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.

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.

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 mu g/m(3), 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 mu g/cm(2), 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

Diesel engines serve many purposes in modern oil and gas extraction activities. Diesel particulate matter (DPM) emitted from diesel engines is a complex aerosol that may cause adverse health effects depending on exposure dose and duration. This study reports on personal breathing zone (PBZ) and area measurements for DPM (expressed as elemental carbon) during oil and gas extraction operations including drilling, completions (which includes hydraulic fracturing), and servicing work. Researchers at the National Institute for Occupational Safety and Health (NIOSH) collected 104 full-shift air samples (49 PBZ and 55 area) in Colorado, North Dakota, Texas, and New Mexico during a four-year period from 2008-2012. The arithmetic mean (AM) of the full shift TWA PBZ samples was 10 µg/m3; measurements ranged from 0.1-52 µg/m3. The geometric mean (GM) for the PBZ samples was 7 µg/m3. The AM of the TWA area measurements was 17 µg/m3 and ranged from 0.1-68 µg/m3. The GM for the area measurements was 9.5 µg/m3. Differences between the GMs of the PBZ samples and area samples were not statistically different (P > 0.05). Neither the Occupational Safety and Health Administration (OSHA), NIOSH, nor the American Conference of Governmental Industrial Hygienists (ACGIH) have established occupational exposure limits (OEL) for DPM. However, the State of California, Department of Health Services lists a time-weighted average (TWA) OEL for DPM as elemental carbon (EC) exposure of 20 µg/m3. Five of 49 (10.2%) PBZ TWA measurements exceeded the 20 µg/m3 EC criterion. These measurements were collected on Sandmover and Transfer Belt (T-belt) Operators, Blender and Chemical Truck Operators, and Water Transfer Operators during hydraulic fracturing operations. Recommendations to minimize DPM exposures include elimination (locating diesel-driven pumps away from well sites), substitution, (use of alternative fuels), engineering controls using advanced emission control technologies, administrative controls (configuration of well sites), hazard communication, and worker training.

Click to increase image sizeClick to decrease image size AcknowledgmentsThe authors wish to thank the operators and service companies (and especially their employees) for participation in the NIOSH Field Effort to Assess Chemical Exposures in Oil and Gas Workers. The authors also thank Corey Butler and James Helmkamp (NIOSH Western States Office) and Charles Hayden and Belinda Johnson (NIOSH Division of Applied Research and Technology) for their efforts and contributions prior to and during the field studies.

This report describes a previously uncharacterized occupational health hazard: work crew exposures to respirable crystalline silica during hydraulic fracturing. Hydraulic fracturing involves high pressure injection of large volumes of water and sand, and smaller quantities of well treatment chemicals, into a gas or oil well to fracture shale or other rock formations, allowing more efficient recovery of hydrocarbons from a petroleum-bearing reservoir. Crystalline silica (frac sand) is commonly used as a proppant to hold open cracks and fissures created by hydraulic pressure. Each stage of the process requires hundreds of thousands of pounds of quartz-containing sand; millions of pounds may be needed for all zones of a well. Mechanical handling of frac sand creates respirable crystalline silica dust, a potential exposure hazard for workers. Researchers at the National Institute for Occupational Safety and Health collected 111 personal breathing zone samples at 11 sites in five states to evaluate worker exposures to respirable crystalline silica during hydraulic fracturing. At each of the 11 sites, full-shift samples exceeded occupational health criteria (e.g., the Occupational Safety and Health Administration calculated permissible exposure limit, the NIOSH recommended exposure limit, or the ACGIH threshold limit value), in some cases, by 10 or more times the occupational health criteria. Based on these evaluations, an occupational health hazard was determined to exist for workplace exposures to crystalline silica. Seven points of dust generation were identified, including sand handling machinery and dust generated from the work site itself. Recommendations to control exposures include product substitution (when feasible), engineering controls or modifications to sand handling machinery, administrative controls, and use of personal protective equipment. To our knowledge, this represents the first systematic study of work crew exposures to crystalline silica during hydraulic fracturing. Companies that conduct hydraulic fracturing using silica sand should evaluate their operations to determine the potential for worker exposure to respirable crystalline silica and implement controls as necessary to protect workers. [Supplementary materials are available for this article. Go to the publisher's online edition of Journal of Occupational and Environmental Hygiene for the following free supplemental resource: a file containing controls and recommendations to limit worker exposures to respirable crystalline silica at hydraulic fracturing work sites.]