Jose Vallarino

Identification of selected hormonally active agents and animal mammary carcinogens in commercial and residential air and dust samples

ABSTRACT In order to characterize typical indoor exposures to chemicals of interest for research on breast cancer and other hormonally mediated health outcomes, methods were developed to analyze air and dust for target compounds that have been identified as animal mammary carcinogens or hormonally active agents and that are used in commercial or consumer products or building materials. These methods were applied to a small number of residential and commercial environments to begin to characterize the extent of exposure to these classes of compounds. Phenolic compounds, including nonylphenol, octylphenol, bisphenol A, and the methoxychlor metabolite 2,2-bis (p-hydroxyphenyl)-1,1,1-trichloroethane (HPTE), were extracted, derivatized, and analyzed by gas chromatography/mass spectrometry (GC/MS)–selective ion monitoring (SIM). Selected phthalates, pesticides, polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs) were extracted and analyzed by GC/MS-SIM. Residential and workplace samples showed detectable levels of twelve pesticides in dust and seven in air samples. Phthalates were abundant in dust (0.3524 μg/g) and air (0.005-2.8 μg/m3). Nonylphenol and its mono- and di-ethoxylates were prevalent in dust (0.82-14 μg/g) along with estrogenic phenols such as bisphenol A and o-phenyl phenol. In this 7-sample pilot study, 33 of 86 target compounds were detected in dust, and 24 of 57 target compounds were detected in air. In a single sample from one home, 27 of the target compounds were detected in dust and 15 in air, providing an indication of chemical mixtures to which humans are typically exposed.

Associations of Cognitive Function Scores with Carbon Dioxide, Ventilation, and Volatile Organic Compound Exposures in Office Workers: A Controlled Exposure Study of Green and Conventional Office Environments.

Background: The indoor built environment plays a critical role in our overall well-being because of both the amount of time we spend indoors (~90%) and the ability of buildings to positively or negatively influence our health. The advent of sustainable design or green building strategies reinvigorated questions regarding the specific factors in buildings that lead to optimized conditions for health and productivity. Objective: We simulated indoor environmental quality (IEQ) conditions in “Green” and “Conventional” buildings and evaluated the impacts on an objective measure of human performance: higher-order cognitive function. Methods: Twenty-four participants spent 6 full work days (0900–1700 hours) in an environmentally controlled office space, blinded to test conditions. On different days, they were exposed to IEQ conditions representative of Conventional [high concentrations of volatile organic compounds (VOCs)] and Green (low concentrations of VOCs) office buildings in the United States. Additional conditions simulated a Green building with a high outdoor air ventilation rate (labeled Green+) and artificially elevated carbon dioxide (CO2) levels independent of ventilation. Results: On average, cognitive scores were 61% higher on the Green building day and 101% higher on the two Green+ building days than on the Conventional building day (p < 0.0001). VOCs and CO2 were independently associated with cognitive scores. Conclusions: Cognitive function scores were significantly better under Green+ building conditions than in the Conventional building conditions for all nine functional domains. These findings have wide-ranging implications because this study was designed to reflect conditions that are commonly encountered every day in many indoor environments. Citation: Allen JG, MacNaughton P, Satish U, Santanam S, Vallarino J, Spengler JD. 2016. Associations of cognitive function scores with carbon dioxide, ventilation, and volatile organic compound exposures in office workers: a controlled exposure study of green and conventional office environments. Environ Health Perspect 124:805–812; http://dx.doi.org/10.1289/ehp.1510037

Criteria air pollutants and toxic air pollutants.

This review presents a brief overview of the health effects and exposures of two criteria pollutants--ozone and particulate matter--and two toxic air pollutants--benzene and formaldehyde. These pollutants were selected from the six criteria pollutants and from the 189 toxic air pollutants on the basis of their prevalence in the United States, their physicochemical behavior, and the magnitude of their potential health threat. The health effects data included in this review primarily include results from epidemiologic studies; however, some findings from animal studies are also discussed when no other information is available. Health effects findings for each pollutant are related in this review to corresponding information about outdoor, indoor, and personal exposures and pollutant sources. ImagesFigure 3Figure 8Figure 9

Flavoring Chemicals in E-Cigarettes: Diacetyl, 2,3-Pentanedione, and Acetoin in a Sample of 51 Products, Including Fruit-, Candy-, and Cocktail-Flavored E-Cigarettes

Background: There are > 7,000 e-cigarette flavors currently marketed. Flavoring chemicals gained notoriety in the early 2000s when inhalation exposure of the flavoring chemical diacetyl was found to be associated with a disease that became known as “popcorn lung.” There has been limited research on flavoring chemicals in e-cigarettes. Objective: We aimed to determine if the flavoring chemical diacetyl and two other high-priority flavoring chemicals, 2,3-pentanedione and acetoin, are present in a convenience sample of flavored e-cigarettes. Methods: We selected 51 types of flavored e-cigarettes sold by leading e-cigarette brands and flavors we deemed were appealing to youth. E-cigarette contents were fully discharged and the air stream was captured and analyzed for total mass of diacetyl, 2,3-pentanedione, and acetoin, according to OSHA method 1012. Results: At least one flavoring chemical was detected in 47 of 51 unique flavors tested. Diacetyl was detected above the laboratory limit of detection in 39 of the 51 flavors tested, ranging from below the limit of quantification to 239 μg/e-cigarette. 2,3-Pentanedione and acetoin were detected in 23 and 46 of the 51 flavors tested at concentrations up to 64 and 529 μg/e-cigarette, respectively. Conclusion: Because of the associations between diacetyl and bronchiolitis obliterans and other severe respiratory diseases observed in workers, urgent action is recommended to further evaluate this potentially widespread exposure via flavored e-cigarettes. Citation: Allen JG, Flanigan SS, LeBlanc M, Vallarino J, MacNaughton P, Stewart JH, Christiani DC. 2016. Flavoring chemicals in e-cigarettes: diacetyl, 2,3-pentanedione, and acetoin in a sample of 51 products, including fruit-, candy-, and cocktail-flavored e-cigarettes. Environ Health Perspect 124:733–739; http://dx.doi.org/10.1289/ehp.1510185

Response to “Comment on ‘Flavoring Chemicals in E-Cigarettes: Diacetyl, 2,3-Pentanedione, and Acetoin in a Sample of 51 Products, Including Fruit-, Candy-, and Cocktail-Flavored E-Cigarettes’”

We appreciate the opportunity to respond to the letter to the editor from Pierce et al. Nowhere do Pierce et al. identify any factual errors in our work; our key findings stand. We will, however, take this opportunity to address several of the points they raised. In their analysis comparing diacetyl in e-cigs to occupational exposure limits (OELs), Pierce et al. selectively chose to evaluate only the median (6.0 µg/e-cigarette for diacetyl and 1.6 µg/e-cigarette for 2,3-pentanedione) from our data to reinforce their point that exposures are below the OEL they derived (176 μg/day for diacetyl). In choosing only the median, Pierce et al. ignored that our study found, in a sample of only 51 of over 7,000 flavors, a flavored e-cigarette with a diacetyl concentration of 238 µg/e-cigarette, which exceeds the 176 µg/day OEL they calculated. There is additional support in the literature showing the potential to exceed their derived OEL, as well, including a paper cited by Pierce et al. Farsalinos et al. (2015) measured diacetyl directly in the liquid of e-cigarettes and then used this to estimate a daily dose (median = 6 μg/day; interquartile range: 26–278 μg/day). The 75th percentile concentration in Farsalinos et al. (2015) exceeds the daily dose limit of 176 µg/day that Pierce et al. used. Therefore, at least 25% of flavored e-cigarettes samples in the Farsalinos et al. (2015) paper would exceed the 176 µg/day limit derived by Pierce et al. We also want to reiterate our position, stated clearly in the discussion section of our paper along with our rationale, that the use of OELs for this population is inappropriate. Our position is in agreement with NIOSH, which published a response to the paper by Farsalinos et al. (2015) in which they stated that OELS are “…not intended to establish “safe” exposure concentrations for consumers or the general public” (Hubbs et al., 2015). Pierce et al. also misrepresent the findings of their own earlier work (Gaffney et al. 2015; Pierce et al. 2014; Pierce et al. 2015) in which diacetyl and 2,3-pentanedione levels were measured. In their letter they stated that “Over the past five years, we have published the results of several studies in which diacetyl and 2,3-pentanedione levels were measured in various consumer products.” As evident by the dates in the in-line citation, all 3 of their papers cited were published within 1.5 years; they do not have a 5-year record of publishing on this topic. Further, the ‘various consumer products’ include only 2 products: cigarettes and coffee. Additionally, in their letter they directly contradict the conclusions in their earlier work. In this letter they state “Gaffney et al. (2015) and Pierce et al. (2015) found that grinding, brewing, and consuming unflavored coffee was associated with airborne diacetyl concentrations that were several times higher than the NIOSH and ACGIH short-term (0.025 and 0.020 ppm, respectively) and 8-hour (0.005 and 0.010 ppm, respectively) OELs for diacetyl.” This is inaccurate and inconsistent with their own paper published in 2015. For workers brewing coffee, they actually state the exact opposite in the Pierce et al. (2015) paper: “None of the individual short-term (15 min) barista samples (maximum of 0.01 ppm) exceeded the proposed NIOSH or ACGIH STELs (0.025 ppm and 0.02 ppm, respectively).” And for customers consuming unflavored coffee, the maximum 8-hour exposure reported in their simulation (0.005 ppm; Table 2) was below the ACGIH 8-hour limit (0.010 ppm), and it was at the NIOSH recommended exposure limit (0.005 ppm), not above it, and certainly not “several times higher” than either limit (Pierce et al. 2015). We further note that Pierce et al. (2015) and Gaffney et al. (2014) appear not to have been peer reviewed, based on the short time between submission and publication (received, revised and accepted all in 3 and 1 days, respectively). Also, the 2 papers are on the same topic, were received by the same journal within 2 days of each other, and contain 6 identical and 12 nearly identical sentences, although only 1 discloses the funding source as being from two companies involved in diacetyl litigation. Furthermore, the exposure data reported in Pierce et al. (2015) were collected not in a coffee shop but in a small kitchen with a very low ventilation rate that we calculate to be well below the ASHRAE minimum ventilation rates for cafeterias/fast food dining of 19 ft3/min/person (ASHRAE 2013). Pierce et al. attempt to minimize risks by comparing flavored e-cigarettes and coffee beans, commenting, “Unless one assumes that unflavored coffee beans pose a serious risk of ‘popcorn lung,’ a rare and oftentimes lethal disease, then one should agree that exposures to airborne diketone levels above the NIOSH and ACGIH OELs are not necessarily indicative of respiratory risk.” They do not seem to be aware that, in fact, several workers at a coffee processing workplace were recently diagnosed with bronchiolitis obliterans (“popcorn lung”), and NIOSH’s investigation found a 2.7-fold elevated standard mortality ratio for obstruction for workers at this site (Bailey et al. 2015). The NIOSH investigation concluded that, “The exposure group working in both coffee flavoring and grinding/packaging of unflavored coffee areas had significantly lower mean ratio of forced expiratory volume in 1 s to forced vital capacity and percent predicted mid-expiratory flow than workers without such exposure,” and “Current workers have occupational lung morbidity associated with high diacetyl and 2,3-pentanedione exposures, which were not limited to flavoring areas.” Finally, Pierce et al.’s comparison of diketone exposures from e-cigarettes and cigarettes, and their assertion of an increase in diketone exposure by not switching to e-cigarettes, misses a major point. Nearly 2 million children have tried e-cigarettes, 160,000 of whom reported that they had not used cigarettes (CDC 2013). Pierce et al. stated, “Ironically, suggesting that diketone levels in e-cigarettes are potentially dangerous could actually lead to higher diketone exposures in the smoking population if smokers decide not to switch to e-cigarettes due to as yet unfounded health concerns.” What about the 160,000 children who tried e-cigarettes who had not used cigarettes? We see no irony. In conclusion, we stand by our work and the facts presented in our paper: diacetyl and other flavoring chemicals are in many flavored e-cigarettes, including flavors, like cupcake and cotton candy, that we deem are particularly appealing to kids. Considering the history of severe and irreversible lung disease associated with some workers who inhaled diacetyl, and the similar exposure pathways for consumers of flavored e-cigarettes, it is prudent to evaluate this potential hazard further, restrict access by youth, and provide consumers with information and warnings similar to those given to workers.

Ozone Decay Rates in Residences

In urban and suburban settings, indoor ozone exposures can represent a significant fraction of an individuals 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.

Air Pollution in Accra Neighborhoods: Spatial, Socioeconomic, and Temporal Patterns

This study examined the spatial, socioeconomic status (SES), and temporal patterns of ambient air pollution in Accra, Ghana. Over 22 months, integrated and continuous rooftop particulate matter (PM) monitors were placed at a total of 11 residential or roadside monitoring sites in four neighborhoods of varying SES and biomass fuel use. PM concentrations were highest in late December and January, due to dust blown from the Sahara. Excluding this period, annual PM(2.5) ranged from 39 to 53 microg/m(3) at roadside sites and 30 to 70 microg/m(3) at residential sites; mean annual PM(10) ranged from 80 to 108 microg/m(3) at roadside sites and 57 to 106 microg/m(3) at residential sites. The low-income and densely populated neighborhood of Jamestown/Ushertown had the single highest residential PM concentration. There was less difference across traffic sites. Daily PM increased at all sites at daybreak, followed by a mid-day peak at some sites, and a more spread-out evening peak at all sites. Average carbon monoxide concentrations at different sites and seasons ranged from 7 to 55 ppm, and were generally lower at residential sites than at traffic sites. The results show that PM in these four neighborhoods is substantially higher than the WHO Air Quality Guidelines and in some cases even higher than the WHO Interim Target 1, with the highest pollution in the poorest neighborhood.

Within-Neighborhood Patterns and Sources of Particle Pollution: Mobile Monitoring and Geographic Information System Analysis in Four Communities in Accra, Ghana

Background Sources of air pollution in developing country cities include transportation and industrial pollution, biomass and coal fuel use, and resuspended dust from unpaved roads. Objectives Our goal was to understand within-neighborhood spatial variability of particulate matter (PM) in communities of varying socioeconomic status (SES) in Accra, Ghana, and to quantify the effects of nearby sources on local PM concentration. Methods We conducted 1 week of morning and afternoon mobile and stationary air pollution measurements in four study neighborhoods. PM with aerodynamic diameters ≤ 2.5 μm (PM2.5) and ≤ 10 μm (PM10) was measured continuously, with matched global positioning system coordinates; detailed data on local sources were collected at periodic stops. The effects of nearby sources on local PM were estimated using linear mixed-effects models. Results In our measurement campaign, the geometric means of PM2.5 and PM10 along the mobile monitoring path were 21 and 49 μg/m3, respectively, in the neighborhood with highest SES and 39 and 96 μg/m3, respectively, in the neighborhood with lowest SES and highest population density. PM2.5 and PM10 were as high as 200 and 400 μg/m3, respectively, in some segments of the path. After adjusting for other factors, the factors that had the largest effects on local PM pollution were nearby wood and charcoal stoves, congested and heavy traffic, loose dirt road surface, and trash burning. Conclusions Biomass fuels, transportation, and unpaved roads may be important determinants of local PM variation in Accra neighborhoods. If confirmed by additional or supporting data, the results demonstrate the need for effective and equitable interventions and policies that reduce the impacts of traffic and biomass pollution.

Household and community poverty, biomass use, and air pollution in Accra, Ghana

Many urban households in developing countries use biomass fuels for cooking. The proportion of household biomass use varies among neighborhoods, and is generally higher in low socioeconomic status (SES) communities. Little is known of how household air pollution varies by SES and how it is affected by biomass fuels and traffic sources in developing country cities. In four neighborhoods in Accra, Ghana, we collected and analyzed geo-referenced data on household and community particulate matter (PM) pollution, SES, fuel use for domestic and small-commercial cooking, housing characteristics, and distance to major roads. Cooking area PM was lowest in the high-SES neighborhood, with geometric means of 25 (95% confidence interval, 21–29) and 28 (23–33) μg/m3 for fine and coarse PM (PM2.5 and PM2.5–10), respectively; it was highest in two low-SES slums, with geometric means reaching 71 (62–80) and 131 (114–150) μg/m3 for fine and coarse PM. After adjustment for other factors, living in a community where all households use biomass fuels would be associated with 1.5- to 2.7-times PM levels in models with and without adjustment for ambient PM. Community biomass use had a stronger association with household PM than households own fuel choice in crude and adjusted estimates. Lack of regular physical access to clean fuels is an obstacle to fuel switching in low-income neighborhoods and should be addressed through equitable energy infrastructure.

Ozone and ozone byproducts in the cabins of commercial aircraft.

The aircraft cabin represents a unique indoor environment due to its high surface-to-volume ratio, high occupant density, and the potential for high ozone concentrations at cruising altitudes. Ozone was continuously measured and air was sampled on sorbent traps, targeting carbonyl compounds, on 52 transcontinental U.S. or international flights between 2008 and 2010. The sampling was predominantly on planes that did not have ozone scrubbers (catalytic converters). Peak ozone levels on aircraft without catalytic convertors exceeded 100 ppb, with some flights having periods of more than an hour when the ozone levels were >75 ppb. Ozone was greatly reduced on relatively new aircraft with catalytic convertors, but ozone levels on two flights whose aircraft had older convertors were similar to those on planes without catalytic convertors. Hexanal, heptanal, octanal, nonanal, decanal, and 6-methyl-5-hepten-2-one (6-MHO) were detected in the aircraft cabin at sub- to low ppb levels. Linear regression models that included the log transformed mean ozone concentration, percent occupancy, and plane type were statistically significant and explained between 18 and 25% of the variance in the mixing ratio of these carbonyls. Occupancy was also a significant factor for 6-MHO, but not the linear aldehydes, consistent with 6-MHOs formation from the reaction between ozone and squalene, which is present in human skin oils.