Correlation between Graphitic Carbon and Elemental Carbon in Diesel Particulate Matter in Workplace Atmospheres.

We investigated the suitability of the graphitic carbon (GC) content of diesel particulate matter (DPM), measured using Raman spectroscopy, as a surrogate measure of elemental carbon (EC) determined by thermal optical analysis. The Raman spectra in the range of 800-1800 cm-1 (including the D mode at ∼1322 cm-1 and the G mode at ∼1595 cm-1) were used for GC identification and quantification. Comparison of the Raman spectra for two certified DPM standards (NIST SRM 1650 and SRM 2975), two types of diesel engine exhaust soot, and three types of DPM-enriched workplace aerosols show that the uncertainty of GC quantification based on the D peak height, G peak height, and the total peak area below D and G peaks was about 6.0, 6.7, and 6.9%, respectively. The low uncertainty for different aerosol types suggested possible use of GC as a surrogate measure of EC in workplace atmospheres. A calibration curve was constructed using two laboratory-aerosolized DPM standards to describe the relationship between GC measured by a portable Raman spectrometer and the EC concentration determined by NIOSH Method 5040. The calibration curve was then applied to determine GC-based estimates of the EC contents of diesel engine exhaust samples from two vehicles and seven air samples collected at a hydraulic fracturing worksite. The GC-EC estimates obtained through Raman measurements agreed well with those found by NIOSH Method 5040 for the same samples at EC filter loadings below 2.86 µg/cm2. The study shows that using an appropriate sample collection method that avoids high filter mass loadings, onsite measurement of GC by a portable or hand-held Raman spectrometer can provide a useful indicator of EC in workplace aerosol.

Exposure assessment of polycyclic aromatic hydrocarbons in refined coal tar sealant applications.

BACKGROUND: Refined coal tar sealant (RCTS) emulsions are used to seal the surface of asphalt pavement. Nine of the 22 polycyclic aromatic hydrocarbons (PAHs) evaluated in this study are classified as known, probable, or possible human carcinogens. Exposure assessment research for RCTS workers has not been published previously. OBJECTIVES: The overall objective of this study was to develop a representative occupational exposure assessment of PAH exposure for RCTS workers based on worksite surveys. The specific aims were to: 1) quantify full-shift airborne occupational exposures to PAHs among RCTS workers; 2) quantify workers' dermal exposures to PAHs; 3) quantify biomarkers of PAH exposure in workers' urine; 4) identify specific job titles associated with RCTS exposure; and 5) apply these results to a biological exposure index to assess risk of potential genotoxicity from occupational exposures. METHODS: A total of twenty-one RCTS workers were recruited from three companies. Personal and area air samples were collected using a modification of NIOSH Method 5515. Dermal exposure was assessed by hand and neck wipes before and after shifts. Twenty-two PAHs were quantified via gas chromatography-mass spectrometry selected ion monitoring. Internal dose was estimated by quantifying select PAH metabolites in pre- and post-shift urine samples using on-line solid phase extraction-high performance liquid chromatography-tandem mass spectrometry. RESULTS: PAH levels in the worker breathing zones were highest for naphthalene, acenaphthene, and phenanthrene, with geometric means of 52.1, 11.4, and 9.8 µg/m3, respectively. Hand wipe levels of phenanthrene, fluoranthene and pyrene were the highest among the 22 PAHs with geometric means of 7.9, 7.7, and 5.5 µg/cm2, respectively. Urinary PAH biomarkers for naphthalene, fluorene, phenanthrene, and pyrene were detected in all workers and were higher for post-shift samples than those collected pre-shift. Urinary concentrations of the metabolite 1-hydroxypyrene were greater than the American Conference of Governmental Industrial Hygienists (ACGIH) Biological Exposure Index (BEI) for this metabolite in 89 percent of post-shift samples collected on the final day of the work week or field survey. Statistically significances were found between concentrations of fluorene, naphthalene, and phenanthrene in the breathing zone of workers and their corresponding urinary PAH biomarkers. Workers were placed in two work place exposure groups: applicators and non-applicators. Applicators had higher total PAH concentrations in personal breathing zone (PBZ) air samples than non-applicators and were more likely to have post-shift hand wipe concentrations significantly higher than pre-shift concentrations. Concentrations of post-shift urinary biomarkers were higher, albeit not significantly, for applicators than non-applicators. CONCLUSIONS: The exposure results from RCTS worker samples cannot be explained by proximal factors such as nearby restaurants or construction. Air and skin concentration levels were substantially higher for RCTS workers than previously published levels among asphalt workers for all PAHs. PAH profiles on skin wipes were more consistent with RCTS sealant product than air samples. Last day post-shift urinary concentrations of 1-hydroxypyrene greatly exceeded the ACGIH BEI benchmark of 2.5 µg/L in 25 of 26 samples, which suggests occupational exposure and risk of genotoxicity. When pyrene and benzo[a]pyrene were both detected, concentration ratios from personal exposure samples were used to calculate the adjusted BEI. Concentrations of 1-hydroxypyrene exceeded the adjusted BEIs for air, hand wipes, and neck wipes in most cases. These results indicate the need to increase safety controls and exposure mitigation for RCTS workers.

Shock Pressure Dependence of Hot Spots in a Model Plastic-Bonded Explosive.

Shock initiation of plastic-bonded explosives (PBX) begins with the formation of so-called "hot spots", which are energetic reactions localized in regions where the PBX microstructure concentrates the input shock wave energy. We developed a model PBX system to study hot spots which consists of a single crystal of the high explosive HMX (cyclotetramethylene-tetranitramine) embedded in a transparent polyurethane binder (J. Phys Chem. A, 2020, 124, 4646-4653). In the current work we use this model system to study the influence of input shock pressure (12-26 GPa) on hot spot generation using micrometer-resolved high-speed imaging and nanosecond-resolved optical pyrometry. By shocking ∼100 HMX single crystals (HMX-SC), two distinct shock pressure thresholds were observed. The threshold for producing single hot spots in some crystals was 15 GPa. At 23 GPa, hot spot density was sufficiently high to lead to rapid deflagration of the entire HMX-SC. It takes about 25 ns after the shock passes for the hot spots to appear to our visible-light detection apparatus which has a noise floor at about 2000 K. That indicates the shock produces nascent hot spots that undergo a thermal explosion that reaches temperatures >2000 K in 25 ns. The initial hot spot temperature is roughly 3800 K which settles down to 3400 K, the adiabatic flame temperature of HMX. The higher initial temperature is attributed to release of stored interfacial strain energy produced by the shock. An initial estimate for the velocity of the flame front originating at an HMX hot spot is 550 m/s.

Continuing the precedent: Financially disadvantaging young people in "unprecedented" COVID-19 times.

The COVID-19 pandemic is both a health and an economic crisis. Economically, lockdowns across Australia have devastated business and industry, creating immediate spikes in under- and unemployment. These impacts intersect with the precarious labour market of casualised and "gig" economy work, where young workers constitute an established and substantial group. While negatively impacting upon many young people's lives, in recent decades precarious employment has also been normalised for young people as they are encouraged to understand themselves as self-reliant and entrepreneurial in their working lives. Yet, these workers have been largely abandoned in the government's economic response to COVID-19. The economic impact and government response to the pandemic substantially disadvantage young people. This article analyses the impact of new government initiatives: the "JobKeeper" wage subsidy scheme, "JobSeeker" payments and early access to superannuation, "JobMaker" economic recovery plan and the redesign of university fees. These initiatives compound preexisting youth policy of low welfare levels, youth wages and high university fees to economically burden young people. Contrasting the repeated expression of anything pandemic related as "unprecedented", we argue that the economic abandonment of young people in the immediate COVID-19 crisis continues a decades-long precedent in Australia of economically disadvantaging young people.

Aerosol Analysis Using Handheld Raman Spectrometer: On-site Quantification of Trace Crystalline Silica in Workplace Atmospheres.

A method for aerosol chemical analysis using handheld Raman spectrometer has been developed and its application to measurement of crystalline silica concentration in workplace atmosphere is described. The approach involves collecting aerosol as a spot sample using a wearable optical aerosol monitor, followed by direct-on-filter quantitative analysis of the spot sample for crystalline silica using handheld Raman spectrometer. The filter cassette of a commercially available optical aerosol monitor (designed to collect aerosol for post-shift analysis) was modified to collect 1.5-mm-diameter spot sample, which provided adequate detection limits for short-term measurements over a few tens of minutes or hours. The method was calibrated using aerosolized α-quartz standard reference material in the laboratory. Two Raman spectrometers were evaluated, one a handheld unit (weighing less than 410 g) and the other a larger probe-based field-portable unit (weighing about 5 kg). The lowest limit of quantification for α-quartz of 16.6 µg m-3 was obtained using the handheld Raman unit at a sample collection time of 1 h at 0.4 l min-1. Short-term measurement capability and sensitivity of the Raman method were demonstrated using a transient simulated workplace aerosol. Workplace air and personal breathing zone concentrations of crystalline silica of workers at a hydraulic fracturing worksite were measured using the Raman method. The measurements showed good agreement with the co-located samples analyzed using the standard X-ray powder diffraction (XRD) method, agreeing within 0.15-23.2% of each other. This magnitude of difference was comparable to the inter- and intra-laboratory analytical precision of established XRD and infrared methods. The pilot study shows that for silica-containing materials studied in this work it is possible to obtain quantitative measurements with good analytical figures of merit using handheld or portable Raman spectrometers. Further studies will be needed to assess matrix interferences and measurement uncertainty for several other types of particle matrices to assess the broader applicability of the method.

Observing Hot Spot Formation in Individual Explosive Crystals Under Shock Compression.

The formation of hot spots in dynamically compressed, plastic-bonded explosives is known to be the primary mechanism by which these materials ignite and initiate, but hot spots are small, fleeting, and hard to observe. Using a microscope equipped with laser-launched, miniflyer plates, we have studied hot spots in small grains of cyclotetramethylene-tetranitramine (HMX) embedded in a polyurethane binder, shocked to about 20 GPa. A nanosecond video with 4 µm spatial resolution is used to observe hot spot formation and growth, while nanosecond optical pyrometry measured temperature. Using individual ∼200 µm nominally single crystals of HMX (HMX-SC), we observed hot spots forming preferentially on corners or edges. These hot spots are about 4000 K. When there are multiple hot spots, the flame propagated along crystal edges, and the crystal is mostly combusted after about 300 ns. Using polycrystalline grains (HMX-PC), 6000 K hot spots are created near internal defects or crystal junctions. However, the thermal mass of the material at 6000 K is quite small, so after those hot spots cool down, the HMX combustion is similar to the single crystals. Comparing a HMX-based polymer-bonded explosive (PBX) to the individual polymer-bonded HMX-SC and HMX-PC grains shows that the myriad hot spots in the PBX are hotter than HMX-SC and colder than HMX-PC, but they persist for a longer time in PBX than in the individual grains.

Comparison and evaluation of urinary biomarkers for occupational exposure to spray adhesives containing 1-bromopropane.

Three metabolites of 1-bromopropane (1-BP) were measured in urine samples collected from 30 workers exposed to 1-BP at two facilities making furniture seat cushions and evaluated for use as biomarkers of exposure. The mercapturic acid metabolite, N-acetyl-S-(n-propyl)-l-cysteine (AcPrCys), 3-bromopropionic acid (3-BPA), and bromide ion levels (Br(-)) were quantitated for this evaluation. The high exposure group consisted of 13 workers employed as adhesive sprayers who assembled foam cushions using 1-BP containing spray adhesives and the low exposure group consisted of 17 non-sprayers, who worked in various jobs without spraying adhesives. All workers' urine voids were collected over the same 48 h period at work, and at home before bedtime, and upon awakening. Urinary AcPrCys and Br(-) levels were elevated in the sprayers compared to that of non-sprayers. Following HPLC-MS/MS analysis of mercapturic acid metabolite levels, 50 urine samples having the highest levels of AcPrCys were analyzed for 3-BPA. No 3-BPA was detected in any of the samples. The data collected from this study demonstrate that AcPrCys and Br(-) are effective biomarkers of 1-BP exposure, but 3-BPA is not.

Evaluation of antineoplastic drug exposure of health care workers at three university-based US cancer centers.

OBJECTIVE: This study evaluated health care worker exposure to antineoplastic drugs. METHODS: A cross-sectional study examined environmental samples from pharmacy and nursing areas. A 6-week diary documented tasks involving those drugs. Urine was analyzed for two specific drugs, and blood samples were analyzed by the comet assay. RESULTS: Sixty-eight exposed and 53 nonexposed workers were studied. Exposed workers recorded 10,000 drug-handling events during the 6-week period. Sixty percent of wipe samples were positive for at least one of the five drugs measured. Cyclophosphamide was most commonly detected, followed by 5-fluorouracil. Three of the 68 urine samples were positive for one drug. No genetic damage was detected in exposed workers using the comet assay. CONCLUSIONS: Despite following recommended safe-handling practices, workplace contamination with antineoplastic drugs in pharmacy and nursing areas continues at these locations.

A pilot respiratory health assessment of nail technicians: symptoms, lung function, and airway inflammation.

BACKGROUND: Recent surveys suggest nail technicians, particularly artificial nail applicators, have increased respiratory symptoms and asthma risk. METHODS: We examined lung function (n = 62) and a marker of airway inflammation, i.e., exhaled nitric oxide (ENO) (n = 43), in a subset of nail technician and control participants in a pilot health assessment. RESULTS: Bivariate analysis of technicians demonstrated that job latency was inversely correlated with FEV1 percent predicted (FEV1PP) (r = -0.34, P = 0.03) and FVCPP (r = -0.32, P = 0.05). Acrylic gel contact hours were inversely correlated with FEV1PP (r = -0.38, P = 0.02) and FVCPP (r = -0.47, P = 0.003). Current smoking was inversely and significantly (P

The psychosocial impacts on families of low-incidence, complex conditions in children: the case of craniopharyngioma.

This paper reports qualitative data from a multidisciplinary, multimethod Craniopharyngioma Child and Family Impact Study conducted at the Royal Children's Hospital, Melbourne. The study aimed to assess the psychosocial impact on children and their families of a childhood craniopharyngioma, a congenital non-hereditary brain tumour that is 'benign' by histology, but often locally invasive. The condition may result in significant morbidity and mortality due to location in the brain, which tends to precipitate multisystemic abnormalities either at the time of presentation, or in conjunction with treatment. The condition has a high survival rate with approximately 90 percent of children alive ten years after diagnosis and although the diagnosis and treatment of craniopharyngioma may result in severe physical and emotional burden for the child and family, there have been few studies to date on the psychosocial impact of this multifaceted condition. Interviews incorporating a purpose-designed Craniopharyngioma Symptom and Treatment Impact Scale were held with 13 families. Impacts on both the family and the children were identified as well as information about the child's coping capacity; parents' fear, uncertainty and trust; family managing and mastery; the experience of hospital; service use and illness specific support. Implications for social work practice are discussed.