Two-Zone Model Application to Breathing Zone and Area Welding Fume Concentration Data

Recent evidence has suggested the potential for wide-ranging health effects that could result from exposure to carbon nanotubes (CNT) and carbon nanofibers (CNF). In response, the National Institute for Occupational Safety and Health (NIOSH) set a recommended exposure limit (REL) for CNT and CNF: 1 μg m−3 as an 8-h time weighted average (TWA) of elemental carbon (EC) for the respirable size fraction. The purpose of this study was to conduct an industrywide exposure assessment among US CNT and CNF manufacturers and users. Fourteen total sites were visited to assess exposures to CNT (13 sites) and CNF (1 site). Personal breathing zone (PBZ) and area samples were collected for both the inhalable and respirable mass concentration of EC, using NIOSH Method 5040. Inhalable PBZ samples were collected at nine sites while at the remaining five sites both respirable and inhalable PBZ samples were collected side-by-side. Transmission electron microscopy (TEM) PBZ and area samples were also collected at the inhalable size fraction and analyzed to quantify and size CNT and CNF agglomerate and fibrous exposures. Respirable EC PBZ concentrations ranged from 0.02 to 2.94 μg m−3 with a geometric mean (GM) of 0.34 μg m−3 and an 8-h TWA of 0.16 μg m−3. PBZ samples at the inhalable size fraction for EC ranged from 0.01 to 79.57 μg m−3 with a GM of 1.21 μg m−3. PBZ samples analyzed by TEM showed concentrations ranging from 0.0001 to 1.613 CNT or CNF-structures per cm3 with a GM of 0.008 and an 8-h TWA concentration of 0.003. The most common CNT structure sizes were found to be larger agglomerates in the 2–5 μm range as well as agglomerates >5 μm. A statistically significant correlation was observed between the inhalable samples for the mass of EC and structure counts by TEM (Spearman ρ = 0.39, P < 0.0001). Overall, EC PBZ and area TWA samples were below the NIOSH REL (96% were <1 μg m−3 at the respirable size fraction), while 30% of the inhalable PBZ EC samples were found to be >1 μg m−3. Until more information is known about health effects associated with larger agglomerates, it seems prudent to assess worker exposure to airborne CNT and CNF materials by monitoring EC at both the respirable and inhalable size fractions. Concurrent TEM samples should be collected to confirm the presence of CNT and CNF.

A commercial rhodizonate-based test kit was evaluated for its potential use in the detection of lead in airborne particulate samples at work sites. Over 350 air samples were collected at abrasive blasting lead paint abatement sites using cellulose ester membrane filters and personal sampling pumps. The filter samples were tested with the chemical spot test and then analyzed by graphite furnace atomic absorption spectrophotometry. No positive readings were recorded for lead masses below 1.3 micrograms Pb/filter, and no negative readings were observed for lead amounts above 8.1 micrograms Pb/filter. Experimental data were statistically molded in an effort to estimate the performance parameters of the spot test kit. The identification limit of the kit was found to be approximately 3.6 microgram/filter sample. For lead mass values above approximately 10 micrograms Pb/filter, 95% confidence of a positive reading was found, while 95% confidence of a negative reading was found for lead masses below approximately 0.6 micrograms Pb/filter. Based on the results of this study the rhodizonate-based test kit for lead demonstrates potential for use in field screening for lead in personal breathing zone and area air samples.

Many states are considering, and some states have actively pursued, banning the use of perchloroethylene (PERC) in dry cleaning establishments. Proposed legislation has led many dry cleaners to consider the use of products that contain greater than 90% n-propyl bromide (n-PB; also called 1-bromopropane or 1-BP). Very little information is known about toxicity and exposure to n-PB. Some n-PB-containing products are marketed as nonhazardous and “green” or “organic.” This has resulted in some users perceiving the solvent as nontoxic and has resulted in at least one significant poisoning incident in New Jersey. In addition, many dry cleaning operators may not realize that the machine components and settings must be changed when converting from PERC to n-PB containing products. Not performing these modifications may result in overheating and significant leaks in the dry cleaning equipment. A preliminary investigation was conducted of the potential exposures to n-PB and isopropyl bromide (iso-PB; also called 2-bromopropane or 2-BP) among dry cleaners in New Jersey who have converted their machines from PERC to these new solvent products. Personal breathing zone and area samples were collected using the National Institute for Occupational Safety and Health Sampling and Analytical Method 1025, with a slight modification to gas chromatography conditions to facilitate better separation of n-PB from iso-PB. During the preliminary investigation, exposures to n-PB among some workers in two of three shops were measured that were greater than the American Conference of Governmental Industrial Hygienists (ACGIH) threshold limit value (TLV) for n-PB. The highest exposure measured among a dry cleaning machine operator was 54 parts per million (ppm) as an 8-hr time-weighted average, which is more than 5 times the ACGIH TLV of 10 ppm. The preliminary investigation also found that the work tasks most likely to result in the highest short-term exposures included the introduction of solvent to the machine, maintenance of the machine, unloading and handling of recently cleaned clothes, and interrupting the wash cycle of the machine. In addition, this assessment suggested that leaks may have contributed to exposure and may have resulted from normal machine wear over time, ineffective maintenance, and from the incompatibility of n-PB with gasket materials.

An on-site, field-portable analytical method for the determination of lead in workplace air samples, based on the use of ultrasonic extraction and anodic stripping voltammetry (ASV), was evaluated. Workplace air samples were obtained using a standard method involving particulate collection onto mixed cellulose ester membrane filters. Samples were collected at work sites where airborne particulates were generated from the abrasive blasting of lead-containing paint on highway bridges. Ultrasonic extraction (UE) of air filter samples in diluted nitric acid, followed by portable ASV, was used for the determination of lead. Also, performance evaluation samples consisting of reference materials of known lead concentration were subjected to the UE-ASV procedure for lead determination. Confirmatory analyses of the air filters and performance evaluation samples subjected to the UE-ASV lead measurement method were conducted by hotplate digestion in concentrated nitric acid and 30% hydrogen peroxide, followed by inductively coupled plasma-atomic emission spectrometric (ICP-AES) determination of lead. Recoveries of lead from performance evaluation materials (when using the UE-ASV method) were found to be quantitative. The performance of the UE-ASV method for lead in air filters was found to be acceptable, as evaluated by comparison with results from hotplate strong acid digestion followed by ICP-AES analysis. Based on the results of this study, the ultrasonic extraction/portable ASV procedure demonstrates potential for the on-site determination of lead in personal breathing zone and area air samples.

<h3>Objective</h3> Welding is a common work activity in a wide variety of industries, including manufacturing, construction and mining. Many Australian workers are exposed to welding fume in the course of their work but there is little published information available on exposure levels and the use of control measures in regard to occupational exposure to welding fume in Australia. This study aimed to provide information on the level of exposure to welding fume in workplaces in Australia and the use of control measures in these workplaces. <h3>Material and Methods</h3> This was a cross-sectional study involving workers at a convenience sample of 20 workplaces in New South Wales. Personal and static samples of welding fume particulates and gases were collected whilst welding was being undertaken. Personal samples were taken from the breathing zone of 67 welders. Eighty-two static samples were also collected and personal real-time ozone monitoring was undertaken for a welder at each of 16 worksites. Observations of the workplace were recorded by study personnel. <h3>Results</h3> The total welding fume particulate concentrations in the breathing zone were above the newly established workplace exposure standard for 61% of the welders. Peak concentrations of ozone were above the short-term exposure limit for most (75%) welders when they had their head over the welding area. Very few workplaces had active ventilation in place and functioning at the time of the worksite visits. The use of respiratory protective equipment was inconsistent; although 54% of welders used powered air-purifying respirators some of the time, about a fifth (22%) used no respiratory protection at all. <h3>Conclusion</h3> This study provides the first comprehensive information on exposure to welding fume particulate and gases in Australian workplaces. The findings suggest there is considerable scope for improvement in the control of exposure to welding fume.

In a study of the effectiveness of glove bags to control asbestos exposures to workers and contamination of the environment, a four-man crew removed asbestos in eight rooms in four schools. The workers had little prior experience using glove bags and received on-the-job training in proper techniques during the early stages of the study. Daily personal breathing zone (PBZ) samples on all workers and short-term (STBZ) and work-area samples for airborne asbestos were collected and analyzed by phase contrast microscopy (PCM). The asbestos fiber concentrations of 67 PBZ samples ranged from 0.002 to 1.41 fibers/cc when asbestos lagging was being removed; 67 percent were greater than 0.2 f/cc. During an accidental release, a short-term (15 minute) concentration of 9.3 f/cc was measured. Asbestos concentrations indicated by 77 area samples were slightly lower, ranging from 0.001 to 0.96 f/cc. For the part of the study that evaluated environmental contamination, various methodologies were used to determine the airborne asbestos concentration for clearance after abatement. Preremoval and postremoval sampling results using aggressive and nonaggressive techniques were analyzed by PCM and transmission electron microscopy (TEM). It was found that aggressive sampling and TEM analysis provided the most sensitive method to evaluate the cleanliness of the work sites that were studied. However, the TEM method has a high inter-laboratory variability, and the polycarbonate filter media used in this study had a highly variable contamination problem. A standard TEM method and a laboratory certification program should be developed to help ensure the reliability of reported TEM results. Exposure concentrations at these four schools indicate that glove bags, as used during this study, did not completely contain the asbestos being removed. Workers were exposed to airborne asbestos above the National Institute for Occupational Safety and Health recommended exposure limit and the Occupational Safety and Health Administration permissible exposure limit. Asbestos concentrations determined by aggressive sampling and TEM analysis indicated a higher level of contamination after removal than before in five of the eight rooms evaluated. Although worker training and experience are important components in performing proper abatement, this study of glove bags did not provide a basis to specify conditions under which adequate containment can be ensured. Because of the uncertainty in controlling exposures during the use of glove bags, it is essential to provide a back-up containment system (e.g., isolation, barriers, negative air), personal protective equipment (e.g., disposable coveralls), and respiratory protection. Froehlich, P.A.; Hollett, B.A.: Evaluation of Glove Bag Containment and Asbestos Abatement Clearance: Methodologies for Asbestos Removal. Appl. Occup. Environ. Hyg. 8(11):937–944; 1993.

Asphalt shingle removal (tear-off) from roofs is a major job task for an estimated 174,000 roofers in the United States. However, a literature search showed that there are no published studies that characterize worker inhalation exposures to asphalt particulates during shingle tear-off. To begin to fill this gap, the present study of inhalation exposures of roofers performing asphalt shingle tear-off was undertaken. The airborne agents of interest were total particulate matter (TP) and organic particulates measured as the benzene-soluble fraction (BSF) of total particulate. The study's objectives were to measure the personal breathing zone (PBZ) exposures of roofing tear-off workers to BSF and TP; and to assess whether these PBZ exposures are different from ambient levels.Task-based PBZ samples (typical duration 1–5 hours) were collected during asphalt shingle tear-off from roofs near Houston, Texas and Denver, Colorado. Samples were analyzed for TP and BSF using National Institute of Occupational Safety and Health (NIOSH) Method 5042. As controls, area samples (typical duration 3–6 hours) were collected on the ground near the perimeter of the tear-off project Because of the presence of significant sources of inorganic particulates in the work environment, emphasis was placed on the BSF data. No BSF exposure higher than 0.25 mg/m3 was observed, and 69% of the PBZ samples were below the limit of detection (LOD). Due to unforeseen confounding, however, statistical comparisons of on-the-roof PBZ samples with on-the-ground area samples posed some special challenges. This confounding grew out of the interaction of three factors: statistical censoring from the left; the strong inverse correlation between LOD concentration and sampling duration; and variation in sampling durations between on-the-ground area samples and on-the-roof PBZ samples.A general linear model analysis of variance (GLM-ANOVA) was applied to help address the confounding. The results of this analysis indicate that personal sample BSF results were not statistically significantly different from the background/area samples.

Employee exposures to airborne contaminants during sugar-beet processing and to welding fumes during facility maintenance were evaluated at a sugar beet mill owned by the American Crystal Sugar Company (ACSCO), in response to a request from ACSCO's management and the American Federation of Grain Millers International Union. During beet processing, personal breathing-zone and general air samples were collected and analyzed for several chemicals and total and respirable particulates of various dusts. Welding fumes were analyzed by inductively coupled plasma/atomic emission spectroscopy of personal filter samples. The following exposures were considered excessive by the most-stringent criteria: lime-kiln helper to total particulates; Weibul storage-bin housekeeper to sugar dust; diffuser operator and charger to formaldehyde; welders and cutters to total welding fumes and specific metals, particularly hexavalent chromium and nickel. High-volume air and settled-dust samples contained crystalline silica representing a potential hazard. Recommendations include improved particulate containment and ventilation, use of respirators where appropriate, and formaldehyde replacement.

Sampling and analysis of airborne resin acids and solvent-soluble material derived from heated colophony (rosin) flux: a method to quantify exposure to sensitizing compounds liberated during electronics soldering

ABSTRACTThe purpose of this study was to compare personal exposures to isoflurane from participants' breathing zone samples during animal anesthesia procedures by the method of anesthetic gas delivery and the waste anesthetic gas (WAG) control method utilized. WAG control methods included passive scavenging using charcoal canisters, active scavenging using a building vacuum system, and various local exhaust ventilation systems such as laboratory fume hoods and capture hoods. Methods of anesthesia delivery included induction chambers, face masks (also known as nose cones), and intubation. Personal breathing zone samples were collected using 3M 3520 Organic Vapor Diffusion Monitors and submitted to an International Organization for Standardization (ISO) 17025 accredited laboratory for analysis.When using face masks and induction chambers as the method of anesthesia delivery, local exhaust ventilation systems were found to be the best WAG control method to mitigate personal exposures to isoflurane. Personal exposures to isoflurane were well-controlled when animals were intubated, regardless of whether passive scavenging with an adsorptive charcoal canister or active scavenging with a building vacuum system was used. Personal exposures to isoflurane were highest when induction chambers and face masks were used for anesthesia delivery, and passive scavenging with adsorptive charcoal canisters were used as the control method. This study served to identify best practice WAG control methods for research and veterinary procedures that involve isoflurane anesthesia.

Recently, researchers have been interested in ternary organic solar cells (OSCs), which improve light absorption, charge separation, and transport efficiency. Small molecule donors such as BTR-Cl and acceptors such as IT-2Cl and Y6 are recognized for their exceptional optical characteristics and well-matched energy levels, making them suitable for ternary OSC. This study aims to identify the optimal thickness range of IT-2Cl, Y6, and BTR-Cl for a ternary layer-by-layer (LbL) OSC configuration by integrating theoretical analysis, optical modeling, and electron generation rate simulations. Transmittance, absorbance, and reflectance (TAR) calculations were used to determine three distinct thickness regions, and representative thicknesses were chosen from each material region for generate rate characterization. Optical transfer matrix-based generate rate simulations using OghmaNano software provided depth-dependent electron generation data, which were analyzed for key characteristics such as maximum and average generation rates, total generation rate, and the first derivative of generate rate trends. The results identified the optimal thickness ranges as 28.4–90.2 nm for IT-2Cl, 33.4–106.2 nm for Y6, and 26.2–83.4 nm for BTR-Cl, balancing photon absorption efficiency and electron generation uniformity by correlating TAR parameters and generating rate characteristics. The findings of this work contribute to identifying optimal thickness ranges for IT-2Cl, Y6, and BTR-Cl based on their respective roles in the active layer of ternary LbL OSC, which can reduce their complexity in optimization.

BackgroundDosimetry for toxicology studies involving carbon nanotubes (CNT) is challenging because of a lack of detailed occupational exposure assessments. Therefore, exposure assessment findings, measuring the mass concentration of elemental carbon from personal breathing zone (PBZ) samples, from 8 U.S.-based multi-walled CNT (MWCNT) manufacturers and users were extrapolated to results of an inhalation study in mice.ResultsUpon analysis, an inhalable elemental carbon mass concentration arithmetic mean of 10.6 μg/m3 (geometric mean 4.21 μg/m3) was found among workers exposed to MWCNT. The concentration equates to a deposited dose of approximately 4.07 μg/d in a human, equivalent to 2 ng/d in the mouse. For MWCNT inhalation, mice were exposed for 19 d with daily depositions of 1970 ng (equivalent to 1000 d of a human exposure; cumulative 76 yr), 197 ng (100 d; 7.6 yr), and 19.7 ng (10 d; 0.76 yr) and harvested at 0, 3, 28, and 84 d post-exposure to assess pulmonary toxicity. The high dose showed cytotoxicity and inflammation that persisted through 84 d after exposure. The middle dose had no polymorphonuclear cell influx with transient cytotoxicity. The low dose was associated with a low grade inflammatory response measured by changes in mRNA expression. Increased inflammatory proteins were present in the lavage fluid at the high and middle dose through 28 d post-exposure. Pathology, including epithelial hyperplasia and peribronchiolar inflammation, was only noted at the high dose.ConclusionThese findings showed a limited pulmonary inflammatory potential of MWCNT at levels corresponding to the average inhalable elemental carbon concentrations observed in U.S.-based CNT facilities and estimates suggest considerable years of exposure are necessary for significant pathology to occur at that level.

Published data on benzene vapor concentrations in work simulation settings were used to examine the predictive ability of a near field/far field vapor dispersion model with an exponentially decreasing vapor emission rate. A given simulation involved two 15-min periods of applying a known volume of benzene-containing liquid to equipment on a worktable in a room with a measured air exchange rate. Replicate personal breathing zone (15-min time-weighted average, TWA) and room area (1-hr TWA) air samples were collected. In our modeling, the benzene vapor concentration in the near field zone (at the worktable) represented the personal breathing zone exposure level, and the benzene vapor concentration in the far field zone represented the room area concentration. Across 10 simulation combinations of two factors (the mass of benzene applied and the room air exchange rate), the mean of the personal breathing zone exposure levels ranged from 0.2 to 9.9 mg m−3, and the mean of the room area concentrations ranged from 0.05 to 5.05 mg m−3. Our model provided reasonably accurate estimates of the measured benzene vapor concentrations. Linear regression of the mean measured personal breathing zone exposure versus the predicted near field concentration yielded slope = 0.93 and r 2 = 0.94; the null hypothesis that the true slope equals one was not rejected (p-value = 0.39). Linear regression of the mean measured room area concentration versus the predicted far field concentration yielded slope = 0.90 and r 2 = 0.94; the null hypothesis that the true slope equals one was not rejected (p-value = 0.20). Other statistical tests showed no significant differences between measured and predicted values. In addition, most predicted concentrations fell within an approximate range of one-half to twofold the respective measured concentrations.

The aim of this study was to evaluate biomarkers of acrylamide exposure, including hemoglobin adducts and urinary metabolites in acrylamide production workers. Biomarkers are integrated measures of the internal dose, and it is total acrylamide dose from all routes and sources that may present health risks. Workers from three companies were studied. Workers potentially exposed to acrylamide monomer wore personal breathing-zone air samplers. Air samples and surface-wipe samples were collected and analyzed for acrylamide. General-area air samples were collected in chemical processing units and control rooms. Hemoglobin adducts were isolated from ethylenediamine teraacetic acid (EDTA)–whole blood, and adducts of acrylamide and glycidamide, at the N-terminal valines of hemoglobin, were cleaved from the protein chain by use of a modified Edman reaction. Full work-shift, personal breathing zone, and general-area air samples were collected and analyzed for particulate and acrylamide monomer vapor. The highest general-area concentration of acrylamide vapor was 350 μg/cm3 in monomer production. Personal breathing zone and general-area concentrations of acrylamide vapor were found to be highest in monomer production operations, and lower levels were in the polymer production operations. Adduct levels varied widely among workers, with the highest in workers in the monomer and polymer production areas. The acrylamide adduct range was 15–1884 pmol/g; glycidamide adducts ranged from 17.8 to 1376 p/mol/g. The highest acrylamide and glycidamide adduct levels were found among monomer production process operators. The primary urinary metabolite N-acetyl-S-(2-carbamoylethyl) cysteine (NACEC) ranged from the limit of detection to 15.4 μg/ml. Correlation of workplace exposure and sentinel health effects is needed to determine and control safe levels of exposure for regulatory standards.

Two industrial hygiene studies were conducted at an alkaline battery plant to evaluate worker exposures to manganese dioxide particulate and the effectiveness of filtering facepiece respirators. The work areas studied included the plant's powder-processing tower and press rooms where manganese was blended, compacted with graphite, and inserted into battery cans. Full-shift personal breathing zone monitoring was conducted to estimate manganese dust exposures of press operators, mechanics, and material handlers. In-facepiece and personal breathing zone air sampling pairs were also collected using a program protection factor protocol to estimate the protection provided by the respirators. Particle size evaluations were made using nylon cyclones and Marple personal multi-stage impactors. All samples were analyzed for manganese by inductively coupled argon plasma, atomic emission spectroscopy via NIOSH analytical method 7300 utilizing a modified acid digestion procedure. Fifty-four, full-shift, time-weighted average (TWA) exposures to total manganese ranged from 0.1 to 5.4 milligrams per cubic meter (mg/m3); worker exposures were substantially lower during a follow-up study due to engineering control improvements. Concurrent area sample comparisons of total and respirable manganese revealed that the respirable particulate mass fractions ranged from 6 to 32 percent, and mass median aerodynamic diameters determined from personal breathing zone air samples were mostly greater than 10 micrometers. Fifteen respirator performance evaluations were conducted using Moldex 2200 respirators fitted with 25 millimeter cassettes and light weight sampling probes. Protection factors ranged from 5 to 220, with a geometric mean and standard deviation of 31 and 2.97, respectively. The 5th percentile protection factor estimate was 5, as calculated from the protection factor distribution for this sample set. In 1995, the American Conference of Governmental Industrial Hygienists (ACGIH) lowered the elemental and inorganic manganese dust Threshold Limit Value (TLV) from 5 mg/m3 to 0.2 mg/m3 to address adverse pulmonary and central nervous system effects and male infertility. Although most personal breathing zone concentrations were above 0.2 mg/m3, none of the in-facepiece concentrations exceeded this concentration. Parkinson's-like symptoms have been reported in the literature for high manganese dust and fume exposures, but the importance of low dust exposures for producing neurological effects is uncertain.