Robotic direct reading device with spatial, temporal, and PID sensors for laboratory VOC exposure assessment.

This study evaluated a novel robotic direct reading method that used a real-time location system to measure the spatial-concentration distribution of volatile organic compounds (VOCs) in a chemistry laboratory. The CEMWIP II is a custom-made sensor that measures VOCs, temperature, humidity, and location, sending data wirelessly in real time to a remote location for display and storage. In this study, the CEMWIP II device was mounted on a robotic platform to create a CEMWIP II-mobile platform. The autonomous mobile platform was released from a corner of the room and allowed to travel randomly along an open floor with the goal of characterizing the spatial distribution of VOCs and identifying their sources in the laboratory. The experiment consisted of 12 runs made of permutations of four corner release sites and four beaker locations, with two beakers containing water and two containing the solvent acetone. The autonomous mobile platform was tasked with locating the two beakers of acetone. The sensor had a detection limit of 100 ppb and the confidence of detecting a source within a 1.46 m2 area was p = 0.0005 by ANOVA. The CEMWIP II-mobile platform was able to measure the spatial distribution of VOCs within a laboratory that were associated with open solvent containers.

Assessing flammable storage cabinets as sources of VOC exposure in laboratories using real-time direct reading wireless detectors.

Herein we present the results of measurements using wireless direct-reading photoionization detector-based gas sensors to quantify concentrations of vapors of volatile organic compounds (VOCs) in and around flammable storage cabinets containing common organic solvents, including acetone, dichloromethane, trichloroethylene, and benzene. Such cabinets are commonly employed in laboratories to contain flammable liquids. A sensor array was deployed in a series of flammable storage cabinets in working laboratories. Measurements in cabinets containing bottles of typical solvents demonstrate that vapor concentrations gradually increase upon closing the cabinet door. The results suggest that these storage units can be a source of vapors of VOCs in laboratories and the unnecessary exposure of laboratory workers to chemical vapors. Ventilation of cabinets tended to lower maximum concentrations of VOCs. However, the efficacy of this engineering control was found to depend on the quality of the cabinet door seal, as well as having debris-free flame arrestors. Opening cabinet doors resulted in release of vapors to the laboratory atmosphere, which represents an unnecessary exposure risk for workers. A countermeasure aimed at improving the seal of previously opened solvent bottles reduced measured concentrations of VOCs in cabinets below the detector's limit of detection.

Evaluation of irritancy and sensitization potential of metalworking fluid mixtures and components.

There are approximately 1.2 million workers exposed to metalworking fluids (MWF), which are used to reduce the heat and friction associated with industrial machining and grinding operations. Irritancy and sensitization potential of 9 National Toxicology Program (NTP) nominated MWFs (TRIM 229, TRIM VX, TRIM SC210, CIMTECH 310, CIMPERIAL 1070, CIMSTAR 3800, SYNTILO 1023, SUPEREDGE 6768, and CLEAREDGE 6584) were examined in a combined local lymph node assay (LLNA). BALB/c mice were dermally exposed to each MWF at concentrations up to 50%. Significant irritation was observed after dermal exposure to all MWFs except CIMTECH 310 and SYNTILO 1023. Of the 9 MWFs, 6 induced greater than a 3-fold increase in lymphocyte proliferation and 7 tested positive in the irritancy assay. TRIM VX yielded the lowest EC3 value (6.9%) with respect to lymphocyte proliferation. Chemical components of TRIM VX identified using HPLC were screened for sensitization potential using structural activity relationship (SAR) modeling and the LLNA. TOPKAT predicted triethanolamine (TEA) as a sensitizer while Derek for Windows predicted only 4-chloro-3-methylphenol (CMP) to be positive for sensitization. When tested in the LLNA only CMP (EC3 = 11.6%) and oleic acid (OA) (EC3 = 29.7%) were identified as sensitizers. Exposure to all tested TRIM VX components resulted in statistically significant irritation. An additive proliferative response was observed when mixtures of the two identified sensitizing TRIM VX components, OA and CMP, were tested in the LLNA. This is one explanation of why the EC3 value of TRIM VX, with respect to lymphocyte proliferation, is lower than those assigned to its sensitizing components.

Biological monitoring for selected herbicide biomarkers in the urine of exposed custom applicators: application of mixed-effect models.

Metabolites and/or parent compounds of the herbicides atrazine, alachlor, metolachlor, cyanazine and the 2-ethylhexyl ester of 2,4-dichlorophenoxyacetic acid (2,4-D) were measured in the urine of 15 custom applicators who each provided from five to seven 24 h urine samples during a 6 week period (n = 87). Each applicator provided a pre-season urine sample and a reference population (n = 46) provided first-morning urine samples. Urinary biomarkers were measured by either immunoassay or gas chromatography. During the spraying season, the geometric mean amount of alachlor mercapturate equivalents (eq.), atrazine eq., 2,4-D and metolachlor mercapturate eq. excreted in 24 h was 17, 19, 110 and 22 nmol, respectively. Mixed-effect models were used to determine predictors of the amount of atrazine eq. and 2,4-D excreted in 24 h. The specific days of herbicide spraying associated with increased biomarker excretion varied for the two analytes, and included one or more days prior to urine collection. This confirms the importance of collecting covariate information on day(s) most relevant to the biomarker of interest. The within-worker variance component, expressed as a geometric standard deviation ((W)GSD range: 2.5-2.9), was substantially larger than the between-worker component ((B)GSD range: 1.3-1.5) for the modeled biomarkers. Alachlor mercapturate eq. and metolachlor mercapturate eq. were detected in more than half of the applicator pre-season urine samples. All biomarkers were detected infrequently in the reference population. Evaluation of non-spray exposure determinants was limited by inclusion of prior day spraying, adjustment for time and the small sample size.

Synthesis, characterization, and use of 2-[(2H(9))butoxy]acetic acid and 2-(3-methylbutoxy)acetic acid as an internal standard and an instrument performance surrogate, respectively, for the gas chromatographic-mass spectrometric determination of 2-butoxyacetic acid, a human metabolite of 2-butoxyethanol.

2-[(2H(9))Butoxy]acetic acid and 2-(3-methylbutoxy)acetic acid were synthesized, mixed with 2-butoxyacetic acid, and separated by capillary gas chromatography on a fused-silica column with a length of 50 m, inside diameter of 0.200 mm, and a "free fatty acid phase" wall coating of 0.3 microm film. 2-[(2H(9))Butoxy]acetic acid, 2-butoxyacetic acid, and 2-(3-methylbutoxy)acetic acid were baseline resolved at retention times of 13.55, 13.78, and 15.20 min; 2-(3-methylbutoxy)acetic acid having a peak efficiency of 360,000. Mass spectrometric detection using selected ion monitoring at m/z 66, 57, and 71 showed linear analytical responses from 0.04 ng to at least 200 ng with a limit of detection of 0.04 ng for 2-butoxyacetic acid.