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Fabrication of Nanoparticle‐Doped Polyvinyl Alcohol‐Cellulose Acetate Membrane and Characterization of the Surface Enhancement

AbstractIn the present study, nanocomposite polymeric membranes are fabricated using polyvinyl alcohol (PVA), cellulose acetate (CA) as polymers, and dimethyl sulfoxide (DMSO) as the solvent. To enhance the performance of the membrane, nanoparticles like TiO2, CaO, CdO, and ZrO are added to the polymeric solution and the doped polymeric solution is cast on a glass plate. Nine combinations of membranes are fabricated with two different concentrations (0.1% and 0.2%) of nanoparticles. The basic properties of the membranes such as density, porosity, viscosity, permeability, pure water flux, and water content are studied for the samples. Membrane pore structure and surface properties are identified and it is found that doping nanoparticles on the surface of membranes improve mechanical strength, stability, pore size, etc., allowing the membranes to perform better in extreme industrial‐level effluent treatment applications. High‐resolution scanning electron microscopy (SEM) shows the homogeneous dispersion of ZrO, TiO2, CaO, and CdO nanoparticles on the surface of the PVA‐CA membrane. The doping of nanoparticles on the PVA‐CA membrane results in improved mechanical strength and good chemical oxidation stability. In comparison, the PCD‐TiO2 sample shows high thermal stability and oxidation stability at high temperatures until 200°C, which has a high potential for treating industrial effluents.

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Dermal Permeation of Biocides and Aromatic Chemicals in Three Generic Formulations of Metalworking Fluids

Metalworking fluids (MWF) are complex mixtures consisting of a variety of components and additives. A lack of scientific data exists regarding the dermal permeation of its components, particularly biocides. The aim of this study was to evaluate the dermal permeation of biocides and other aromatic chemicals in water and in three generic soluble oil, semi-synthetic, and synthetic MWF types in order to evaluate any differences in their permeation profiles. An in vitro flow-through diffusion cell study was performed to determine dermal permeation. An infinite dose of different groups of chemicals (6 biocides and 29 aromatic chemicals) was applied to porcine skin, with perfusate samples being collected over an 8-h period. Perfusate samples were analyzed by gas chromatography/mass spectrometry (GC-MS) and ultra-performance liquid chromatography/mass spectroscopy (UPLC-MS), and permeability was calculated from the analysis of the permeated chemical concentration–time profile. In general, the permeation of chemicals was highest in aqueous solution, followed by synthetic, semi-synthetic, and soluble oil MWF. The absorption profiles of most of the chemicals including six biocides were statistically different among the synthetic and soluble oil MWF formulations, with reduced permeation occurring in oily formulations. Permeation of almost all chemicals was statistically different between aqueous and three MWF formulation types. Data from this study show that permeation of chemicals is higher in a generic synthetic MWF when compared to a soluble oil MWF. This indicates that a soluble oil MWF may be safer than a synthetic MWF in regard to dermal permeation of chemicals to allow for an increased potential of systemic toxicity. Therefore, one may conclude that a synthetic type of formulation has more potential to produce contact dermatitis and induce systemic toxicological effects. The dilution of these MWF formulations with water may increase dermal permeability of biocides, allowing for an enhanced risk for systemic toxicological effects and dermatitis potential.

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Size Distribution of Airborne Mist and Endotoxin-Containing Particles in Metalworking Fluid Environments

The objective of the study was to investigate size-selective concentrations of airborne particles and endotoxin in metalworking fluid (MWF) environments. The experiments were conducted under two conditions: (1) MWF collected in the field was aerosolized with a laboratory-scale simulator (MWF simulator) in the laboratory; and (2) MWFs were aerosolized during routine field operations. All experiments included size-selective measurement of airborne concentrations of particle numbers and endotoxin mass using an electrical low-pressure impactor. During field sampling, the total microbial and endotoxin concentrations in the air were also measured with a BioSampler, and the mass concentration of MWF mists was measured with a photometer. Airborne particle concentrations were highest in the fine particle size ranges in the areas affected by MWFs. Relatively high concentrations of endotoxin were detected at particle size below 0.39 μm, which is smaller than the size of intact bacterial cells. The total microbial and endotoxin analysis revealed high microbial contamination in one sampling site although the total particle mass was not elevated. It was concluded that MWF sites can be contaminated with high concentrations of fine particles, and these fine particles may contain microbial components, such as endotoxin. The results call for the size-selective measurement of particles and endotoxin for more comprehensive exposure assessment in MWF facilities.

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Metalworking Fluid Mist Occupational Exposure Limits: A Discussion of Alternative Methods

NIOSH published a recommended exposure limit (REL) for metalworking fluids (MWF) in 1998 that was designed to prevent respiratory disorders associated with these industrial lubricants. The REL of 0.4 mg/m3 (as a time-weighted average for up to 10 hours) was for the fraction of aerosol corresponding to deposition in the thoracic region of the lungs. This nonregulatory occupational exposure limit (OEL) corresponded to approximately 0.5 mg/m3 for total particulate mass. Although this REL was designed to prevent respiratory disorders from MWF exposures, NIOSH acknowledged that exposures below the REL may still result in occupational asthma and hypersensitivity pneumonitis—two of the most significant respiratory illnesses associated with MWF. In the 8 years since the publication of the NIOSH MWF REL, neither the Occupational Safety and Health Administration (OSHA) nor the American Conference of Governmental Industrial Hygienists (ACGIH®) has recommended an exposure limit for water-soluble MWF specifically, other than their previous exposure limits for mineral oil. An informal effort to benchmark companies involved in the manufacture of automobiles and automotive parts in North America indicated that most companies are using the NIOSH MWF REL as a guide for the purchase of new equipment. Furthermore, most companies have adopted a goal to limit exposures to below 1.0 mg/m3. We failed to find any company that has strictly enforced an OEL of 1.0 mg/m3 through the use of either administrative controls or personal protective equipment, when engineering controls failed to bring the exposures to below this limit. We also found that most companies have failed to implement specific medical surveillance programs for those employees exposed to MWF mist above 1.0 mg/m3. Organization Resources Counselors (ORC) published in 1999 (on their website) a “best practices” manual for maintaining MWF systems and reducing the likelihood of MWF-related illnesses. The emphasis of this approach was on control techniques, and there was no assignment of a specific OEL for MWF due to the wide variety of fluids that exist. The ORC did suggest that maintaining exposure levels to below 2.0 mg/m3 would assist in minimizing upper respiratory complaints associated with MWF. Although the ORC manual indicated that MWF vary in composition and no single OEL is likely to be appropriate for all such fluids, it adopted a very similar concept to control banding, placing all MWF operations into a single band using similar (if not identical) controls. OSHA, in lieu of adopting a 6B health standard for MWF, has also published a voluntary “best practices” manual on their website. Their document drew heavily from the work of ORC and also incorporated information from the 1998 NIOSH MWF criteria document. Industrial users of MWF need to have guidance, such as an OEL, to determine when either engineering, administrative controls, or personal protective equipment must be implemented to protect their employees. The purpose of this article is to explore various approaches that might be taken to result in a single or multiple limits for exposures to MWF and its components. Approaches such as control banding are discussed in terms of an alternative to the use of an OEL.

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History and results of the two inter‐laboratory round robin endotoxin assay studies on cotton dust

In the US cotton industry, airborne cotton dust levels are regulated, and other countries are moving to specify safety limits for airborne endotoxins. There is concern about potential respiratory health hazards associated with agricultural and other organic dusts. In laboratories, ranking which samples have high and low levels of endotoxin is usually in good agreement between laboratories. When different laboratories assay identical samples, the levels differ. The objective of this research was to evaluate the intra- and inter-laboratory variability for 13 laboratories measuring endotoxin in cotton dust. Two inter-laboratory round robin endotoxin assay studies were conducted using cotton dust. In the first round robin, each laboratory used their normal in-house assay method and then used a common extraction protocol. In the second round robin, a common extraction protocol and endotoxin assay kit was used. The intra-laboratory results had small variations but inter-laboratory results had very high variations. The inter-laboratory results using a common extraction protocol showed reduced differences. Using the same extraction protocol and endotoxin assay kit, the intra-laboratory variation was small and inter-laboratory variation was reduced but not enough for inter-laboratory agreement. Most of the laboratories were able to discern between the high and low endotoxin concentration dusts. Standardization has reduced the differences in results between laboratories and possibly further standardization may bring closer inter-laboratory agreement.

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