-methyl-2,4-nonanedione (3-MND) produces a strong aroma. In this study, the effect of furan fatty acids and 3-MND on odor reversion in soybean oil was investigated. Our findings suggest that the observed light-induced off-odor was likely attributable to the furan fatty acids present in the oil through the generation of 3-MND. While 3-MND may not be directly responsible for the development of light-induced off-odor, this compound appears to be involved because off-odor was detected in canola oil samples containing added 3-MND. In addition, in the present work, 3-hydroxy-3-methyl-2,4-nonanedione, which is derived from 3-MND, was identified for the first time in light-exposed soybean oil and shown to be one of the compounds responsible for odor reversion.

The Broadly Tuned Odorant Receptor OR1A1 is Highly Selective for 3-Methyl-2,4-nonanedione, a Key Food Odorant in Aged Wines, Tea, and Other Foods.

Key food odorants are the most relevant determinants by which we detect, recognize, and hedonically evaluate the aroma of foods and beverages. Odorants are detected by our chemical sense of olfaction, comprising a set of approximately 400 different odorant receptor types. However, the specific receptor activity patterns representing the aroma percepts of foods or beverages, as well as the key food odorant agonist profiles of single-odorant receptors, are largely unknown. We aimed to establish comprehensive key food odorant agonist profiles of 2 unrelated, broadly tuned receptors, OR1A1 and OR2W1, that had been associated thus far with mostly non-key food odorants and shared some of these agonists. By screening both receptors against 190 key food odorants in a cell-based luminescence assay, we identified 14 and 18 new key food odorant agonists for OR1A1 and OR2W1, respectively, with 3-methyl-2,4-nonanedione emerging as the most potent agonist for OR1A1 by 3 orders of magnitude, with a submicromolar half maximal effective concentration. 3-Methyl-2,4-nonanedione has been associated with a prune note in oxidized wine and is an aroma determinant in tea and apricots. Further screening against the entire set of 391 human odorant receptors revealed that 30 or 300 µmol/L 3-methyl-2,4-nonanedione activated only 1 receptor, OR1A1, suggesting a unique role of OR1A1 for the most sensitive detection of this key food odorant in wine, tea, and other food matrices.