Ryan F. LeBouf

Formulation and stability of a novel artificial human sweat under conditions of storage and use

A limitation of most artificial sweat formulations used for in vitro assessment of chemical release from materials in contact with skin have little biological relevance to human sweat. The purposes of this paper are to provide guidance for preparation of a novel artificial sweat with chemical constituents at concentrations that match human sweat and to characterize chemical stability. The artificial sweat was characterized under conditions of use (with and without sebum at 36 degrees C) and storage (without sebum at -4, 4, and 23 degrees C) over 28 days by gas chromatography-mass spectroscopy, high-performance liquid chromatography, enzymatic assay kits, and ion-selective electrodes. Seven indicator constituents were tracked: sodium, chloride, glucose, lactic acid, urea, pantothenic acid, and alanine. With or without sebum at 36 degrees C, the sweat solvent was chemically stable for 14 days. Storage by refrigeration at 4 degrees C retained the chemical integrity of the solvent longest. Based on these results, the solvent should be used within 14 days of preparation. The artificial sweat model presented herein is most similar to human sweat and has applications as a dissolution solvent, donor solution in diffusion cells, or vehicle for patch testing. This sweat model may aid researchers in understanding potential release and percutaneous absorption of chemicals in contact with human skin surface liquids.

Characterization of silver nanoparticles in selected consumer products and its relevance for predicting children’s potential exposures

Due to their antifungal, antibacterial, antiviral, and antimicrobial properties, silver nanoparticles (AgNPs) are used in consumer products intended for use by children or in the home. Children may be especially affected by the normal use of consumer products because of their physiological functions, developmental stage, and activities and behaviors. Despite much research to date, childrens potential exposures to AgNPs are not well characterized. Our objectives were to characterize selected consumer products containing AgNPs and to use the data to estimate a childs potential non-dietary ingestion exposure. We identified and cataloged 165 consumer products claiming to contain AgNPs that may be used by or near children or found in the home. Nineteen products (textile, liquid, plastic) were selected for further analysis. We developed a tiered analytical approach to determine silver content, form (particulate or ionic), size, morphology, agglomeration state, and composition. Silver was detected in all products except one sippy cup body. Among products in a given category, silver mass contributions were highly variable and not always uniformly distributed within products, highlighting the need to sample multiple areas of a product. Electron microscopy confirmed the presence of AgNPs. Using this data, a childs potential non-dietary ingestion exposure to AgNPs when drinking milk formula from a sippy cup is 1.53 μg Ag/kg. Additional research is needed to understand the number and types of consumer products containing silver and the concentrations of silver in these products in order to more accurately predict childrens potential aggregate and cumulative exposures to AgNPs.

Identification and Measurement of Diacetyl Substitutes in Dry Bakery Mix Production

In 2008, a company using multiple buttermilk flavorings in the production of dry bakery mixes replaced one liquid flavoring containing 15–20% diacetyl with a proprietary substitute meant to lower occupational risk for diacetyl-related bronchiolitis obliterans. Subsequently, the National Institute for Occupational Safety and Health (NIOSH) evaluated buttermilk flavoring-related exposures at this companys facility, with a focus on measuring ketones by several methods. Volatile organic compounds (VOCs) were evaluated in the headspaces of six bulk flavorings samples, including the substitute buttermilk flavoring. Ketones were evaluated in workplace air via area and personal samples collected during batch preparation of the substitute buttermilk flavoring and production of a bakery mix containing the same flavoring. Air samples were evaluated using five different methods: NIOSH 2549, Modified OSHA PV2118, OSHA 1013, NIOSH Draft Procedure SMP2, and evacuated canisters. Of five buttermilk flavorings from five different flavorings manufacturers, diacetyl was present in four, including the substitute flavoring; acetoin in two; 2,3-pentanedione in four; 2,3-hexanedione in one; and 2,3-heptanedione in three. Among material safety data sheets (MSDS) for four flavorings, only one listed a hazardous ingredient, which was acetoin. The predominant flavoring ingredient identified in the headspace of the substitute flavoring was 2,3-pentanedione; all other chemicals noted above were also present. Diacetyl and 2,3-pentanedione were measured in workplace air via evacuated canisters. In one area and one personal air sample, 2,3-pentanedione was measured by OSHA Method 1013 at concentrations of 78 and 91 ppb, respectively. Without their or the employers knowledge, workers who used buttermilk flavorings were exposed to substitute ketones from many flavorings manufacturers. Because 2,3-pentanedione, 2,3-hexanedione, and 2,3-heptanedione all share the same functional α-diketone group as diacetyl, these compounds also may share diacetyls mechanism of toxicity. Until more is known about 2,3-pentanedione and other α-diketone compounds, they should not be assumed to be safe. Companies using artificial buttermilk flavorings should use a precautionary approach that assumes these flavorings pose a health risk and limit exposures through engineering and administrative controls and use of personal protective equipment.

Dermal exposure potential from textiles that contain silver nanoparticles

Abstract Background: Factors that influence exposure to silver particles from the use of textiles are not well understood. Objectives: The aim of this study was to evaluate the influence of product treatment and physiological factors on silver release from two textiles. Methods: Atomic and absorbance spectroscopy, electron microscopy, and dynamic light scattering (DLS) were applied to characterize the chemical and physical properties of the textiles and evaluate silver release in artificial sweat and saliva under varying physiological conditions. One textile had silver incorporated into fiber threads (masterbatch process) and the other had silver nanoparticles coated on fiber surfaces (finishing process). Results: Several complementary and confirmatory analytical techniques (spectroscopy, microscopy, etc.) were required to properly assess silver release. Silver released into artificial sweat or saliva was primarily in ionic form. In a simulated “use” and laundering experiment, the total cumulative amount of silver ion released was greater for the finishing process textile (0·51±0·04%) than the masterbatch process textile (0·21±0·01%); P<0·01. Conclusions: We found that the process (masterbatch vs finishing) used to treat textile fibers was a more influential exposure factor than physiological properties of artificial sweat or saliva.

Characterization of cleaning and disinfecting tasks and product use among hospital occupations

BACKGROUND Healthcare workers have an elevated prevalence of asthma and related symptoms associated with the use of cleaning/disinfecting products. The objective of this study was to identify and characterize cleaning/disinfecting tasks and products used among hospital occupations. METHODS Workers from 14 occupations at five hospitals were monitored for 216 shifts, and work tasks and products used were recorded at five-minute intervals. The major chemical constituents of each product were identified from safety data sheets. RESULTS Cleaning and disinfecting tasks were performed with a high frequency at least once per shift in many occupations. Medical equipment preparers, housekeepers, floor strippers/waxers, and endoscopy technicians spent on average 108-177 min/shift performing cleaning/disinfecting tasks. Many occupations used products containing amines and quaternary ammonium compounds for >100 min/shift. CONCLUSIONS This analysis demonstrates that many occupations besides housekeeping incur exposures to cleaning/disinfecting products, albeit for different durations and using products containing different chemicals.

Emission of particulate matter from a desktop three-dimensional (3D) printer

ABSTRACT Desktop three-dimensional (3D) printers are becoming commonplace in business offices, public libraries, university labs and classrooms, and even private homes; however, these settings are generally not designed for exposure control. Prior experience with a variety of office equipment devices such as laser printers that emit ultrafine particles (UFP) suggests the need to characterize 3D printer emissions to enable reliable risk assessment. The aim of this study was to examine factors that influence particulate emissions from 3D printers and characterize their physical properties to inform risk assessment. Emissions were evaluated in a 0.5-m3 chamber and in a small room (32.7 m3) using real-time instrumentation to measure particle number, size distribution, mass, and surface area. Factors evaluated included filament composition and color, as well as the manufacturer-provided printer emissions control technologies while printing an object. Filament type significantly influenced emissions, with acrylonitrile butadiene styrene (ABS) emitting larger particles than polylactic acid (PLA), which may have been the result of agglomeration. Geometric mean particle sizes and total particle (TP) number and mass emissions differed significantly among colors of a given filament type. Use of a cover on the printer reduced TP emissions by a factor of 2. Lung deposition calculations indicated a threefold higher PLA particle deposition in alveoli compared to ABS. Desktop 3D printers emit high levels of UFP, which are released into indoor environments where adequate ventilation may not be present to control emissions. Emissions in nonindustrial settings need to be reduced through the use of a hierarchy of controls, beginning with device design, followed by engineering controls (ventilation) and administrative controls such as choice of filament composition and color.

Exposure to volatile organic compounds in healthcare settings

Objectives To identify and summarise volatile organic compound (VOC) exposure profiles of healthcare occupations. Methods Personal (n=143) and mobile area (n=207) evacuated canisters were collected and analysed by a gas chromatograph/mass spectrometer to assess exposures to 14 VOCs among 14 healthcare occupations in five hospitals. Participants were volunteers identified by their supervisors. Summary statistics were calculated by occupation. Principal component analysis (PCA) was used to reduce the 14 analyte inputs to five orthogonal factors and identify occupations that were associated with these factors. Linear regressions were used to assess the association between personal and mobile area samples. Results Exposure profiles differed among occupations; ethanol had the highest geometric mean (GM) among nursing assistants (∼4900 and ∼1900 µg/m3, personal and area), and 2-propanol had the highest GM among medical equipment preparers (∼4600 and ∼2000 µg/m3, personal and area). The highest total personal VOC exposures were among nursing assistants (∼9200 µg/m3), licensed practical nurses (∼8700 µg/m3) and medical equipment preparers (∼7900 µg/m3). The influence of the PCA factors developed from personal exposure estimates varied by occupation, which enabled a comparative assessment of occupations. For example, factor 1, indicative of solvent use, was positively correlated with clinical laboratory and floor stripping/waxing occupations and tasks. Overall, a significant correlation was observed (r=0.88) between matched personal and mobile area samples, but varied considerably by analyte (r=0.23–0.64). Conclusions Healthcare workers are exposed to a variety of chemicals that vary with the activities and products used during activities. These VOC profiles are useful for estimating exposures for occupational hazard ranking for industrial hygienists as well as epidemiological studies.

Respiratory symptoms and lung function abnormalities related to work at a flavouring manufacturing facility

Objectives To better understand respiratory symptoms and lung function in flavouring manufacturing workers. Methods We offered a questionnaire and lung function testing to the current workforce of a flavouring manufacturing facility that had transitioned away from diacetyl and towards substitutes in recent years. We examined symptoms, spirometric parameters and diffusing capacity measurements by exposure variables, including facility tenure and time spent daily in production areas. We used linear and logistic regression to develop final models adjusted for age and smoking status. Results A total of 367 (93%) current workers participated. Shortness of breath was twice as common in those with tenure ≥7 years (OR 2.0, 95% CI 1.1 to 3.6). Other chest symptoms were associated with time spent daily in production. Participants who spent ≥1 h daily in production areas had twice the odds of any spirometric abnormality (OR 2.3; 95% CI 1.1 to 5.3) and three times the odds of low diffusing capacity (OR 2.8; 95% CI 0.9 to 9.4) than other participants. Mean spirometric parameters were significantly lower in those with tenure ≥7 years and those who spent ≥1 h daily in production. Mean diffusing capacity parameters were significantly lower in those with tenure ≥7 years. Differences in symptoms and lung function could not be explained by age, smoking status or employment at another flavouring plant. Conclusions Symptoms and lung function findings were consistent with undiagnosed or subclinical obliterative bronchiolitis and associated with workplace exposures. Further efforts to lower exposures to flavouring chemicals, including diacetyl substitutes, are warranted.

Respiratory Morbidity in a Coffee Processing Workplace With Sentinel Obliterative Bronchiolitis Cases

RATIONALE Obliterative bronchiolitis in former coffee workers prompted a cross-sectional study of current workers. Diacetyl and 2,3-pentanedione levels were highest in areas for flavoring and grinding/packaging unflavored coffee. METHODS We interviewed 75 (88%) workers, measured lung function, and created exposure groups based on work history. We calculated standardized morbidity ratios (SMRs) for symptoms and spirometric abnormalities. We examined health outcomes by exposure groups. RESULTS SMRs were elevated 1.6-fold for dyspnea and 2.7-fold for obstruction. 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. CONCLUSION Current workers have occupational lung morbidity associated with high diacetyl and 2,3-pentanedione exposures, which were not limited to flavoring areas.

Validation of evacuated canisters for sampling volatile organic compounds in healthcare settings

Healthcare settings present a challenging environment for assessing low-level concentrations of specific volatile organic compounds (VOCs) in the presence of high background concentrations of alcohol from the use of hand sanitizers and surface disinfectants. The purposes of this laboratory-based project were to develop and validate a sampling and analysis methodology for quantifying low-level VOC concentrations as well as high-level alcohol concentrations found together in healthcare settings. Sampling was conducted using evacuated canisters lined with fused silica. Gas chromatography/mass spectrometry analysis was performed using preconcentration (for ppb levels) and loop injection (for ppm levels). For a select list of 14 VOCs, bias, precision, and accuracy of both the preconcentration and loop injection methods were evaluated, as was analyte stability in evacuated canisters over 30 days. Using the preconcentration (ppb-level) method, all validation criteria were met for 13 of the 14 target analytes-ethanol, acetone, methylene chloride, hexane, chloroform, benzene, methyl methacrylate, toluene, ethylbenzene, m,p-xylene, o-xylene, alpha-pinene, and limonene. Using the loop injection (ppm-level) method, all validation criteria were met for each analyte. At ppm levels, alpha-pinene and limonene remained stable over 21 days, while the rest of the analytes were stable for 30 days. All analytes remained stable over 30 days at ppb levels. This sampling and analysis approach is a viable (i.e., accurate and stable) methodology that will enable development of VOC profiles for mixed exposures experienced by healthcare workers.