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The authors critically reviewed published lists of nano-objects and their physico-chemical properties deemed important for risk assessment and discussed metrological challenges associated with the development of nanoscale reference materials (RMs). Five lists were identified that contained 25 (classes of) nano-objects; only four (gold, silicon dioxide, silver, titanium dioxide) appeared on all lists. Twenty-three properties were identified for characterisation; only (specific) surface area appeared on all lists. The key themes that emerged from this review were: 1) various groups have prioritised nano-objects for development as 'candidate RMs' with limited consensus; 2) a lack of harmonised terminology hinders accurate description of many nano-object properties; 3) many properties identified for characterisation are ill-defined or qualitative and hence are not metrologically traceable; 4) standardised protocols are critically needed for characterisation of nano-objects as delivered in relevant media and as administered to toxicological models; 5) the measurement processes being used to characterise a nano-object must be understood because instruments may measure a given sample in a different way; 6) appropriate RMs should be used for both accurate instrument calibration and for more general testing purposes (e.g., protocol validation); 7) there is a need to clarify that where RMs are not available, if '(representative) test materials' that lack reference or certified values may be useful for toxicology testing and 8) there is a need for consensus building within the nanotechnology and environmental, health and safety communities to prioritise RM needs and better define the required properties and (physical or chemical) forms of the candidate materials. [ABSTRACT FROM AUTHOR]

Accurate characterization of nanomaterial properties is a critical component of any nanotoxicology testing strategy. Data that describes the performance of various laboratories in measuring the characteristics of the same nanomaterial are scarce. We conducted an inter-laboratory study to evaluate 'real-world' precision and bias of specific surface area measurements using a powered material containing sub-30 nm primary crystallites. Each participant was provided a sample of NIST Standard Reference Material 1898 (Titanium Dioxide Nanomaterial) and a sample preparation and analysis protocol. Based on results from 19 laboratories, overall performance was good. Estimates of precision ranged from 0.10 to 3.96 % and measurement bias was generally within ±5 % of the certified surface area value of the material. Between-laboratory variability accounted for 91 % of the total variance and is likely explained by gravimetric errors. Reliable determination of intrinsic nanomaterial properties such as surface area will permit development of protocols for toxicity testing, verification of laboratory proficiency, and consistency in interpretation of toxicity study data. [ABSTRACT FROM AUTHOR]

Laboratory measurements of ultrafine titanium dioxide (TiO2) particulate matter loaded on filters were made using three field portable methods (X-ray fluorescence (XRF), laser-induced breakdown spectroscopy (LIBS), and Fourier-transform infrared (FTIR) spectroscopy) to assess their potential for determining end-of-shift exposure. Ultrafine TiO2 particles were aerosolized and collected onto 37 mm polycarbonate track-etched (PCTE) filters in the range of 3 to 578 μg titanium (Ti). Limit of detection (LOD), limit of quantification (LOQ), and calibration fit were determined for each measurement method. The LOD's were 11.8, 0.032, and 108 μg Ti per filter, for XRF, LIBS, and FTIR, respectively and the LOQ's were 39.2, 0.11, and 361 μg Ti per filter, respectively. The XRF calibration curve was linear over the widest dynamic range, up to the maximum loading tested (578 μg Ti per filter). LIBS was more sensitive but, due to the sample preparation method, the highest loaded filter measurable was 252 μg Ti per filter. XRF and LIBS had good predictability measured by regressing the predicted mass to the gravimetric mass on the filter. XRF and LIBS produced overestimations of 4% and 2%, respectively, with coefficients of determination (R²) of 0.995 and 0.998. FTIR measurements were less dependable due to interference from the PCTE filter media and overestimated mass by 2% with an R² of 0.831. [ABSTRACT FROM AUTHOR]

Background Skin surface pH is known to influence the dissolution and partitioning of chemicals and may influence exposures that lead to skin diseases. Non-clinical environments (e.g. workplaces) are highly variable, thereby presenting unique measurement challenges that are not typically encountered in clinical settings. Hence, guidelines are needed for consistent measurement of skin surface pH in environments that are difficult to control. Methods An expert workshop was convened at the 5th International Conference on Occupational and Environmental Exposure of Skin to Chemicals to review available data on factors that could influence the determination of skin surface pH in non-clinical settings with emphasis on the workplace as a worst case scenario. Results The key elements of the guidelines are: (i) minimize, to the extent feasible, the influences of relevant endogenous (anatomical position, skin health, time of day), exogenous (hand washing, barrier creams, soaps and detergents, occlusion), environmental (seasonality), and measurement (atmospheric conditions) factors; (ii) report pH measurements results as a difference or percent change (not absolute values) using a measure of central tendency and variability; and (iii) report notable deviations from these guidelines and other relevant factors that may influence measurements. Conclusion Guidelines on the measurement and reporting of skin surface pH in non-clinical settings should promote consistency in data reporting, facilitate inter-comparison of study results, and aid in understanding and preventing occupational skin diseases. [ABSTRACT FROM AUTHOR]

Exposure to some manufactured beryllium compounds via skin contact or inhalation can cause sensitization. A portion of sensitized persons who inhale beryllium may develop chronic beryllium disease (CBD). Little is understood about exposures to naturally occurring beryllium minerals. The purpose of this study was to assess the bioaccessibility of beryllium from bertrandite ore. Dissolution of bertrandite from two mine pits (Monitor and Blue Chalk) was evaluated for both the dermal and inhalation exposure pathways by determining bioaccessibility in artificial sweat (pH 5.3 and pH 6.5), airway lining fluid (SUF, pH 7.3), and alveolar macrophage phagolysosomal fluid (PSF, pH 4.5). Significantly more beryllium was released from Monitor pit ore than Blue Chalk pit ore in artificial sweat buffered to pH 5.3 (0.88 ± 0.01% vs. 0.36 ± 0.00%) and pH 6.5 (0.09 ± 0.00% vs. 0.03 ± 0.01%). Rates of beryllium released from the ores in artificial sweat were faster than previously measured for manufactured forms of beryllium (e.g., beryllium oxide), known to induce sensitization in mice. In SUF, levels of beryllium were below the analytical limit of detection. In PSF, beryllium dissolution was biphasic (initial rapid diffusion followed by latter slower surface reactions). During the latter phase, dissolution half-times were 1,400 to 2,000 days, and rate constants were ~7 × 10 g/(cm·day), indicating that bertrandite is persistent in the lung. These data indicate that it is prudent to control skin and inhalation exposures to bertrandite dusts. [ABSTRACT FROM AUTHOR]

Objective The aim of this study was to evaluate the validity of aj ob exposure matrix (JEM) constructed for the period 1994-1999. Historical exposure estimates (HEE) for the JEM were constructed for all j ob and year combinations by applying temporal factors reflecting annual change in area air measurements (1994-1998) to the personal baseline exposure estimates (BEE) collected in 1999. The JEM was generated for an epidemiologic study to examine quantitative exposure-response relationships with sensitization and chronic beryllium disease. Methods The validity of the BEE and HEE was evaluated by comparing them with a validation dataset of independently collected personal beryllium exposure measurements from 1999 and 1994-1998, respectively. Agreement between the JEM and validation data was assessed using relative bias and concordance correlation coefficients (CCC). Results The BEE and HEE overestimated the measured exposures in their respective validation datasets by 8% and 6%, respectively. The CCC reflecting the deviation of the fitted line from the concordance line, showed good agreement for both BEE (CCC=0.80) and HEE (CCC=0.72). Proportional difference did not change with exposure levels or by process area and year. Overall, the agreement between the JEM and validation estimates (from combined HEE and BEE) was high (CCC=0.77). Conclusions This study demonstrated that the reconstructed beryllium exposures at a manufacturing facility were reliable and can be used in epidemiologic studies. [ABSTRACT FROM AUTHOR]

Objectives Exposure-response relations for beryllium sensitization (BeS) and chronic beryllium disease (CBD) using aerosol mass concentration have been inconsistent, although process-related risks found in most studies suggest that exposure-dependent risks exist. We examined exposure-response relations using personal exposure estimates in a beryllium worker cohort with limited work tenure to minimize exposure misclassification. Methods The population comprised workers employed in 1999 with six years or less tenure. Each completed a work history questionnaire and was evaluated for immunological sensitization and CBD. A job-exposure matrix was combined with work histories to create individual estimates of average, cumulative, and highest-job-worked exposure for total, respirable, and submicron beryllium mass concentrations. We obtained odds ratios from logistic regression models for exposure-response relations, and evaluated process-related risks. Results Participation was 90.7% (264/291 eligible). Sensitization prevalence was 9.8% (26/264), with 6 sensitized also diagnosed with CBD (2.3%, 6/264). A general pattern of increasing sensitization prevalence was observed as exposure quartile increased. Both total and respirable beryllium mass concentration estimates were positively associated with sensitization (average and highest job), and CBD (cumulative). Increased sensitization prevalence was identified in metal/oxide production, alloy melting and casting, and maintenance, and for CBD in melting and casting. Lower sensitization prevalence was observed in plant-area administrative work. Conclusions Sensitization was associated with average and highest job exposures, and CBD was associated with cumulative exposure. Both total and respirable mass concentrations were relevant predictors of risk. New process-related risks were identified in melting and casting and maintenance. [ABSTRACT FROM AUTHOR]

Objectives Previous epidemiologic studies of beryllium sensitization (BeS) and chronic beryllium disease (CBD) have reported inconsistent exposure-response relationships, likely due to exposure misclassification. The objective of this study was to develop historical estimates of size-selective personal exposure to beryllium for an epidemiologic study. Methods In 1999, a cross-sectional survey of workers hired after 1 January 1994 was conducted at a beryllium production facility. Personal exposure data from two air sampling surveys conducted in 1999 were used to obtain total, respirable, and submicron particle baseline exposure estimates (BEE) for a job-exposure matrix (JEM). General area air samples collected from 1994-1999 were used to estimate annual changes in exposures (temporal factors) for 24 different process areas. Historical exposure estimates (HEE) were calculated by applying the temporal factors to the BEE. Workers were assigned HEE based on their work history, and their historical exposure profile was summarized as cumulative, average, or highest-ever job exposure. Results Changes in exposure over a 6-year period were observed in 10 of the 24 process areas with an overall mean decline of 18% per year. The overall total exposure for study participants over their work tenure ranged from: 0.001-34.44 µg/m3-year, 0.01-16.26 µg/m3, and 0.01-17.54 µg /m3 for cumulative, average, and highestever job, respectively. For respirable exposures, the ranges were: 0.001-15.54 µg/m3-year, 0.01-3.56 pg/m3, 0.01-5.54 µg /m3 for cumulative, average, and highest-ever job, respectively. Conclusions Using this JEM, exposure-response relationships for BeS and CBD can be explored over a range of exposure metrics such as total, respirable, and submicron beryllium mass concentrations, including summary measures such as cumulative, average, or highest exposures, with the ultimate objective of elucidating a quantitative exposure-response relationship. [ABSTRACT FROM AUTHOR]

Inhalation toxicology studies generally use the Brunauer, Emmett, and Teller (BET) gas adsorption method to measure total surface area of particles whereas occupational exposures are more readily measured by real-time mobility-based surface areas or active surface area measured with diffusion charger-based instruments. Three surface area measurement methods were studied: filter-based inert gas adsorption (BET method), diffusion charging, and mobility-based methods. The goal of the project was to investigate and develop a correlation between the measurement methods. The experimental design consisted of measuring surface area in a series of five trials for each of two powder types, fine and ultrafine titanium dioxide with primary particle sizes of 440 and 20 nm, respectively, and two aerosol concentrations. Diffusion charger instruments tended to underestimate the total particle surface area measured by the BET, but were well correlated with mobility-based surface areas obtained from a scanning mobility particle sizer. Filter-based gas adsorption methods and diffusion charging methods provide different but valuable information on total and active surface areas of particles, respectively. Results indicate they should not be used as predictors of one another. [ABSTRACT FROM AUTHOR]

Synopsis Materials in contact with liquids on the human skin surface may dissolve and permeate into skin. Release and permeation of chemicals in contact with skin is often estimated in vitro using artificial skin liquids, although sebum lipids are generally not included in these models. The purposes of this research were to develop a representative artificial sebum that contains the appropriate types of lipids at levels that match human values and quantitatively characterize the model to understand its utility for in vitro testing. Artificial sebum that consisted of 10 lipids at proportions that closely resembled human sebum was characterized using thin layer chromatography under a variety of storage and use conditions (dry and liquid, 4°C and 32°C, with and without vitamin E) for 28 days. Levels of sebum constituents maintained in solution and dry at 4°C were stable through the duration of the test period. Levels of all sebum lipids maintained dry at 32°C were stable in the presence of vitamin E; however, squalene oxidized rapidly in the absence of vitamin E. Liquids on the human skin surface consist of sebum and sweat with minor amounts of cellular debris and intercellular lipid from the stratum corneum. The relative importance of each component for release of chemicals from materials in contact with skin will depend upon the type of material (metal, organic, etc.). A model artificial sebum was formulated and characterized to aid researchers in understanding potential release of chemicals from materials in contact with skin and subsequent partitioning and absorption. [ABSTRACT FROM AUTHOR]

Context: Although chronic beryllium disease (CBD) is clearly an immune-mediated granulomatous reaction to beryllium, acute beryllium disease (ABD) is commonly considered an irritative chemical phenomenon related to high exposures. Given reported new cases of ABD and projected increased demand for beryllium, we aimed to reevaluate the pathophysiologic associations between ABD and CBD using two cases identified from a survey of beryllium production facility workers. Case Presentation: Within weeks after exposure to beryllium fluoride began, two workers had systemic illness characterized by dermal and respiratory symptoms and precipitous declines in pulmonary function. Symptoms and pulmonary function abnormalities improved with cessation of exposure and, in one worker, recurred with repeat exposure. Bronchoalveolar lavage fluid analyses and blood beryllium lymphocyte proliferation tests revealed lymphocytic alveolitis and cellular immune recognition of beryllium. None of the measured air samples exceeded 100 μg/m3, and most were < 10 μg/m3, lower than usually described. In both cases, lung biopsy about 18 months after acute illness revealed noncaseating granulomas. Years after first exposure, the workers left employment because of CBD. Discussion: Contrary to common understanding, these cases suggest that ABD and CBD represent a continuum of disease, and both involve hypersensitivity reactions to beryllium. Differences in disease presentation and progression are likely influenced by the solubility of the beryllium compound involved. Relevance to Practice: ABD may occur after exposures lower than the high concentrations commonly described. Prudence dictates limitation of further beryllium exposure in both ABD and CBD. [ABSTRACT FROM AUTHOR]

As many as 30,000 workers in the United States of America are exposed to cemented tungsten carbides (CTC), alloys composed primarily of tungsten carbide and cobalt, which are used in cutting tools. Inhalation of cobalt-containing particles may be sufficient for the development of occupational asthma, whereas tungsten carbide particles in association with cobalt particles are associated with the development of hard metal disease (HMD) and lung cancer. Historical epidemiology and exposure studies of CTC workers often rely only on measures of total airborne cobalt mass concentration. In this study, we characterized cobalt- and tungsten-containing aerosols generated during the production of CTC with emphasis on (1) aerosol “total” mass (n=252 closed-face 37 mm cassette samples) and particle size-selective mass concentrations (n=108 eight-stage cascade impactor samples); (2) particle size distributions; and (3) comparison of exposures obtained using personal cassette and impactor samplers. Total cobalt and tungsten exposures were highest in work areas that handled powders (e.g., powder mixing) and lowest in areas that handled finished product (e.g., grinding). Inhalable, thoracic, and respirable cobalt and tungsten exposures were observed in all work areas, indicating potential for co-exposures to particles capable of getting deposited in the upper airways and alveolar region of the lung. Understanding the risk of CTC-induced adverse health effects may require two exposure regimes: one for asthma and the other for HMD and lung cancer. All sizes of cobalt-containing particles that deposit in the lung and airways have potential to cause asthma, thus a thoracic exposure metric is likely biologically appropriate. Cobalt-tungsten mixtures that deposit in the alveolar region of the lung may potentially cause HMD and lung cancer, thus a respirable exposure metric for both metals is likely biologically appropriate. By characterizing size-selective and co-exposures as well as multiple exposure pathways, this series of papers offer an approach for developing biologically meaningful exposure metrics for use in epidemiology.Journal of Exposure Science and Environmental Epidemiology (2009) 19, 475–491; doi:10.1038/jes.2008.37; published online 16 July 2008 [ABSTRACT FROM AUTHOR]

Cobalt, chromium and nickel are among the most commonly encountered contact allergens in the workplace, all used in the production of cemented tungsten carbides (CTC). Exposures to these metal-containing dusts are frequently associated with skin sensitization and/or development of occupational asthma. The objectives of this study were to assess the levels of cobalt, chromium and nickel on work surfaces and on workers’ skin in three CTC production facilities. At least one worker in each of 26 work areas (among all facilities) provided hand and neck wipe samples. Wipe samples were also collected from work surfaces frequently contacted by the 41 participating workers. Results indicated that all surfaces in all work areas were contaminated with cobalt and nickel, with geometric means (GMs) ranging from 4.1 to 3057 μg/100 cm2 and 1.1–185 μg/100 cm2, respectively; most surfaces were contaminated with chromium (GM=0.36–67 μg/100 cm2). The highest GM levels of all metals were found on control panels, containers and hand tools, whereas lowest levels were on office and telecommunication equipment. The highest GM levels of cobalt and nickel on skin were observed among workers in the powder-handling facility (hands: 388 and 24 μg; necks: 55 and 6 μg, respectively). Levels of chromium on workers’ skin were generally low among all facilities. Geometric standard deviations associated with surface and skin wipe measurements among work areas were highly variable. Exposure assessment indicated widespread contamination of multiple sensitizing metals in these three facilities, suggesting potential transfer of contaminants from surfaces to skin. Specific action, including improved housekeeping and training workers on appropriate use and care of personal protective equipment, should be implemented to reduce pathways of skin exposure. Epidemiologic studies of associated adverse health effects will likely require more biologically relevant exposure metrics to improve the ability to detect exposure–response relationships.Journal of Exposure Science and Environmental Epidemiology (2009) 19, 423–434; doi:10.1038/jes.2008.33; published online 4 June 2008 [ABSTRACT FROM AUTHOR]

Fused filament fabrication three-dimensional (FFF 3-D) printing is thought to be environmentally sustainable; however, significant amounts of waste can be generated from this technology. One way to improve its sustainability is via distributed recycling of plastics in homes, schools, and libraries to create feedstock filament for printing. Risks from exposures incurred during recycling and reuse of plastics has not been incorporated into life cycle assessments. This study characterized contaminant releases from virgin (unextruded) and recycled plastics from filament production through FFF 3-D printing. Waste polylactic acid (PLA) and acrylonitrile butadiene styrene (ABS) plastics were recycled to create filament; virgin PLA, ABS, high and low density polyethylenes, high impact polystyrene, and polypropylene pellets were also extruded into filament. The release of particles and chemicals into school classrooms was evaluated using standard industrial hygiene methodologies. All tasks released particles that contained hazardous metals (e.g., manganese) and with size capable of depositing in the gas exchange region of the lung, i.e., granulation of waste PLA and ABS (667 to 714 nm) and filament making (608 to 711 nm) and FFF 3-D printing (616 to 731 nm) with waste and virgin plastics. All tasks released vapors, including respiratory irritants and potential carcinogens (benzene and formaldehyde), mucus membrane irritants (acetone, xylenes, ethylbenzene, and methyl methacrylate), and asthmagens (styrene, multiple carbonyl compounds). These data are useful for incorporating risks of exposure to hazardous contaminants in future life cycle evaluations to demonstrate the sustainability and circular economy potential of FFF 3-D printing in distributed spaces. [Display omitted] [ABSTRACT FROM AUTHOR]

Owing to the absence of readily available certified particulate reference materials (RMs), most analytical methods used to determine particulate contaminant levels in workplace or other environments are validated using solution RMs, which do not assess the robustness of the digestion step for all forms and sizes of particles in a sample. A library of particulate RMs having a range of chemical forms and particle sizes is needed to support a shift in method evaluation strategies to include both solution and particulate RMs. In support of creating this library, we characterized bulk and physically size separated fractions of beryllium oxide (BeO) particles recovered from the machining fluid sludge of an industrial ceramic products grinding operation. Particles were large agglomerates of compact, crystalline BeO primary particles having diameters on the order of several micrometers. As expected, the particle surface area was independent of sieve size, with a range from 3.61 m2/g (53–63-μm fraction) to 4.82 m2/g (355–600-μm fraction). The density was near the theoretical value (3.01 g/cm3). The data support more detailed characterization of the sludge materials for use as size-selective RMs. This work illustrates an approach that can be used to develop RMs that are difficult to digest. [ABSTRACT FROM AUTHOR]