{"id":2819,"date":"2018-03-27T18:56:37","date_gmt":"2018-03-27T21:56:37","guid":{"rendered":"https:\/\/www.nachodelatorre.com.ar\/mosconi\/?p=2819"},"modified":"2018-03-27T18:56:37","modified_gmt":"2018-03-27T21:56:37","slug":"toxicidad-de-los-residuos-gaseosos-y-solidos-de-disparos-con-armas-de-fuego-en-poligonos-cerrados","status":"publish","type":"post","link":"https:\/\/www.fie.undef.edu.ar\/ceptm\/?p=2819","title":{"rendered":"Toxicidad de los residuos gaseosos y s\u00f3lidos de disparos con armas de fuego en pol\u00edgonos cerrados"},"content":{"rendered":"

<\/u>Los disparos con armas de fuego, producen residuos de la combusti\u00f3n de los materiales energ\u00e9ticos empleados como propulsantes, as\u00ed como metales pesados en part\u00edculas de diferentes tama\u00f1os. En el caso particular de la pr\u00e1ctica de tiro que se desarrolla en pol\u00edgonos cerrados, dependiendo de la eficiencia de los sistemas de ventilaci\u00f3n, las dimensiones de la instalaci\u00f3n, el n\u00famero de disparos que se realizan, el tipo de munici\u00f3n y propulsante, el aire contiene diversos metales y componentes gaseosos que generan variados niveles de toxicidad.<\/p>\n

Among the studied metals, Pb concentrations were highest; however, OSHA limit values were only exceeded in one case, when also the highest numbers of gun shots were made. The majority of Pb particles were in fractions >120\u2005nm. Although concentrations of Cu, Ni, and Zn were significantly lower than Pb, they were more often present as nanoparticles (<120\u2005nm). This increases their harmfulness, as nanoparticles can easily penetrate the cardiovascular and nervous systems. To decrease the potential health risks of heavy metals at shooting ranges, more efficient ventilation, optimization of the number of gunshots, and the use of lead\u2010free ammunition should be implemented.<\/p>\n

\n

1 Introduction<\/h3>\n

Small firearm shooting practice is regularly conducted at indoor shooting ranges. Depending on the efficiency of the ventilation, number of fired gunshots, ammunition type and propellant, and other factors, air can contain various metals, such as Cu, Pb, Zn, and Sb, and gaseous components such as CO, CO2<\/sub>, NO, NO, NH3<\/sub>, HCN, and CH4<\/sub>\u00a01<\/a>–9<\/a>. Although lead\u2010free ammunition does not produce Pb, various metals (e.\u2009g. Cu, Zn, B, K, Fe), as well as organic compounds such as polyaromatic hydrocarbons and aldehydes, are present\u00a08<\/a>,\u00a010<\/a>,\u00a011<\/a>. Organic compounds in ammunition are found in the propellant powder and primer mixture. Inorganic compounds derive mostly from the primer mixture, case, and bullet\u00a09<\/a>. Altogether those energetic materials with metal fumes can be significant source of particles at shooting ranges\u00a012<\/a>.<\/p>\n

Metals occur in ambient air as particulate matter (PM) in different size fractions and their health effects have been studied widely. PM has been associated with cardiovascular and respiratory morbidity and mortality due to both short\u2010 and long\u2010term exposure\u00a013<\/a>,\u00a014<\/a>. Many epidemiological studies have analysed the health effects of PM from traffic and residential heating\u00a015<\/a>. Few studies have investigated heavy metals at indoor shooting ranges in relation to potential adverse health effects and most focused on lead (Pb). They found lead\u2010containing ammunition can produce elevated levels of lead in the blood\u00a016<\/a>–21<\/a>. Exposure to lead may produce several health symptoms, such as hypertension, hyper\u2010reflexia, tremors, and upper extremity weakness\u00a022<\/a>. People may also develop problems with cognition, memory, attention, language, and motor skills\u00a023<\/a>. It has also been shown that using lead\u2010free ammunition and\/or more efficient ventilation can reduce exposure to lead\u00a024<\/a>.<\/p>\n

Particulate matter (PM) differs in size and nano\u2010sized ultrafine particles (<100\u2005nm) are considered most harmful, because of their high penetrability to the lungs\u00a025<\/a>,\u00a026<\/a>. When interacting with cells, PM nanoparticles can induce lipid peroxidation, cause intracellular oxidative stress, increase cytosolic calcium ion concentration, activate EGF receptors, and disrupt normal electron transport leading to oxidative stress\u00a027<\/a>. Metal oxide nanoparticles (MeONPs) have been known to cause cytotoxicity; the most harmful MeONPs are Tl2<\/sub>O\/Tl2<\/sub>, Ag2<\/sub>O, and Au2<\/sub>O\/Au2<\/sub>O3<\/sub>\u00a0[28]. When airborne metals at indoor shooting ranges\u00a09<\/a>\u00a0form oxides, the most toxic to human health could be PbO\/PbO2<\/sub>, MgO, NiO, ZnO, and CuO\u00a028<\/a>. NiO is known to induce apoptosis by repressing SIRT1\u00a029<\/a>. Lung inflammation and cytotoxicity were observed in rats exposed to Cu2<\/sub>O3<\/sub>\u00a030<\/a>. ZnO nanoparticles cause cytotoxicity, apoptosis, cell cycle alternations, and genetic damage\u00a031<\/a>. One study revealed that CuO is more hazardous than PbO or ZnO, but because the heterogeneity of PbO suspensions does not allow (eco)toxicity assessments, its hazard score was low and it could actually be a higher risk\u00a032<\/a>. Thus, hazardousness seems to depend on the model and parameters used.<\/p>\n

The aim of this study was to assess lead (Pb), copper (Cu), nickel (Ni), and zinc (Zn) concentrations in particulate matter at indoor military shooting ranges.<\/p>\n<\/div>\n

\n

2 Experimental Section<\/h3>\n
\n

2.1 Sample Collection<\/h4>\n

Measurements of particulate matter (PM) were done with ELPI+ (Electrical Low Pressure Impactor) (Dekati Ltd.). It classifies particles according to their aerodynamic diameter and enables real\u2010time measurement of particle size distribution and concentration in the size range 6\u2005nm\u201310\u2005\u03bcm. Particles that enter the impactor unit are separated using 14 different stages (filters) according to their aerodynamic size and behaviour. Particle samples were collected \u2013 over two hours \u2013 at three shooting ranges (SR) (Figure\u20051<\/a>), and lead (Pb), copper (Cu), nickel (Ni), and zinc (Zn) concentrations analysed later in a laboratory. Background measurements were done at SR1 at night with no gunfire (Figure\u20052<\/a>). In SR1 and SR2, samples were collected on two separate days; at SR3, measurements were conducted on a single day. During shooting training, Heckler & Koch USP (9\u00d719\u2005mm) pistols were used at SR1 and SR2, and Makarovs (9\u00d718\u2005mm) at SR3. Details of the ammunition are given in Table\u20051<\/a>. Temperature, humidity, and air pressure were monitored during sample collection, and ventilation systems were working at normal settings.<\/p>\n

\n
\"\"<\/a>
\n
Figure 1<\/strong><\/p>\n
Open in figure viewer<\/a>PowerPoint<\/a><\/div>\n<\/div>\n
\n

The shooting ranges (photos are distorted for security purposes<\/i>).<\/p>\n<\/div>\n<\/figcaption><\/figure>\n<\/section>\n

\n
\"\"<\/a>
\n
Figure 2<\/strong><\/p>\n
Open in figure viewer<\/a>PowerPoint<\/a><\/div>\n<\/div>\n
\n

Particulate matter (PM) concentrations (\u03bcg\/m3<\/sup>) in different fractions at the shooting ranges. A and B indicate different shooting days.<\/p>\n<\/div>\n<\/figcaption><\/figure>\n<\/section>\n

\n
Table 1.\u00a0<\/span>Gun and ammunition types, and number of gunshots fired at each shooting range.<\/header>\n
\n\n\n\n\n\n\n\n\n\n
Shooting range<\/th>\nShooting day<\/th>\nFirearm type<\/th>\nAmmunition type<\/th>\nNumber of gunshots<\/th>\n<\/tr>\n<\/thead>\n
1<\/td>\nA<\/td>\nHeckler & Koch, 9\u00d719\u2005mm<\/td>\nm\/39B, 6.75\u2005g<\/td>\n720<\/td>\n<\/tr>\n
1<\/td>\nB<\/td>\nHeckler & Koch, 9\u00d719\u2005mm<\/td>\nm\/39B, 6.75\u2005g<\/td>\n480<\/td>\n<\/tr>\n
2<\/td>\nA<\/td>\nHeckler & Koch, 9\u00d719\u2005mm<\/td>\nMagtech Luger FMJ, 8\u2005g<\/td>\n510<\/td>\n<\/tr>\n
2<\/td>\nB<\/td>\nHeckler & Koch, 9\u00d719\u2005mm<\/td>\nUnknown<\/td>\n270<\/td>\n<\/tr>\n
3<\/td>\n <\/td>\nMakarov, 9\u00d718\u2005mm<\/td>\nBarnaul, 6\u2005g<\/td>\n875<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n<\/div>\n<\/div>\n<\/div>\n
\n

2.2 Laboratory Methods<\/h4>\n

ELPI+ filters were analysed using an Agilent 7500 Series ICP\u2010MS instrument and Vista\u2010MPX CCD Simultaneous ICP\u2010OES (Agilent Technologies). The samples were dissolved in J.T. Baker nitric acid and diluted in Simplicity UV Millipore purified water. Internal Standard Stock Solution (100\u2005mg\/ml of Li, Sc, Ge, Rh, In, Tb, Lu, and Bi in 10\u2009% HNO3<\/sub>) was used for IPC\u2010MS. ICP\u2010OS was calibrated using the Environmental Calibration Standard. Calibration graphs were made according to the Cot #QCCS\u201026 \u201cQuality Control Standard 26\u201d solvent. Argon (Ar) gas was used for calibration.<\/p>\n

Samples were dissolved from the filters using 5\u2005ml concentrated nitric acid while being microwaved (1600\u2005W, 200\u2009\u00b0C, 3447.38\u2005kPa, 10\u2005minutes duration). The Teflon containers were left to cool\u2010down to room temperature. The solution was filtered through a paper filter into a 25\u2005ml volumetric flask and filled with water to the mark.<\/p>\n

Regarding the calibration charts, the squared correlation coefficient\u00a0r<\/i>2<\/sup>\u00a0of ICP\u2010OES was 0.99995 and ICP\u2010MS 0.9995. Spectral interferences were minimized and only less interfered isotopes were measured. Cu and Pb were measured with ICP\u2010OES, and Ni and Zn with ICP\u2010MS.<\/p>\n<\/div>\n<\/div>\n

\n

3 Results<\/h3>\n

Background particulate matter (PM) concentrations at shooting range 1 (SR1) were highest in fractions of 0.76 and 8.10\u2005\u03bcm (coarse particle mode), and lowest in fraction 0.01\u2005\u03bcm (Aitken mode). Average background PM concentration across fractions was 5.4\u2005\u03bcg\/m3<\/sup>\u00a0(maximum 10.5\u2005\u03bcg\/m3<\/sup>). Compared to concentrations during shooting, background levels were up to two orders of magnitude lower.<\/p>\n

During shooting training at SR1, PM concentrations were highest on the first measurement day (A) when more shots were fired (Figure\u20052<\/a>, Table\u20051<\/a>). Among the fractions, the highest proportion of PM was 0.20\u2005\u03bcm in diameter. On the second day (B), the 0.20\u2005\u03bcm fraction remained highest, but differences between fractions 0.48\u20138.10\u2005\u03bcm were non\u2010significant. Average PM concentration during shooting at SR1 on the first day (A) was 271.4\u2005\u03bcg\/m3<\/sup>(maximum 1161.4\u2005\u03bcg\/m3<\/sup>); the second day (B) average was 90.7\u2005\u03bcg\/m3<\/sup>\u00a0(maximum 126.4\u2005\u03bcg\/m3<\/sup>). At SR2, PM concentration was highest in fraction 0.31\u2005\u03bcm on the first day (A) and 0.48\u2005\u03bcm on the second day (B). On the first day (A), the average PM concentration was 19.6\u2005\u03bcg\/m3<\/sup>\u00a0(maximum 65.7\u2005\u03bcg\/m3<\/sup>) and on the second day 28.9\u2005\u03bcg\/m3<\/sup>\u00a0(maximum 151.9\u2005\u03bcg\/m3<\/sup>). At SR3, PM concentrations differed somewhat from SR1 and SR2, with coarser particles \u2013 PM in fractions of 1.22\u2005\u03bcm and 1.94\u2005\u03bcm \u2013 highest. The average concentration was 26.8\u2005\u03bcg\/m3<\/sup>(maximum 70.9\u2005\u03bcg\/m3<\/sup>).<\/p>\n

Lead (Pb), Copper (Cu), Nickel (Ni), and Zinc (Zn) concentrations were analysed from ELPI+ impactor PM samples. The highest concentration of Pb was found at SR1 on the first day (A) and the lowest at SR3, with average concentrations of 54.3 and 6.1\u2005\u03bcg\/m3<\/sup>, respectively (Figure\u20053<\/a>). Maximum concentration of Pb (150.0\u2005\u03bcg\/m3<\/sup>) was in the PM fraction 1.95\u2005\u03bcm. Average concentration of Cu was highest at SR2 on the first day (2.7\u2005\u03bcg\/m3<\/sup>) and lowest at SR1 on the first day (0.8\u2005\u03bcg\/m3<\/sup>). Maximum concentration of Cu (4.0\u2005\u03bcg\/m3<\/sup>) was collected in the smallest analysed fraction (0.01\u2005\u03bcm) at SR2 on the first day. Average concentration of Ni was highest at SR2 on the first day (0.3\u2005\u03bcg\/m3<\/sup>) and lowest at SR1 on the second day (0.1\u2005\u03bcg\/m3<\/sup>). Maximum concentration of Ni was 0.6\u2005\u03bcg\/m3<\/sup>\u00a0in the fraction 1.22\u2005\u03bcm at SR1 on the first day. Average concentration of Zn was highest (0.7\u2005\u03bcg\/m3<\/sup>) at SR2 on the first day and lowest (0.3\u2005\u03bcg\/m3<\/sup>) at SR2 on the second day. Maximum concentration of Zn was 2.0\u2005\u03bcg\/m3<\/sup>\u00a0in the larger fraction 8.10\u2005\u03bcg at SR2 on the first day.<\/p>\n

\n
\"\"<\/a>
\n
Figure 3<\/strong><\/p>\n
Open in figure viewer<\/a>PowerPoint<\/a><\/div>\n<\/div>\n
\n

Lead (Pb), copper (Cu), nickel (Ni), and zinc (Zn) concentrations (\u03bcg\/m3<\/sup>) at the shooting ranges. A and B indicate different shooting days.<\/p>\n<\/div>\n<\/figcaption><\/figure>\n<\/section>\n<\/div>\n

\n

4 Discussion<\/h3>\n

In the current study, particulate matter (PM) concentrations and its proportions of lead (Pb), copper (Cu), nickel (Ni), and zinc (Zn) were analysed at indoor military shooting ranges during small firearms shooting training. As all ammunition contained Pb, high levels of lead in the air were expected. Earlier studies have shown that lead\u2010containing ammunition can result in high levels of lead in blood\u00a033<\/a>\u00a0and cause various health problems among shooters\u00a019<\/a>. To decrease these problems, ventilation settings should be set to get the most efficient air pollution removal possible, and lead\u2010free ammunition used. The higher number of gunshots fired at SR1 during the first day produced significantly higher levels of lead in the air.<\/p>\n

Our analysis also showed gunfire produced in nano\u2010size fractions (<120\u2005nm) more Ni, Cu, and Zn particles compared to Pb; though, lead had the highest concentrations in larger PM fractions. Among the shooting ranges, SR1 had most nano\u2010size particles produced during shootings, followed by SR2 on the second measurement day. In general, concentrations were highest at SR1 and lowest at SR3, despite the highest number of gunshots having been fired at the latter range. The main explanation of this counterintuitive result could be the different firearm and or ammunition used as well as differences in the ventilation.<\/p>\n

The problem of high heavy metal levels military personnel can be exposed to has been noted before\u00a020<\/a>. Current knowledge is mostly limited to the toxicity of lead, because most ammunition contains it\u00a016<\/a>,\u00a021<\/a>,\u00a034<\/a>. According to Occupational Safety and Health Administration (OSHA) standards, employees should not be exposed to over 50\u2005\u03bcg\/m3<\/sup>\u00a0of airborne lead averaged over an eight hour period, and action must be taken if the concentration is 30\u2005\u03bcg\/m3<\/sup>\u00a0or more\u00a035<\/a>. Our study involved military personnel and their exposure time was two hours during our measurements. If we recalculate this on an eight hour basis, only at SR1 on one day were OSHA Pb standards exceeded.<\/p>\n

We also found Ni, Cu, and Zn in significant concentrations, and the potential adverse health effects of exposure to these metals have been shown in\u2005vitro\u00a028<\/a>,\u00a029<\/a>,\u00a036<\/a>. Moreover, it has been noted that occupationally exposed people have a higher risk of respiratory tract cancer due to inhalation of nickel and copper\u00a037<\/a>. Recently, there has been an increase in the use of systemic serum amyloid A as a biomarker of inflammation in relation to exposure to zinc and especially copper\u2010containing metal fumes and particles\u00a038<\/a>. In study animals, exposure to occupational levels of air\u2010borne ZnO nanoparticles has resulted in inflammation of lung tissue, myocardial and DNA damage, and inflammation and apoptosis have been recognized\u00a039<\/a>.<\/p>\n

This is the first large\u2010scale study conducted at multiple indoor military shooting ranges that has concentrated on nano\u2010sized particles. As the replacement of micrometer\u2010sized metal fuel powders in gas\u2010generating solid propellants with nanosized metal powders has become a common trend in the design of new types of propellants in recent decades, that could decrease the average size of the particles\u00a040<\/a>. As we did not change any indoor parameters during the measurements, and shooters used the same ammunition types as during normal training, our results reflect the situation on a usual shooting day. A limitation of the study could be that only four metals were analysed due to the very small concentrations in the smallest PM fractions, nor did we measure ventilation parameters. Our measurements at the different shooting ranges are not fully comparable, because of differences in the speed of air exchange, guns and ammunation. In addition, we could not influence the number of gunshots fired at each SR, or collect any information about the shooters due to security reasons.<\/p>\n

Future studies should measure ventilation parameters, such as ventilation rates, and could analyse a larger number of compounds if a high enough number of shots are made. New studies could also compare different ammunition types, i.\u2009e. Pb\u2010containing to Pb\u2010free, and how their use could affect human health. Another important aspect could be biomonitoring of Ni, Cu, and Zn \u2013 to compliment the already widely implemented Pb biomonitoring \u2013 among personnel to study the health effects of heavy metals.<\/p>\n<\/div>\n

\n

5 Conclusions<\/h3>\n

Among the studied metals, Pb concentrations were highest and on one day at shooting range 1 exceeded the standards set by the OSHA. More efficient ventilation, minimizing the number of gunshots, and the use of lead\u2010free ammunition could help to fulfil the OSHA requirements. Cu, Ni, and Zn were relatively more often present as nanoparticles (<120\u2005nm), which increases the health risks.<\/p>\n<\/div>\n

Fuente:<\/strong>\u00a0https:\/\/onlinelibrary.wiley.com<\/a><\/em><\/p>\n","protected":false},"excerpt":{"rendered":"

Los disparos con armas de fuego, producen residuos de la combusti\u00f3n de los materiales energ\u00e9ticos empleados como propulsantes, as\u00ed como metales pesados en part\u00edculas de… <\/p>\n","protected":false},"author":1,"featured_media":0,"comment_status":"closed","ping_status":"closed","sticky":false,"template":"","format":"standard","meta":[],"categories":[18,29,24],"tags":[],"_links":{"self":[{"href":"https:\/\/www.fie.undef.edu.ar\/ceptm\/index.php?rest_route=\/wp\/v2\/posts\/2819"}],"collection":[{"href":"https:\/\/www.fie.undef.edu.ar\/ceptm\/index.php?rest_route=\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/www.fie.undef.edu.ar\/ceptm\/index.php?rest_route=\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/www.fie.undef.edu.ar\/ceptm\/index.php?rest_route=\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"https:\/\/www.fie.undef.edu.ar\/ceptm\/index.php?rest_route=%2Fwp%2Fv2%2Fcomments&post=2819"}],"version-history":[{"count":0,"href":"https:\/\/www.fie.undef.edu.ar\/ceptm\/index.php?rest_route=\/wp\/v2\/posts\/2819\/revisions"}],"wp:attachment":[{"href":"https:\/\/www.fie.undef.edu.ar\/ceptm\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=2819"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.fie.undef.edu.ar\/ceptm\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=2819"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.fie.undef.edu.ar\/ceptm\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=2819"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}