Exposure to lead-free frangible firing emissions containing copper and ultrafine particulates leads to increased oxidative stress in firing range instructors.

BACKGROUND: Since the introduction of copper based, lead-free frangible (LFF) ammunition to Air Force small arms firing ranges, instructors have reported symptoms including chest tightness, respiratory irritation, and metallic taste. These symptoms have been reported despite measurements determining that instructor exposure does not exceed established occupational exposure limits (OELs). The disconnect between reported symptoms and exposure limits may be due to a limited understanding of LFF firing byproducts and subsequent health effects. A comprehensive characterization of exposure to instructors was completed, including ventilation system evaluation, personal monitoring, symptom tracking, and biomarker analysis, at both a partially enclosed and fully enclosed range. RESULTS: Instructors reported symptoms more frequently after M4 rifle classes compared to classes firing only the M9 pistol. Ventilation measurements demonstrated that airflow velocities at the firing line were highly variable and often outside established standards at both ranges. Personal breathing zone air monitoring showed exposure to carbon monoxide, ultrafine particulate, and metals. In general, exposure to instructors was higher at the partially enclosed range compared to the fully enclosed range. Copper measured in the breathing zone of instructors, on rare occasions, approached OELs for copper fume (0.1 mg/m3). Peak carbon monoxide concentrations were 4-5 times higher at the partially enclosed range compared to the enclosed range and occasionally exceeded the ceiling limit (125 ppm). Biological monitoring showed that lung function was maintained in instructors despite respiratory symptoms. However, urinary oxidative stress biomarkers and urinary copper measurements were increased in instructors compared to control groups. CONCLUSIONS: Consistent with prior work, this study demonstrates that symptoms still occurred despite exposures below OELs. Routine monitoring of symptoms, urinary metals, and oxidative stress biomarkers can help identify instructors who are particularly affected by exposures. These results can assist in guiding protective measures to reduce exposure and protect instructor health. Further, a longitudinal study is needed to determine the long-term health consequences of LFF firing emissions exposure.

Comprehensive characterization of firing byproducts generated from small arms firing of lead-free frangible ammunition.

Following the introduction of lead-free frangible ammunition in United States Air Force small arms firing ranges, Combat Arms instructors have routinely reported experiencing adverse health symptoms during live fire training exercises, including sore throat, cough, and headache. Previous studies have found that these symptoms occur despite occupational exposure limits not being exceeded. To better characterize the potential source and mechanisms for health symptoms, a comprehensive characterization of the physicochemical properties of gases and aerosols emitted during the firing of the M9 pistol and M4 rifle using lead-free frangible ammunition was completed. Weapons were fired within a sealed chamber using a remote firing mechanism. A suite of direct-reading instruments and collection-based analytical methods were used to determine the composition of the emissions. Emissions were dominated by carbon monoxide and ultrafine particles. Other prevalent gases included carbon dioxide, ammonia, formaldehyde, hydrogen cyanide, and nitric oxide when measured using Fourier-transform infrared spectroscopy. An electrical, low-pressure impactor showed that, on average, the count median diameter immediately after firing was 36 ± 4 nm (n = 10 rounds) and 32 ± 3 nm (n = 14 rounds) for the M9 pistol and M4 rifle, respectively. Analytical methods were used to determine that emitted particles were primarily composed of soot, copper, and potassium, with trace amounts of calcium, silicon, sodium, sulfur, and zinc. Results from this research confirm prior work and expand upon the characterization of emissions generated from firing lead-free frangible ammunition. By employing multiple methods to measure and analyze data we were able to quantify both total and respirable particle fractions and determine particle morphology and composition. Characterization of the emissions provides insight into potential exposure risks that may lead to the development of adverse health symptoms allowing for the development of strategies for risk mitigation.

Video Exposure Monitoring and Position Tracking for Evaluating Particulate and Gas Exposures in a Fully Enclosed Small Arms Firing Range.

The exposure environment in small arms firing ranges is dynamic since ventilation conditions vary in space and time and instructors continuously move around throughout the range. Understanding the impact of engineering controls and instructor behavior on the levels of particulates and gases in the breathing zone is required for providing recommendations to mitigate exposure. In this study, video exposure monitoring (VEM) and position tracking technologies were used in conjunction with real-time measurements of ultrafine particle (UFP) and carbon monoxide (CO) exposures in the breathing zone of instructors in an enclosed small arms firing range. VEM was completed using Enhanced Video Analysis of Dust Exposure 2.1 developed by the National Institute for Occupational Safety and Health. With this program, video recordings of Combat Arms instructor activity were synced with exposure data collected in real-time during small arms training. Position tracking was completed using a system by Pozyx, which uses ultra-wideband (UWB) technology. Position tracking data was aligned with real-time sensor data via time-synchronization. VEM identified that the largest peaks in UFP and CO concentrations generally occurred when instructors were close to the firing line assisting shooters during live fire and when instructors were located near the center of the range near the back wall where the air supplies transition between the Left-Hand-Side (LHS) and Right-Hand-Side (RHS). The UWB position tracking results agreed with the VEM results, confirming that peak exposures occurred when firing range instructors were near the center of the range close to the back wall where the LHS and RHS air supplies transition. Without these exposure visualization technologies, this observation could not have been made. Thus, exposure visualization is a valuable tool to identify gaps in exposure assessment, although future technologies should focus on automation to expedite analysis.

Monthly Variations in Perfluorinated Compound Concentrations in Groundwater.

Large-scale manufacturing of poly- and perfluorinated compounds in the second half of the 20th century has led to their ubiquity in the environment, and their unique structure has made them persistent contaminants. A recent drinking water advisory level issued by the United States Environmental Protection Agency lowered the advisory level concentration of perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) from 200 nanograms per liter and 400 nanograms per liter, respectively, to 70 nanograms per liter separately or combined. Small temporal variations in PFOS and PFOA concentrations could be the difference between meeting or exceeding the recommended limit. In this study, newly sampled data from a contaminated military site in Alaska and historical data from former Pease Air Force Base were collected. Data were evaluated to determine if monthly variations within PFOS and PFOA existed. No statistically significant temporal trend was observed in the Alaska data, while the results from Pease, although statistically significant, showed the spread of observed contaminant concentrations around the fitted line is broad (as indicated by the low R² values), indicating that collection date has little value in predicting contaminant concentrations. Though not currently the subject of a US EPA health advisory, data on perfluorobutanesulfonic acid (PFBS), perfluorohexane sulfonic acid (PFHxS), perfluoroheptanoic acid (PFHpA), and perfluorononanoic acid (PFNA) were collected for each site and their average concentrations evaluated.