Development of a method to determine workers' personal exposure levels to glyphosate.

OBJECTIVES: We aimed to develop a method to determine workers' personal exposure levels to N-(phosphonomethyl)glycine (glyphosate) for their risk assessments. METHODS: The proposed method was assessed as follows: recovery, stability of samples on storage, method limit of quantification, and reproducibility. Glyphosate in air was sampled using an air-sampling cassette containing a glass fiber filter. Ultrapure water was used to extract glyphosate from sampler filters. After derivation with 9-fluorenylmethyloxycarbonyl chloride, samples were analyzed by high-performance liquid chromatography using a fluorescence detector. RESULTS: Spiked samples indicated an overall recovery of 101%. After 7 days of storage at 4°C, recoveries were approximately 100%. The method limit of quantification was 0.060 µg/sample. Relative standard deviations representing overall reproducibility, defined as precision, were 1.4%-1.8%. CONCLUSIONS: The method developed in this study allows 4-h personal exposure monitoring of glyphosate at 0.250-500 µg/m3 . Thus, this method can be used to estimate worker exposure to glyphosate.

Exposure assessment of nanotitanium oxide powder handling using real-time size-selective particle number concentration measurements and X-ray fluorescence spectrometry -The possibility of exposure to nonagglomerated nanomaterials during the handling of nanomaterial fine powders.

In this study, airborne particles were collected using filters, and the particle number concentrations were measured in two nanotitanium dioxide (nanoTiO2)-manufacturing plants. Real-time particle size measurements were performed using both optical and scanning mobility particle sizer and X-ray fluorescence spectrometry (XRF). The respirable particles collected using filters were used to analyze Ti concentrations in the workplace air of two factories engaged in nanoTiO2 powder bagging processes. The XRF analysis revealed sufficient sensitivity to measure 0.03 mg/m3, which is 1/10 the concentration of the recommended occupational exposure limit of nanoTiO2 in both stationary sampling and personal exposure sampling settings. In a factory where outside air was directly introduced, micron-sized aggregated particles were generated because of factory operations; however, nanosized and submicron-sized particles were not observed owing to high background concentrations of incidental nanoparticles. Alternatively, in another factory where particles from the outside air were removed using a high-efficiency particulate air filter, work-related nanoparticles were released. The findings of this study suggest that in nanoparticle powder handling processes, a nanoparticle exposure risk exists in the form of nonagglomerated state in nanoparticle powder handling processes.

Evaluation of exposure risk in the weaving process of MWCNT-coated yarn with real-time particle concentration measurements and characterization of dust particles.

Various applications of multiwalled carbon nanotubes (MWCNT) have been developed. One of these applications is an efficient sheet heating element that is woven from MWCNT-coated yarn. In this research, we assessed the exposure to MWCNT and/or the probability of particle release from broken MWCNT-coated yarn during the weaving process. This was accomplished using particle concentrations, microscopic observation, and carbon analysis. In the weaving process, neither an increase in the number of particles nor a difference in particle-size distribution was observed. In the scanning electron micrographic observation, nanosize MWCNT particles were not detected, but there were micron-size particles containing MWCNT as fragments of the yarn. Carbon analysis showed the concentration of micron-size particles containing MWCNT did not exceed 0.0053 mg-C/m(3) around the loom. This value was much lower than the respirable dust mass concentration. Most of micron-size particles seemed to originate from polyester yarn without MWCNT coating. It is recommended that workers use conventional (even not specialized for nanoparticles) personal protective equipment such as respirators and gloves to prevent exposure to respirable-size MWCNT-containing particles. The probability of MWCNT fall-off from the MWCNT-coated yarn was not detected by transmission electron microscopic observation of MWCNT-coated yarn before or after the weaving process.

A proposal of method for evaluating airborne MWCNT concentration.

As multi-wall carbon nanotubes (MWCNTs) come to be used in a wider range of products, increasing production is expected to result in greater exposure of workers to MWCNTs. In this research, we present a method for evaluating the concentration of MWCNT aerosols distinctively on the basis of the elemental carbon (EC) concentration. Respirable dust is sampled using a Sioutas cascade impactor (SCI) for a certain volume of workplace air. The SCI can collect size-segregated particles having aerodynamic diameters of 2.5 µm, 1.0 µm, 0.5 µm, 0.25 µm and <0.25 µm. MWCNTs in sampled particles are determined by carbon analysis. Based on the phenomenon that MWCNTs easily aggregate/agglomerate, the present procedure for distinguishing MWCNTs uses the EC in particles larger than 1 µm as an index of MWCNT; the EC is oxidized at a high temperature, 920°C, in carbon analysis. We propose a three-step procedure for distinguishing between MWCNT aerosol and atmospheric particulate matter, and for measuring MWCNT concentrations in workplace air on the basis of EC concentration.

[Airborne particles in a multi-wall carbon nanotube production plant: observation of particle emission and personal exposure 1: Measurement in the packing process].

OBJECTIVES: In order to assess the exposure risks of multiwall carbon nanotubes (MWCNT) for packing workers, we carried out real-time monitoring in the two types of packing facilities of MWCNT, and exposure measurements for the packing workers. METHODS: In the real-time monitoring, a scanning mobility particle sizer (SMPS) and an optical particle counter (OPC) were used to measure nanoscale particles and sub-micron/micron scale particles, respectively. A personal sampler with PM 4.0 was used to measure the personal exposures in the packing facilities. RESULTS: One of the packing facilities is manually operated and the other is automated. The concentrations of airborne dust in both facilities were almost the same as each other at 0.24 mg/m(3) (total dust). However, the results of personal exposure measurements were quite different between the two facilities. The exposure concentrations of workers in the manually and automated operations were 2.39/0.39 (total/respirable) mg/m(3) and 0.29/0.08 (total/respirable) mg/m(3), respectively. From the time series study, submicron scale particles were released into the workplace air when the CNT products were put into temporary container bags from a hopper and manually packed into shipping bags. However, the task-related nanoscale particle release was not observed. CONCLUSIONS: The manual packing operation is one of the "hot spots" in MWCNT production facilities, and automation brings much improvement to reduce MWCNT exposure.

A simple direct injection method for GC/MS analysis of PAHs in particulate matter.

A simple direct injection method for analysis of polycyclic aromatic hydrocarbons (PAHs) or other organic components of particulate matter by gas chromatography/mass spectrometry (GC/MS) was developed. This method uses a small custom brass capsule to insert a particulate sample deposited on a quartz fiber filter or powdery sample directly into a GC injector inlet. This approach was applied in the analysis of PAHs in diesel emissions and other particulate samples, which are introduced into the GC and analyzed by MS using selected ion monitoring mode. Quantitation is based on the concentration of PAHs in a standard reference material (SRM), which are certified by US National Institute of Standard Technology to avoid matrix effects on extraction efficiency. A standard filter is prepared by deposition of small amount of SRM of diesel particulate or ambient PM on quartz fiber filter. By this method, the linearity for 12 kinds of PAHs (3 to 6 rings) was demonstrated from 0.022 mg to 0.65 mg of SRM 1650. The linearity of BaP, for example, was confirmed from 0.028 to 0.845 ng. The reproducibility of this method determined by analyzing the standard filter was 15.4%. By selecting an appropriate SRM as a standard material, this method is applicable for analyzing PAHs in fine particulate matter of less than 1 microm from various origins. Preliminary results for a series of ambient particulate matter, roadside PM, diesel soot and sidestream smoke, are presented. This method enables analysis of organic chemical substances, for example PAHs, in PM without any pretreatment using organic solvent, and without any expensive modification of GC instrument.

Dissolution of functional materials and rare earth oxides into pseudo alveolar fluid.

The dissolution rates of rare earth oxides and two types of rare earth containing functional materials into water, saline solution, and Gamble's fluid were measured in order to evaluate the biological effects of rare earth-containing functional materials. The tested materials were yttrium, lanthanum, cerium and neodymium oxides, and neodymium-boron-iron magnet alloy (NdBFe) and lanthanum-mish-metal-nickel-cobalt (LmNiCo) hydrogen-containing alloy. The dissolution rates of the rare earth oxides were very low, resulting in concentrations of rare earth elements in the test solutions of the order of ppb. In the most extreme case, Gamble's fluid dissolved 1,400 times more of the rare earth oxides than pure water. Fairly high concentration of neodymium were found in the dissolving fluids, which means that trace neodymium present as an impurity in each rare earth oxide dissolved preferentially. For yttrium oxide, the ratio of neodymium to yttrium that dissolved in the saline solution was greater than 78,000 to 1, taking into account the amount of each that was originally present in the yttrium oxide.

Diesel exhaust particles in the work environment and their analysis.

Diesel engines are widely used in industries, for example transportation, mining, and construction, because they efficiently produce high power. In diesel exhaust particles (DEP), the number of ultrafine particles, less than around 100 nm, is dominant in contrast to mass size distribution. Carcinogenic PAHs may be adsorbed on DEP at high concentrations. As occupational exposure usually occurs near emission sources, workers are likely to be exposed to high concentration DEP. The exhaust emissions of diesel engines have become lower by modification of the engines and fuels, and introduction of filters and catalysts, thus it has become more difficult to monitor mass and chemical components in DEP. New technology and instruments are being introduced to characterize DEP especially chemically. Recently, quick analytical methods without extraction, and continuous or semi-continuous methods have been introduced. This article will review 1) Elemental Carbon (EC) monitors, 2) analytical methods of individual PAH without solvent extraction, and 3) continuous PAH monitor, because EC and PAH are typical constituents for DEP.