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.

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.

Measurement of area and personal breathing zone concentrations of diesel particulate matter (DPM) during oil and gas extraction operations, including hydraulic fracturing.

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.

Occupational exposures to respirable crystalline silica during hydraulic fracturing.

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.

DNA-nanostructure-assembly by sequential spotting.

BACKGROUND: The ability to create nanostructures with biomolecules is one of the key elements in nanobiotechnology. One of the problems is the expensive and mostly custom made equipment which is needed for their development. We intended to reduce material costs and aimed at miniaturization of the necessary tools that are essential for nanofabrication. Thus we combined the capabilities of molecular ink lithography with DNA-self-assembling capabilities to arrange DNA in an independent array which allows addressing molecules in nanoscale dimensions. RESULTS: For the construction of DNA based nanostructures a method is presented that allows an arrangement of DNA strands in such a way that they can form a grid that only depends on the spotted pattern of the anchor molecules. An atomic force microscope (AFM) has been used for molecular ink lithography to generate small spots. The sequential spotting process allows the immobilization of several different functional biomolecules with a single AFM-tip. This grid which delivers specific addresses for the prepared DNA-strand serves as a two-dimensional anchor to arrange the sequence according to the pattern. Once the DNA-nanoarray has been formed, it can be functionalized by PNA (peptide nucleic acid) to incorporate advanced structures. CONCLUSIONS: The production of DNA-nanoarrays is a promising task for nanobiotechnology. The described method allows convenient and low cost preparation of nanoarrays. PNA can be used for complex functionalization purposes as well as a structural element.

Online Multiperson Tracking-by-Detection from a Single, Uncalibrated Camera.

In this paper, we address the problem of automatically detecting and tracking a variable number of persons in complex scenes using a monocular, potentially moving, uncalibrated camera. We propose a novel approach for multiperson tracking-by-detection in a particle filtering framework. In addition to final high-confidence detections, our algorithm uses the continuous confidence of pedestrian detectors and online-trained, instance-specific classifiers as a graded observation model. Thus, generic object category knowledge is complemented by instance-specific information. The main contribution of this paper is to explore how these unreliable information sources can be used for robust multiperson tracking. The algorithm detects and tracks a large number of dynamically moving people in complex scenes with occlusions, does not rely on background modeling, requires no camera or ground plane calibration, and only makes use of information from the past. Hence, it imposes very few restrictions and is suitable for online applications. Our experiments show that the method yields good tracking performance in a large variety of highly dynamic scenarios, such as typical surveillance videos, webcam footage, or sports sequences. We demonstrate that our algorithm outperforms other methods that rely on additional information. Furthermore, we analyze the influence of different algorithm components on the robustness.

Immobilization of different biomolecules by atomic force microscopy.

BACKGROUND: Micrometer resolution placement and immobilization of probe molecules is an important step in the preparation of biochips and a wide range of lab-on-chip systems. Most known methods for such a deposition of several different substances are costly and only suitable for a limited number of probes. In this article we present a flexible procedure for simultaneous spatially controlled immobilization of functional biomolecules by molecular ink lithography. RESULTS: For the bottom-up fabrication of surface bound nanostructures a universal method is presented that allows the immobilization of different types of biomolecules with micrometer resolution. A supporting surface is biotinylated and streptavidin molecules are deposited with an AFM (atomic force microscope) tip at distinct positions. Subsequent incubation with a biotinylated molecule species leads to binding only at these positions. After washing streptavidin is deposited a second time with the same AFM tip and then a second biotinylated molecule species is coupled by incubation. This procedure can be repeated several times. Here we show how to immobilize different types of biomolecules in an arbitrary arrangement whereas most common methods can deposit only one type of molecules. The presented method works on transparent as well as on opaque substrates. The spatial resolution is better than 400 nm and is limited only by the AFM's positional accuracy after repeated z-cycles since all steps are performed in situ without moving the supporting surface. The principle is demonstrated by hybridization to different immobilized DNA oligomers and was validated by fluorescence microscopy. CONCLUSIONS: The immobilization of different types of biomolecules in high-density microarrays is a challenging task for biotechnology. The method presented here not only allows for the deposition of DNA at submicrometer resolution but also for proteins and other molecules of biological relevance that can be coupled to biotin.

Cutting off the nose to save the penis.

INTRODUCTION: The average bicycle police officer spends 24 hours a week on his bicycle and previous studies have shown riding a bicycle with a traditional (nosed) saddle has been associated with urogenital paresthesia and sexual dysfunction. AIM: The objective of this study was to assess the effectiveness of the no-nose bicycle saddle as an ergonomic intervention and their acceptance among male bicycle police officers. METHODS: Bicycle police officers from five U.S. metropolitan areas were recruited for this study. Officers completed: (i) the International Index of Erectile Function Questionnaire (IIEF); (ii) computerized pressure measurements at the points of contact on the bicycle; the handlebars, the pedals, and the saddle; (iii) one night of nocturnal Rigiscan assessment; (iv) penile vibrotactile sensitivity threshold assessed by computerized biothesiometery. Officers selected a no-nose saddle for their bicycles and were asked to use the intervention saddle exclusively for 6 months, at which point they were retested. MAIN OUTCOME MEASURES: Perineal pressure, urogenital numbness, penile vibrotactile sensitivity threshold, erectile function as measure by International Index of Erectile Function Questionnaire (IIEF) and Rigiscan. RESULTS: After 6 months, 90 men were reassessed. Only three men had returned to a traditional saddle. The results are presented for those who used the no-nose saddle continuously for 6 months. There was a 66% reduction in saddle contact pressure in the perineal region (P < 0.001). There was a significant improvement in penis tactile sensation (P = 0.015). There was a significant improvement in erectile function assessed by IIEF (P = 0.015). There were no changes noted in the Rigiscan measures. The number of men indicating they had not experienced urogential paresthesia while cycling for the preceding 6 months, rose from 27% to 82% using no-nose saddles. CONCLUSIONS: (i) With few exceptions, bicycle police officers were able to effectively use no-nose saddles in their police work. (ii) Use of no-nose saddles reduced most perineal pressure. (iii) Penile health improved after 6 month using no-nose saddles as measured by biothesiometry and IIEF. There was no improvement in Rigiscan(R) measure after 6 months of using no nose saddles, suggesting that a longer recovery time may be needed..

Effect of bicycle saddle designs on the pressure to the perineum of the bicyclist.

PURPOSE: Increasing awareness of an association between bicycling and male sexual dysfunction has led to the appearance of a variety of bicycle saddles that share the design objective of reducing pressure in the groin of the cyclist by removal of the narrow protruding nose of the saddle. This study compared three of these saddle designs to a traditional sport/road racing saddle with a narrow protruding nose in terms of pressure in the region of the perineum (groin) of the cyclist. METHODS: Saddle, pedal, and handlebar contact pressure were measured from 33 bicycle police patrol officers pedaling a stationary bicycle at a controlled cadence and workload. Pressure was characterized over the saddle as a whole and over a region of the saddle assumed to represent pressure on the cyclist's perineum located anteriorly to the ischial tuberosities. RESULTS: The traditional sport/racing saddle was associated with more than two times the pressure in the perineal region than the saddles without a protruding nose (P < 0.01). There were no significant differences in perineal pressure among the nontraditional saddles. Measures of load on the pedals and handlebars indicated no differences between the traditional saddle and those without protruding noses. This finding is contradictory to those studies suggesting a shift toward greater weight distribution on the handlebars and pedals when using a saddle without a nose. CONCLUSIONS: The recommendation of a saddle without a narrow protruding nose appears to be justified to reduce pressure to the perineum of the bicyclist.

Nocturnal penile tumescence and rigidity testing in bicycling patrol officers.

A health assessment study was conducted in response to complaints of groin numbness in a bicycling police unit. Seventeen male cyclists were compared with 5 nonbiking men. The cyclists rode an average of 5.4 hours per day, and 91% indicated they experienced groin numbness on occasion. Each man wore the RigiScan Plus Rigidity Assessment System for one normal sleep session. Pressure measurements were also taken between the cyclist and the bicycle saddle. The percentage of sleep sessions that recorded an erectile event was significantly lower in the cyclists than it was in noncyclists (cyclists 27.1%; noncyclists 42.8%; P =.008). This duration percentage is negatively correlated with average hours a day that cyclists rode their bikes (r = -.41; P =.05), the number of days a week they rode (r = -.55; P =.009), and the average pressure exerted on the nose of the bike saddle (r = -.39; P =.08). The other measures of erectile quality (tumescence activity units [TAUs] and rigidity activity units [RAUs] of both the base and tip of the penis) were lower in the cyclists, but did not reach statistical significance. The number of hours cyclists rode during the day of RigiScan Plus assessment was negatively correlated with penis tip RAU (r = -.41; P =.04), and tip TAU (r = -.45; P =.04). These data suggest that prolonged bicycle riding may have negative effects on nocturnal erectile function and indicate a need for innovative bicycle saddle designs.