Characterizing and Comparing Emissions of Dust, Respirable Crystalline Silica, and Volatile Organic Compounds from Natural and Artificial Stones.

The frequency of cases of accelerated silicosis associated with exposure to dust from processing artificial stones is rapidly increasing globally. Artificial stones are increasingly popular materials, commonly used to fabricate kitchen and bathroom worktops. Artificial stones can contain very high levels of crystalline silica, hence cutting and polishing them without adequate exposure controls represents a significant health risk. The aim of this research was to determine any differences in the emission profiles of dust generated from artificial and natural stones when cutting and polishing. For artificial stones containing resins, the nature of the volatile organic compounds (VOCs) emitted during processing was also investigated. A selection of stones (two natural, two artificial containing resin, and one artificial sintered) were cut and polished inside a large dust tunnel to characterize the emissions produced. The inhalable, thoracic, and respirable mass concentrations of emissions were measured gravimetrically and the amount of crystalline silica in different size fractions was determined by X-ray diffraction. Emissions were viewed using scanning electron microscopy and the particle size distribution was measured using a wide range aerosol spectrometer. VOCs emitted when cutting resin-artificial stones were also sampled. The mass of dust emitted when cutting stones was higher than that emitted when polishing. For each process, the mass of dust generated was similar whether the stone was artificial or natural. The percentage of crystalline silica in bulk stone is likely to be a reasonable, or conservative, estimate of that in stone dust generated by cutting or polishing. Larger particles were produced when cutting compared with when polishing. For each process, normalized particle size distributions were similar whether the stone was artificial or natural. VOCs were released when cutting resin-artificial stones. The higher the level of silica in the bulk material, the higher the level of silica in any dust emissions produced when processing the stone. When working with new stones containing higher levels of silica, existing control measures may need to be adapted and improved in order to achieve adequate control.

Measurement of Diacetyl and 2,3-Pentanedione in the Coffee Industry Using Thermal Desorption Tubes and Gas Chromatography-Mass Spectrometry.

Diacetyl is a potentially harmful chemical that is used as an artificial flavouring in the food industry and may also be generated during processing of some natural products including coffee. In Europe, an 8-h time weighted average occupational exposure limit (TWA-OEL) of 20 ppb has been adopted for diacetyl, together with a short-term exposure limit (STEL) of 100 ppb. A new measurement method involving sampling on thermal desorption tubes and analysis by gas chromatography-mass spectrometry has been used to investigate potential exposure to diacetyl, and the related compound 2,3-pentanedione, at eight companies involved in the coffee industry including large- and small-scale manufacturers and coffee shops. A total of 124 static and personal samples were collected. In the majority of personal samples airborne concentrations of diacetyl were <5 ppb, with those at coffee shops generally <1 ppb. However, diacetyl concentrations in ~40% of the long-term personal samples, mainly originating from one site, were found to be in excess of the newly adopted European TWA-OEL of 20 ppb. Diacetyl concentrations up to 400 ppb were detected on the static samples, with the highest values occurring during grinding of roasted coffee beans. 2,3-Pentanedione was also detected in most of the samples at airborne concentrations around half of those for diacetyl. A significant number of other volatile organic compounds (VOCs) were also detected at sub-ppm concentrations, including acetoin, aliphatic carboxylic acids, aldehydes, ketones and esters, methylfuran, furfural and furfuryl-based alcohols and ketones, and nitrogen containing compounds, such as pyridines and pyrazines. In laboratory tests, diacetyl emissions generated during heating of whole beans were found to be significantly lower than those from heating the same beans after grinding. Diacetyl emissions from both ground and whole beans were also found to be significantly dependent on temperature.

A New Method for Workplace Monitoring of Airborne Diacetyl and 2,3-Pentanedione Using Thermal Desorption Tubes and Gas Chromatography-Mass Spectrometry.

Diacetyl is a potentially harmful chemical that is used as an artificial flavouring in the food industry and may also be generated during processing of some natural products including coffee. In Europe, an 8-h time weighted average occupational exposure limit (TWA-OEL) of 20 ppb has been adopted for diacetyl, together with a short-term exposure limit (STEL) of 100 ppb. A sensitive new measurement method for diacetyl, and the related compound 2,3-pentanedione has been developed and evaluated. The new method uses Tenax TA sorbent tubes as the sampling media with analysis by thermal desorption (TD) and gas chromatography-mass spectrometry (GC-MS). The sample tubes are suitable for both active (pumped) and passive (diffusive) sampling. Diacetyl is stable on the sample tubes for at least 3 months but 2,3-pentanedione requires analysis within a month. Sample recovery is unaffected by changes in relative humidity and the presence of acetic acid. For short-term sampling, active sampling is recommended. The safe sampling volume for diacetyl is 3 litres which, at a flow rate of 100 ml min-1, equates to a maximum recommended sampling time of 30 min. For long-term samples, in particular collection of personal samples, passive sampling is recommended. Diffusive uptake rates have been determined for both diacetyl and 2,3-pentanedione on Tenax TA tubes fitted with standard diffusion heads over sampling periods of 1 to 8 h. Analytical limits of detection are approximately 0.2 ng for diacetyl and 0.1 ng for 2,3-pentanedione. These values equate to airborne concentrations of around 0.04 ppb of diacetyl and 0.02 ppb of 2,3-pentanedione for a 1.5-litre active sample and 0.3 ppb of diacetyl and 0.1 ppb of 2,3-pentanedione for an 8-h passive sample. In the case of passive sampling, this limit of detection is less than 1/50th of the new European TWA-OEL for diacetyl of 20 ppb. The method can also be used to identify the presence of other volatile organic compounds at sub-ppm concentrations.

Performance testing protocol for closed-system transfer devices used during pharmacy compounding and administration of hazardous drugs.

OBJECTIVES: The United States National Institute for Occupational Safety and Health (NIOSH) is developing a protocol to assess the containment performance of closed system transfer devices (CSTDs) when used for drug preparation (task 1) and administration (task 2) and published a draft protocol in September 2016. Nine possible surrogates were proposed by NIOSH for use in the testing. The objectives of this study were to: (A) select the most appropriate surrogate; (B) validate the NIOSH protocol using this surrogate; and (C) determine the containment performance of four commercial CSTDs as compared with an open system of needle and syringe using the validated NIOSH protocol. METHODS: 2-Phenoxyethanol (2-POE) was selected as a surrogate based on its water solubility, Henry's volatility constant, detectability by mass spectrometry, and non-toxicity. Standard analytical validation methods including system suitability, limit of detection (LOD), and limit of quantitation (LOQ) as well as system cleaning validation were performed. The amount of 2-POE released when the CSTDs were manipulated according to two tasks defined by NIOSH was determined using mass spectrometry coupled to thermal desorption and gas chromatography. This approach allows sensitivity of detection below 1 part per billion (ppb). Equashield, Tevadaptor (OnGuard), PhaSeal, and ChemoClave were assessed according to manufacturers' instructions for use. RESULTS: 2-POE was tested and validated for suitability of use within the NIOSH protocol. A simple and efficient cleaning protocol achieved consistently low background values, with an average value, based on 85 measurements, of 0.12 ppb with a 95% confidence interval (CI) of ±0.16 ppb. This gives an LOD for the tests of 0.35 ppb and an LOQ of 0.88 ppb. The Equashield, Tevadaptor (OnGuard), and PhaSeal devices all showed average releases, based on 10 measurements from five tests, that were less than the LOQ (i.e. < 0.88 ppb), while the ChemoClave Vial Shield with Spinning Spiros showed average releases of 2.9±2.3 ppb and 7.5±17.9 ppb for NIOSH tasks 1 and 2 respectively at the 95% confidence level. The open system of needle and syringe showed releases, based on two measurements from a single test, of 4.2±2.2 ppb and 5.1±1.7 ppb for NIOSH tasks 1 and 2 respectively at the 95% confidence level. CONCLUSIONS: 2-POE proved to be an ideal surrogate for testing of CSTDs using the NIOSH protocol. We propose that a CSTD can be qualified using the NIOSH testing approach if the experimental LOQ is less than 1 ppb and the release values are below the LOQ. Equashield, Tevadaptor (OnGuard), and PhaSeal meet these acceptance criteria and can therefore all be qualified as CSTDs, but the ChemoClave system does not and so would not qualify as a CSTD.

Evaluation of the stability of a mixture of volatile organic compounds on sorbents for the determination of emissions from indoor materials and products using thermal desorption/gas chromatography/mass spectrometry.

The standard method for the determination of volatile organic compounds (VOCs) in indoor and test chamber air (ISO 16000-6:2011) specifies sampling onto the sorbent Tenax TA followed by analysis using thermal desorption/gas chromatography/mass spectrometry (TD/GC/MS). The informative Annex D to the standard suggests the use of multi-sorbent samplers to extend the volatility range of compounds which can be determined. The aim of this study was to investigate the storage performance of Tenax TA and two multi-sorbent tubes loaded with a mixture of nine VOCs of relevance for material emissions testing. The sorbent combinations tested were quartz wool/Tenax TA/Carbograph™ 5TD and quartz wool/Tenax TA/Carbopack™ X. A range of loading levels, loading conditions (humidities and air volume), storage times (1-4 weeks) and storage conditions (refrigerated and ambient) were investigated. Longer term storage trials (up to 1 year) were conducted with Tenax TA tubes to evaluate the stability of tubes used for proficiency testing (PT) of material emissions analyses. The storage performance of the multi-sorbent tubes tested was found to be equal to that for Tenax TA, with recoveries after 4 weeks storage of within about 10% of the amounts loaded. No consistent differences in recoveries were found for the different loading or storage conditions. The longer term storage trials also showed good recovery for these compounds, although two other compounds, hexanal and BHT, were found to be unstable when stored on Tenax TA. The results of this study provide confidence in the stability of nine analytes for up to 4 weeks on two multi-sorbent tubes for material emissions testing and the same compounds loaded on Tenax TA sorbent for a recently introduced PT scheme for material emissions testing.

MDHS 25 revisited: part 2, modified sampling and analytical procedures applied to HDI-based isocyanates.

The method that is probably the most commonly used worldwide for the determination of total organic isocyanates (NCO) in air is the Health and Safety Executive method, MDHS 25/3, Organic Isocyanates in Air, and its variants. This paper summarizes some of the research and development work carried out by Health and Safety Laboratory on this method since its publication in 1999 with the eventual aim of incorporating this work in an updated version of MDHS 25 (i.e. MDHS 25/4). The work falls into two main areas: use of liquid chromatography/mass spectrometry (LC/MS) as an alternative to liquid chromatography with electrochemical and ultraviolet/visible detection (LC/EC/UV) and evaluation of 'solid-phase' sampling techniques as an alternative to the impinger-filter combination stated in MDHS 25/3. This paper deals primarily with HDI-based NCO but some comments regarding aromatic NCO (MDI and TDI) are included for completeness. An LC/MS/MS version of MDHS 25/3 has been developed that gives improved performance to the 'classical' version of MDHS 25/3 using EC/UV detection. The LC/MS/MS offers significant advantages over the EC/UV version of MDHS 25/3 in that it is more sensitive, provides improved identification, and has been found to be easier to use. The solid-phase samplers evaluated were a double-thickness glass-fibre (GF/B) filter coated with 1-(2-methoxyphenyl)piperazine (MP) reagent in an IOM (Institute of Occupational Medicine) sampling head ('FIN-MP' sampler) and an MP-impregnated polyurethane foam sponge (PUF) with an MP-coated glass-fibre (GF/A) backup filter also in an IOM sampling head ('Rudzinski' sampler). Both samplers were found to give acceptable performance for the sampling of oligomeric HDI in workplace air and in laboratory simulations when compared to the impinger-filter combination at levels corresponding to the UK short-term limit (70 µg m(-3)). For practical reasons, the FIN-MP sampler was the preferred alternative.

Determination of dithiocarbamate pesticides in occupational hygiene sampling devices using the isooctane method and comparison with an automatic thermal desorption (ATD) method.

Two new methods for the determination of dithiocarbamate pesticides in occupational hygiene sampling devices are described. Dithiocarbamate spiked occupational hygiene sampling devices, consisting of glass fibre (GF/A) filters, cotton pads, cotton gloves and disposable overalls, were reduced under acidic conditions and the CS2 evolved as a decomposition product was extracted into isooctane. The isooctane was then analysed using gas chromatography with mass spectrometry, for CS2, which provided a quantitative result for dithiocarbamates. Recoveries obtained were generally within a 70-110% range and reproducibilities better than 15% RSD were typically achieved. The method has been successfully applied to samples collected during occupational exposure surveys. A second method employing automatic thermal desorption-gas chromatography-mass spectrometry (ATD-GC-MS) has also been developed and applied to the direct analysis of GF/A (airborne) samples. The method relies on the thermal degradation of dithiocarbamates to release CS2, which is used to quantify the analytes. Thiram spiked GF/A filters gave an average recovery of 107% with an RSD of 4%. The performance of the two analytical methods were directly compared by analysing sub-portions of GF/A filters collected during a survey to evaluate occupational exposures to thiram during seed treatment operations. Both methods performed well for the analysis of airborne (GF/A) samples and produced results in good agreement. ATD-GC-MS is the preferred method for studies involving GF/A (airborne) samples only. Because of the wider applicability of the isooctane method for other sampling devices, it is the preferred choice when carrying out surveys which require a dermal as well as respirable exposure assessment.