Stephen G. Whittaker

Quantification and Statistical Modeling—Part I: Breathing-Zone Concentrations of Monomeric and Polymeric 1,6-Hexamethylene Diisocyanate

We conducted a repeated exposure-assessment survey for task-based breathing-zone concentrations (BZCs) of monomeric and polymeric 1,6-hexamethylene diisocyanate (HDI) during spray painting on 47 automotive spray painters from North Carolina and Washington State. We report here the use of linear mixed modeling to identify the primary determinants of the measured BZCs. Both one-stage (N = 98 paint tasks) and two-stage (N = 198 paint tasks) filter sampling was used to measure concentrations of HDI, uretidone, biuret, and isocyanurate. The geometric mean (GM) level of isocyanurate (1410 microg m(-3)) was higher than all other analytes (i.e. GM < 7.85 microg m(-3)). The mixed models were unique to each analyte and included factors such as analyte-specific paint concentration, airflow in the paint booth, and sampler type. The effect of sampler type was corroborated by side-by-side one- and two-stage personal air sampling (N = 16 paint tasks). According to paired t-tests, significantly higher concentrations of HDI (P = 0.0363) and isocyanurate (P = 0.0035) were measured using one-stage samplers. Marginal R(2) statistics were calculated for each model; significant fixed effects were able to describe 25, 52, 54, and 20% of the variability in BZCs of HDI, uretidone, biuret, and isocyanurate, respectively. Mixed models developed in this study characterize the processes governing individual polyisocyanate BZCs. In addition, the mixed models identify ways to reduce polyisocyanate BZCs and, hence, protect painters from potential adverse health effects.

Quantification and Statistical Modeling—Part II: Dermal Concentrations of Monomeric and Polymeric 1,6-Hexamethylene Diisocyanate

We conducted a quantitative dermal and inhalation exposure assessment of monomeric and polymeric 1,6-hexamethylene diisocyanates (HDI) in 47 automotive spray painters from North Carolina and Washington State. We report here the use of linear mixed modeling (LMM) to identify the primary determinants of dermal exposure. Dermal concentrations of HDI, uretidone, biuret, and isocyanurate were significantly higher in 15 painters who did not wear coveralls or gloves (N = 51 paint tasks) than in 32 painters who did wear coveralls and gloves (N = 192 paint tasks) during spray painting. Regardless of whether protective clothing was worn, isocyanurate was the predominant species measured in the skin [geometric mean (GM) = 33.8 ng mm(-3)], with a 95% detection rate. Other polyisocyanates (GM < or = 0.17 ng mm(-3)) were detected in skin during <23% of the paint tasks. According to marginal R(2) statistics, mixed models generated in this study described no <36% of the variability in dermal concentrations of the different polyisocyanates measured in painters who did not wear protective clothing. These models also described 55% of the variability in dermal concentrations of isocyanurate measured in all painters (N = 288 paint tasks). The product of analyte-specific breathing-zone concentration (BZC) and paint time was the most significant variable in all the models. Through LMM, a better understanding of the exposure pathways governing individual polyisocyanate exposures may be achieved. In particular, we were able to establish a link between BZC and dermal concentration, which may be useful for exposure reconstruction and quantitatively characterizing the protective effect of coveralls and gloves. This information can be used to reduce dermal exposures and better protect automotive spray painters from potential adverse health effects.

Urine 1,6-hexamethylene diamine (HDA) levels among workers exposed to 1,6-hexamethylene diisocyanate (HDI).

Urinary 1,6-hexamethylene diamine (HDA) may serve as a biomarker for systemic exposure to 1,6-hexamethylene diisocyanate (HDI) in occupationally exposed populations. However, the quantitative relationships between dermal and inhalation exposure to HDI and urine HDA levels have not been established. We measured acid-hydrolyzed urine HDA levels along with dermal and breathing-zone levels of HDI in 48 automotive spray painters. These measurements were conducted over the course of an entire workday for up to three separate workdays that were spaced approximately 1 month apart. One urine sample was collected before the start of work with HDI-containing paints and subsequent samples were collected during the workday. HDA levels varied throughout the day and ranged from nondetectable to 65.9 microg l(-1) with a geometric mean and geometric standard deviation of 0.10 microg l(-1) +/- 6.68. Dermal exposure and inhalation exposure levels, adjusted for the type of respirator worn, were both significant predictors of urine HDA levels in the linear mixed models. Creatinine was a significant covariate when used as an independent variable along with dermal and respirator-adjusted inhalation exposure. Consequently, exposure assessment models must account for the water content of a urine sample. These findings indicate that HDA exhibits a biphasic elimination pattern, with a half-life of 2.9 h for the fast elimination phase. Our results also indicate that urine HDA level is significantly associated with systemic HDI exposure through both the skin and the lungs. We conclude that urinary HDA may be used as a biomarker of exposure to HDI, but biological monitoring should be tailored to reliably capture the intermittent exposure pattern typical in this industry.

Characterizing the Health and Safety Needs of the Collision Repair Industry

Production workers in the collision repair industry are potentially exposed to many harmful chemicals, including isocyanates. Of particular concern is the burden of work-related asthma in this industry that likely reflects exposures to the isocyanates in two-part paints. The main objectives of this study were to gather information about: (i) the collision repair industry business model, (ii) the number of collision repair production workers potentially exposed to isocyanates, (iii) additional chemical and physical exposures of concern, (iv) current health and safety practices in the industry, (v) the health and safety perceptions and needs of business owners and managers, and (vi) strategies to reduce exposure and increase employer and worker awareness. Data were gathered using a combination of key informant interviews, field investigations, and a statewide needs assessment survey. Although a response bias cannot be excluded, the 69% response rate suggests that the survey results are likely representative of Washington States collision repair industry. Collision repair was determined to be a male-dominated industry chiefly comprising small, nonunionized, family-run businesses. Many shops face numerous safety and health challenges resulting from a combination of misinformation within the industry, insufficient funds to address workplace health and safety concerns, and social barriers to enforcing best practices within the shops. Most notably, inappropriate selection and use of respirators and gloves likely contribute significantly to isocyanate exposures. Collision repair workers are potentially exposed to a variety of additional chemical and physical hazards that deserve attention. This industry requires health and safety intervention of both an educational campaign and technical assistance. Any such intervention must account for the financial, demographic, and social characteristics of this industry.

Airborne isocyanate exposures in the collision repair industry and a comparison to occupational exposure limits.

Isocyanate exposure was evaluated in 33 spray painters from 25 Washington State autobody shops. Personal breathing zone samples (n = 228) were analyzed for isophorone diisocyanate (IPDI) monomer, 1,6-hexamethylene diisocyanate (HDI) monomer, IPDI polyisocyanate, and three polyisocyanate forms of HDI. The objective was to describe exposures to isocyanates while spray painting, compare them with short-term exposure limits (STELs), and describe the isocyanate composition in the samples. The composition of polyisocyanates (IPDI and HDI) in the samples varied greatly, with maximum amounts ranging from up to 58% for HDI biuret to 96% for HDI isocyanurate. There was a significant inverse relationship between the percentage composition of HDI isocyanurate to IPDI and to HDI uretdione. Two 15-min STELs were compared: (1) Oregons Occupational Safety and Health Administration (OR-OSHA) STEL of 1000 μg/m3 for HDI polyisocyanate, and (2) the United Kingdoms Health and Safety Executive (UK-HSE) STEL of 70 μg NCO/m3 for all isocyanates. Eighty percent of samples containing HDI polyisocyanate exceeded the OR-OSHA STEL while 98% of samples exceeded the UK-HSE STEL. The majority of painters (67%) wore half-face air-purifying respirators while spray painting. Using the OR-OSHA and the UK-HSE STELs as benchmarks, 21% and 67% of painters, respectively, had at least one exposure that exceeded the respirators OSHA-assigned protection factor. A critical review of the STELs revealed the following limitations: (1) the OR-OSHA STEL does not include all polyisocyanates, and (2) the UK-HSE STEL is derived from monomeric isocyanates, whereas the species present in typical spray coatings are polyisocyanates. In conclusion, the variable mixtures of isocyanates used by autobody painters suggest that an occupational exposure limit is required that includes all polyisocyanates. Despite the limitations of the STELs, we determined that a respirator with an assigned protection factor of 25 or greater is required to protect against isocyanate exposures during spray painting. Consequently, half-face air-purifying respirators, which are most commonly used and have an assigned protection factor of 10, do not afford adequate respiratory protection.

Development of a Permeation Panel to Test Dermal Protective Clothing Against Sprayed Coatings

OBJECTIVES Design, construct, and characterize an apparatus to evaluate dermal protective clothing for resistance to polymerizing materials. Specifically, we evaluated the permeation of the most common glove material used in automotive collision repair (0.10-0.13 mm or 4-5 mil latex) with representative isocyanate-containing clear coats. Our ultimate goal is to make informed recommendations on dermal protective materials to prevent isocyanate exposures and reduce the likelihood of occupational illness in automotive collision repair and other industries. METHODS A novel permeation panel was developed to assess dermal protective clothing. With this apparatus, up to eight test materials may be evaluated under typical-spray application conditions. Solid collection media comprised of 1-(2-pyridyl)-piperazine (2-PP)-coated fiberglass filters or colorimetric SWYPE™ pads were placed behind test materials to capture permeants. The 2-PP-coated filters were subsequently analyzed using a modified OSHA42/PV2034 method. Color change in the SWYPEs provided an immediate field estimate of breakthrough time. In addition, Teflon filters were mounted proximal to the permeation cells to measure the mass of clear coat applied to the panel and to evaluate loading homogeneity. This study evaluated the permeation of isocyanates through 0.10-0.13 mm latex glove material at a fixed time (30 min post-spraying) and over a time course (6-91 min post-spraying). RESULTS Monomers 1,6-hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) permeated through (0.10-0.13 mm) latex glove material under typical glove use conditions (30 min). The latex glove material exhibited immediate breakthrough, with a permeation rate of 2.9 ng min(-1) cm(-2). The oligomeric forms of HDI and IPDI did not permeate the latex glove material. The spray application at 71 ± 5 °F was fairly homogeneous (33.7 ± 8 mg weight of dry clear coat per 5 cm(2)). CONCLUSIONS The permeation panel is a viable method to assess dermal protective clothing performance against polymerizing materials. Thin (0.10-0.13 mm) latex gloves were determined to be ineffective barriers to the isocyanates commonly found in clear coats. Because this type of glove is used frequently in auto body shops, the potential for isocyanate exposure is of concern. Permeation tests with other dermal protective clothing materials and other clear coat formulations are needed to make recommendations about alternative materials.

Work-related asthma in the spray-on truck bed lining industry.

Objective: The objective of this study was to identify work-related asthma (WRA) workers’ compensation claims associated with methylene diphenyl diisocyanate (MDI) exposure in the spray-on truck bed lining industry and estimate the asthma incidence rate in this industry. Methods: The authors conducted a descriptive study of workers’ compensation claims meeting an established surveillance case definition for WRA. Results: Eight WRA workers’ compensation claims were identified in the truck bed lining industry in Washington State for a claims incidence rate of 200 per 10,000 full-time equivalent. The medical evaluation of the cases was inadequate because none of the truck bed lining cases had medical testing to objectively link their asthma to the workplace. Conclusions: The rate of work-related asthma in the truck bed lining industry is excessive and suggests a need for significant intervention, including improvements in the clinical assessment provided to MDI-exposed workers.

Hemoglobin adducts in workers exposed to 1,6-hexamethylene diisocyanate

We investigated the utility of 1,6-hexamethylene diamine (HDA) hemoglobin adducts as biomarkers of exposure to 1,6-hexamethylene diisocyanate (HDI) monomer. Blood samples from 15 spray painters applying HDI-containing paint were analyzed for hemoglobin HDA (HDA-Hb) and N-acetyl-1,6-hexamethylene diamine (monoacetyl-HDA-Hb) by GC-MS. HDA-Hb was detected in the majority of workers (≤1.2–37 ng/g Hb), whereas monoacetyl-HDA-Hb was detected in one worker (0.06 ng/g Hb). The stronger, positive association between HDA-Hb and cumulative HDI exposure (r2 = 0.3, p < 0.06) than same day exposure (p ≥ 0.13) indicates long-term elimination kinetics for HDA-Hb adducts. This association demonstrates the suitability of HDA-Hb adducts for further validation as a biomarker of HDI exposure.

Survey of Dermal Protection in Washington State Collision Repair Industry

Substantial exposure to isocyanates may occur during spray painting in autobody shops, yet information is lacking on the efficacy of the protective clothing used during spray painting. We investigated the personal and workplace factors associated with painters’ dermal protection use during a large-scale exposure assessment study. Survey data indicated that 69% of painters always used gloves, with latex gloves (47%) and nitrile gloves (34%) used most frequently. Among latex glove users, 53% used thin latex (0.05–0.13 mm), 6% used medium latex (0.15–0.20 mm), and 12% used thick latex (> 0.20 mm). Among nitrile glove users, 27% used thin nitrile and 45% used medium nitrile. Sixty-three percent of painters always used coveralls, 44% preferring one particular brand. Although overspray presents an opportunity for dermal exposure to the neck and face, only 19% of painters protected these areas with personal protective equipment. Painters who always used coveralls were more likely to use gloves (odds ratio = 7.9, p = 0.061). Painters who reported ever having smoked cigarettes used gloves (p = 0.05) and coveralls (p = 0.04) more frequently. Painters who sprayed more than 34 clear coat jobs per month used coveralls most frequently (p = 0.038). Exact logistic regressions along with random sample calculations indicated that the survey results were independent of the shops. Because of the small sample size in this study, future research is warranted to corroborate these results. Studying the effectiveness of gloves and coveralls against polyurethane paints and understanding the underlying motivators and preferences for painters and business owners is needed for the development of best practices for the selection and use of dermal protection.

Occupational Carbon Monoxide Poisoning in Washington State, 2000–2005

Washington State workers’ compensation data can be used to guide prevention efforts focused on occupational carbon monoxide (CO) poisoning. Between 2000 and 2005, a total of 345 individual claims comprising 221 different exposure incidents were identified for the 6-year time period. The construction industry had 43 (20%) CO incidents, followed by wholesale trade with 32 (15%), and agriculture with 27 (12%) incidents. Fuel-powered forklifts caused 29% of all incidents, while autos/trucks/buses were responsible for 26%. The number of forklift incidents in fruit packing and cold storage companies declined significantly from 1994 through 2007 (Spearmans rho = 0.6659, p < 0.01). While this study used multiple medical records from workers’ compensation claims to identify CO poisoning, a surveillance system that lacks extensive medical records may rely principally on carboxyhemoglobin (COHb) tests. This study demonstrated that 71% of the identified workers’ compensation claims had associated COHb tests. The recurrence and timing of CO poisoning as well as control of the CO-generating source were determined. Approximately 8% of all work sites had recurring CO poisoning incidents. Two percent experienced a recurrent incident within 16 days of the initial incident, and 6% experienced a recurrent incident between 16 days and 3 years after the initial incident. Sixty-seven percent of claimants exposed to CO were not in direct control of the CO-generating source; this has implications for CO prevention and underscores the need for all employees to be trained on CO hazards.