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Communication

Can Isotopes Be Used as Lead Tracers in Shooting-Range Soils?

by
Andrés Rodríguez-Seijo
1,2,3,*,
Knut Endre Sjåstad
4 and
Vladislav Chrastný
5
1
Interdisciplinary Centre of Marine and Environmental Research (CIIMAR), University of Porto, Terminal de Cruzeiros do Porto de Leixões, Av. General Norton de Matos s/n, 4450-208 Matosinhos, Portugal
2
Biology Department, Faculty of Sciences, University of Porto, 4169-007 Porto, Portugal
3
Área de Edafoloxía e Química Agrícola, Facultade de Ciencias, Universidade de Vigo, 32004 Ourense, Spain
4
National Criminal Investigation Service (KRIPOS), P.O. Box 8163, 0034 Oslo, Norway
5
Faculty of Environmental Sciences, Czech University of Life Sciences Prague, Kamýcká 129, Praha 6, Suchdol, 165 21 Prague, Czech Republic
*
Author to whom correspondence should be addressed.
Submission received: 28 July 2022 / Revised: 7 August 2022 / Accepted: 31 August 2022 / Published: 1 September 2022

Abstract

:
Lead isotopes have been widely used to assess the sources of Pb in the soil environment since lead isotopes ratios have a specific signature that allows us to use them as environmental tracers. However, some lead sources are difficult to be identified. This article contains the lead isotope data from soils and shot pellets collected in an abandoned shooting range (NW Spain). Twelve soil and three-shot pellet samples were randomly collected and analyzed using MC-ICP-MS. The isotope ratios are shown, and analyses proved that Pb originated predominantly from the used shot pellets. Contaminated soils exhibited an isotopic composition (206Pb/207Pb, 208Pb/204Pb, 206Pb/204Pb and 208Pb/206Pb) close to some shot pellets from different manufacturers. These results offer new, valuable data for other researchers working on lead contamination research and the identification sources of Pb for adjacent areas to shooting-range facilities and for wildlife ecotoxicology. Still, the use of several ammunitions derived from different sources, such as recycled Pb, showed that it is hard to identify the lead source and these kinds of facilities.

1. Introduction

Due to natural and anthropogenic causes, lead is a widely distributed element in all ecosystems, including the most remote ones. Lead has four stable isotopes (208Pb, 206Pb, 207Pb and 204Pb) whose ratios depend on the U/Th ratio, geological and environmental conditions, etc. Whereas 204Pb is not radiogenic and does not change significantly over time, the first three forms are radiogenic and come from the decomposition of 238U, 235U and 232Th, respectively [1,2,3,4]. In this sense, the isotopic ratio of Pb, released both from natural or anthropogenic sources, is maintained during physical and physicochemical processes. As a result, lead isotope ratios are frequently used in environmental studies as environmental tracers to identify potential lead sources [1,2,3,4,5,6]. Determinations by MC-ICP-MS (multiple-collector inductively coupled plasma mass spectrometry) allow us the measurement of very low concentrations in different environmental samples, being also a perfect and helpful tool for the analysis of isotopes of different elements with accuracies of up to ±0.001% [1,2,4,7,8,9,10,11].
Military and civilian shooting activities are a significant source of lead contamination to the environment, including soil biota, e.g., [5,12,13,14,15], and different works have been carried out with lead isotopes to assess their use as potential tracers of contamination by lead for wild fauna or humans near polluted areas by lead, such as mining soils, civilian/military shooting fields and hunting areas [1,5,16,17,18,19,20,21,22]. However, the knowledge and use of lead isotopes for soils from civilian and military shooting areas is still not well studied and requires attention [5,8,12,17,21,22,23] since lead isotopes signatures can be very different, due to different ammunition origins, and sometimes, the isotope identification can be overlapped with topsoil signatures [5]. More data are needed to improve databases about soil contamination by lead ammunition and their potential risk for plants and wildlife fauna.
This study reported lead isotopic data from an abandoned trap shooting range facility in NW Spain, with lead concentrations ranging from 80 to 720 mg kg−1 as pseudototal amounts and significant contents of bioavailable lead due to the acidic soil pH [23]. Additionally, higher levels of polycyclic aromatic hydrocarbons (PAHs) were found as a result of the usage of clay pigeons for shooting activities [14], and lead contamination was seen throughout the soil profile at various soil depths [24]. Here, we showed the lead isotope ratios (207Pb/204Pb, 208Pb/204Pb, 206Pb/204Pb, 208Pb/206Pb and 206Pb/207Pb) from 3 shot pellets and 12 soil samples from various locations in the shooting range facility. Lead isotope ratios from soils and shots pellets were measured by MC-ICP-MS. They were compared with isotopic data from previously published ammunition debris (shot pellets, civilian and/or military bullets).

2. Experimental Design, Materials, and Methods

Sample Locations and Lead Content in Soils and Shoot Pellets, and Their Measurements of Lead Isotopes by MC-ICP-MS

The studied soils in this work were previously characterized, and their results were published in different works [14,23,24]. For this work, we have used the same soil samples previously analyzed (0–15 cm depth), with different degrees of contamination and distance from the firing point, while the lead contents were analyzed using X-ray fluorescence (XRF) [23,24]. The stable lead isotopes in the analyzed soils (204Pb, 206Pb, 207Pb and 208Pb) were determined in all the samples according to the methodology indicated by [3,4,25]. Lead stable isotope ratio measurements were performed with MC-ICP-MS (Thermo-Finnigan Neptune) at CACTI-UVigo (Universidade de Vigo, Vigo, Spain), and the lead contents in blank samples were less than 0.1 ppb (detected signal was lower than 0.002 V). Detailed conditions about isotope analysis were previously reported [4], and all samples were analyzed in duplicate. The MC-ICP-MS and instrumental parameters for isotope ratio analysis and the Pb stable isotope ratios in reference material SRM 981 (NIST) are indicated in the Supplementary Material (Tables S1 and S2).
Regarding the shoot pellets, they were randomly selected from all ammunition debris collected from the studied soils and during the soil sieving for physicochemical analysis. Due to the shooting range facility being abandoned in 1999, we cannot assess the manufacturer of these shoots’ pellets. In this sense, shoot pellets showed different degrees of weathering, such as irregular surfaces, slightly brown crust, and lower weight than expected [24]. Samples were digested according to the methodologies indicated by different authors [5,18,26], and isotope ratios were carried out using the same methods as for soil samples. After that, soil samples and shot pellets were compared with isotopic data from probable sources [27,28,29,30,31,32]: leaded petrol, burned coal, natural background, waste incinerators, industrial sources and other ammunition types (bullets, shot pellets, etc.).

3. Results and Discussion

We found that stable isotope ratios for studied soils ranged between 1.123 and 1.1709 for 206Pb/207Pb and between 2.084 and 2.134 for 208Pb/206Pb (Table 1). These values were very similar to values indicated by [5] for lead isotopes from hunting areas in Spain and within the range stated by [12] for agricultural soils contaminated by civilian shooting activities in the Czech Republic. However, these values were lower than those reported by [22] for military soils in South Korea, with 206Pb/207Pb ratios ranging from 1.171 to 1.199, and for sediments near hunting areas (1.17–1.18, Table 1) [33]. When comparing these values with different natural or anthropogenic lead sources, these data suggest that lead ammunition is the primary source of lead in these soils (Figure 1). Although some samples can have a similar isotope ratio to industrial sources (Figure 1), the study zone is in a small town (around 20,000 inhabitants) without significant lead-related industries.
However, the range of isotope ratios for collected shot pellets differed with 206Pb/207Pb ratios of 1.1155, 1.1691 and 1.211, while 208Pb/206Pb ratios were 2.1431, 2.1016 and 2.0309, respectively (Table 2). Interestingly, the one-shot pellet showed for the 206Pb/207Pb ratio a value of 1.1691, and 2.1016 for 208Pb/206Pb, a value very similar to the different soil samples, suggesting that it was primarily used in this installation (Figure 2b). This higher variability is expected in shooting ranges because shooting pellets can have different origins and manufacturers with Pb from various lead ores, as reviewed by [14,24,34,35,36] for lead ammunition, even with the use of recycled lead for shoot pellets, such as ‘home-made’ ammunition that could mask lead origin specificity [34,35,36,37,38]. As indicated by [36,38], remanufacturing or reloading cartridges involves reusing previously fired cases and reloading these with the other components, including primers and propellants. As highlighted by [34], when various lead sources are recycled from a different product (e.g., mix of recycled batteries and other uses), the distinctive isotopic ratio may become progressively less characteristic, and therefore, the source determination can be more complex [19,34,36,37]. When the shot pellets ratio was compared with other shot pellet manufacturers (Table 2, Figure 2), it suggested a potential European origin for the potentially most used pellet, with similar ratios as indicated by different authors for European manufacturers [5,39,40]. Additionally, it was interesting to see that one-shot pellets have a lead isotope rate very similar to American lead pellets, suggesting the use of American manufacturers (Figure 2a,b). However, this shooting range was abandoned several years ago, and we cannot know which ammunitions were mainly used to compare and verify our results.

Research Implications of the Present Data

Lead isotope ratios have been widely used to differentiate sources of environmental lead in several environmental matrices due to lead released to the environment (e.g., exhausted from gasoline, and industrial sources) maintaining a characteristic signature and usually does not change during the manufacturing processes [1,2,3,4,5,6,9,10,11,12,21,37]. However, our results showed the difficulties of using isotopic signatures from lead ammunition as tracers of lead in shooting or hunting areas and their potential use in wildlife studies due to the different use of different ammunition sources from different world regions or different origins from previous uses [34,35,36,37,38,47]. This fact is that the manufacture of lead ammunition (e.g., bullets or shotgun pellets) can have various sources, such as mining, recycling and mixing scrap metal, car batteries, etc. Additionally, some shooting ranges can recover some spent ammunition that can be recycled, remanufactured and reused for shotgun cartridges [34,36,37,38,47,48]. During the fusion processes, the purification and addition of other additives, such as Sb, are aggregation phenomena that make the projectiles from the same box and manufacturer have different ratios and compositions, making it impossible to relate to the brand/batch manufacture. In this sense, Gulson et al. [9] also remarked that comparison with published literature could be difficult since several papers only show data from major isotope 207Pb/206Pb and 208Pb/206Pb ratios, or sometimes only 207Pb/206Pb ratios, a problem that we found in our study since several papers only published one isotope ratio, as highlighted in Table 2. Finally, there are some possible issues in the interpretation of soil contamination arising from the lead due to the use of primers (e.g., Pb styphnate, C6HN3O8Pb or lead peroxide PbO2) that ignite in the firearm barrel to provide the propulsion to the projectile, and they should also be considered [48].

4. Conclusions

Studies about lead source identification with lead ammunition in wildlife fauna or flora should be cautioned. However, we need more data on lead isotopes and soils contaminated by shooting/hunting activities to generate a robust database with lead shooting pellets or lead ratios from shooting ranges. In the cases where lead isotopes are measured, all isotopic ratios should be measured and published, not only one ratio (e.g., 207Pb/206Pb) (Table 2). The data we offer here could be helpful for researchers involved in forensic sciences or lead tracers, such as the toxicological effects of lead in wildlife fauna.

Supplementary Materials

The following supporting information can be downloaded at: https://0-www-mdpi-com.brum.beds.ac.uk/article/10.3390/app12178803/s1, Table S1: Operating parameter settings of the Thermo-Finnigan Neptune MC-ICP-MS and instrumental parameters for isotope ratio analysis, Table S2: Pb stable isotope ratios in reference material SRM 981 (NIST).

Author Contributions

A.R.-S.: Conceptualization, Methodology, Formal analysis, Investigation, Writing—original draft, Writing—review and editing, Funding acquisition, K.E.S.: Conceptualization, Methodology, Writing—original draft; V.C.: Conceptualization; Methodology, Writing—review and editing. All authors have read and agreed to the published version of the manuscript.

Funding

This research was supported by Project CGL2013-45494-R (Ministerio de Economía y Competitividad, Spain) and by national funds through F.C.T. (Foundation for Science and Technology, Portugal) within the scope of UIDB/04423/2020 and UIDP/04423/2020. A.R.S. would like to acknowledge the F.C.T. and CIIMAR for their contract under the Scientific Employment Stimulus-Individual 2017 program (CEECIND/03794/2017) and MCIN/AEI/UVigo for their contract JdCi under the “Actuación financiada por IJC2020-044197-I/MCIN/AEI/10.13039/501100011033 y por la Unión Europea NextGenerationEU”/PRTR”. V.C. also wants to acknowledge the 19-15405S Grant Agency of the Czech Republic.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

All generated data are published in this version.

Acknowledgments

A.R.-S. would like to thank CACTI-Uvigo technicians for their technical support.

Conflicts of Interest

The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or in the decision to publish the results.

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Figure 1. Scatter plot for 208Pb/206Pb versus 206Pb/207Pb of lead isotope ratios for different environmental components in the vicinity of the study area. Data from [27,28,29,30,31,32].
Figure 1. Scatter plot for 208Pb/206Pb versus 206Pb/207Pb of lead isotope ratios for different environmental components in the vicinity of the study area. Data from [27,28,29,30,31,32].
Applsci 12 08803 g001
Figure 2. (a) Scatter plot for 208Pb/206Pb versus 206Pb/207Pb of lead isotope ratios for different shot pellet and ammunition manufacturers and studied soils. “Not indicated” means that authors have not reported a probable origin of shot pellet manufacturer/brand. (b) Detail of the crowded central region. Data compiled from [5,16,17,18,19,20,21,22,26,33,34,39,41,42,43,44,45].
Figure 2. (a) Scatter plot for 208Pb/206Pb versus 206Pb/207Pb of lead isotope ratios for different shot pellet and ammunition manufacturers and studied soils. “Not indicated” means that authors have not reported a probable origin of shot pellet manufacturer/brand. (b) Detail of the crowded central region. Data compiled from [5,16,17,18,19,20,21,22,26,33,34,39,41,42,43,44,45].
Applsci 12 08803 g002
Table 1. According to the literature, lead stable isotopes ratios from different shooting range soils and soil sediments near shooting and hunting areas. Measurement precision is indicated according to the different studies—average values.
Table 1. According to the literature, lead stable isotopes ratios from different shooting range soils and soil sediments near shooting and hunting areas. Measurement precision is indicated according to the different studies—average values.
SampleSoil UseDepth (cm)Pb mg kg−1206Pb/204Pb207Pb/204Pb208Pb/204Pb208Pb/206Pb206Pb/207Pb208Pb/207PbCountryReference
Soils
Contaminated SoilCivilian shooting range0–1582.7118.315.63438.3622.0961.17-SpainThis study
Contaminated SoilCivilian shooting range0–15195.518.28715.63438.3772.0981.169-SpainThis study
Contaminated SoilCivilian shooting range0–15160.917.47915.55237.2722.1321.123-SpainThis study
Contaminated SoilCivilian shooting range0–15259.6118.23615.62538.2972.0991.167-SpainThis study
Contaminated SoilCivilian shooting range0–15187.4618.25815.63438.3362.0991.167-SpainThis study
Contaminated SoilCivilian shooting range0–15277.3818.22415.62638.2942.1011.166-SpainThis study
Contaminated SoilCivilian shooting range0–15222.8218.26715.62838.3452.0981.168-SpainThis study
Contaminated SoilCivilian shooting range0–15378.1718.2315.62938.3072.1011.166-SpainThis study
Contaminated SoilCivilian shooting range0–15366.1618.23115.62738.2992.11.166-SpainThis study
Contaminated SoilCivilian shooting range0–15724.8518.17415.61738.2042.1021.163-SpainThis study
Contaminated SoilCivilian shooting range0–15402.0818.26815.63338.3692.11.168-SpainThis study
Contaminated SoilCivilian shooting range0–15442.7817.5915.5637.522.1341.129-SpainThis study
Control soilCivilian shooting range0–1582.3618.46315.6538.4942.0841.179-SpainThis study
Contaminated SoilCivilian shooting range0–5-----1.166-Czech Republic[12]
Contaminated SoilCivilian shooting range5–15-----1.154-Czech Republic[12]
Contaminated SoilCivilian shooting range15–30-----1.165-Czech Republic[12]
Contaminated SoilCivilian shooting range30–x-----1.187-Czech Republic[12]
Control soilCivilian shooting range0–5-----1.181-Czech Republic[12]
Control soilCivilian shooting range5–15-----1.181-Czech Republic[12]
Control soilCivilian shooting range15–30-----1.178-Czech Republic[12]
Control soilCivilian shooting range30–x-----1.188-Czech Republic[12]
Contaminated SoilShooting range0–251432----1.1332.407Netherlands[21]
Contaminated SoilShooting range0–252362----1.1332.407Netherlands[21]
Contaminated SoilShooting range0–251432----1.1332.407Netherlands[21]
Contaminated SoilShooting range0–252362----1.1332.407Netherlands[21]
Contaminated SoilHunting area0–5----2.0961.171-Spain[5]
Contaminated SoilHunting area0–5----2.0941.162-Spain[5]
Contaminated SoilHunting area0–5----2.1071.158-Spain[5]
Contaminated SoilHunting area0–5----2.1081.153-Spain[5]
Contaminated SoilHunting area0–5----2.1141.154-Spain[5]
Contaminated SoilHunting area0–5----2.111.154-Spain[5]
Contaminated SoilHunting area0–5----2.1061.152-Spain[5]
Contaminated SoilMilitary shooting range028,04018.5315.6938.77-1.182.47South Korea[22]
Contaminated SoilMilitary shooting range5–1524,04318.2615.4538.21-1.182.47South Korea[22]
Contaminated SoilMilitary shooting range15–3019,76318.515.6538.96-1.182.49South Korea[22]
Contaminated SoilMilitary shooting range0512718.4615.5338.09-1.192.45South Korea[22]
Contaminated SoilMilitary shooting range5–15414718.6315.5338.22-1.22.46South Korea[22]
Contaminated SoilMilitary shooting range15–3018518.6215.7739.08-1.182.48South Korea[22]
Contaminated SoilMilitary shooting range011,13718.615.8838.9-1.172.45South Korea[22]
Contaminated SoilMilitary shooting range5–15529715.1415.1135.98-12.38South Korea[22]
Contaminated SoilMilitary shooting range15–30429316.6716.5639.62-1.012.39South Korea[22]
Control soilMilitary shooting range01418.8216.140.7-1.172.53South Korea[22]
Control soilMilitary shooting range5–152118.2115.5538.73-1.172.49South Korea[22]
Control soilMilitary shooting range15–303318.5515.9540.03-1.162.51South Korea[22]
Sediments
Contaminated sedimentHunting area-25.86 2.08431.18302.4693Spain[33]
Contaminated sedimentHunting area-31.17 2.08751.18032.4649Spain[33]
Contaminated sedimentHunting area-12.56 2.09071.17682.4630Spain[33]
“-” not indicated.
Table 2. The average lead isotopic signature of the studied shot pellets and shot pellets from different brands.
Table 2. The average lead isotopic signature of the studied shot pellets and shot pellets from different brands.
ManufacturerAmmunition Type206Pb/207Pb208Pb/206Pb208Pb/204Pb206Pb/204Pb207Pb/204Pb207Pb /208PbCountry of Origin (Manufacturer)Country of StudyReference
-Shotgun pellet1.21102.030938.555018.984415.5330--SpainThis study
-Shotgun pellet1.16912.101638.411018.277915.6769--SpainThis study
-Shotgun pellet1.11552.143137.157017.348015.6347--SpainThis study
RemingtonShotgun pellet1.2276-----USAUSA[41]
WinchesterShotgun pellet1.2290-----USAUSA[41]
RemingtonShotgun pellet1.2308-----USAUSA[41]
-Shotgun pellet1.22972.0009-19.3050---USA[41]
-Shotgun pellet1.22302.0110-19.1900---Canada[19]
-Shotgun pellet1.1560------Czech Republic[12]
-Shotgun pellet1.2300-----USAArgentina[42]
-Shotgun pellet1.2239-----ArgentinaArgentina[42]
-Shotgun pellet1.1668------Argentina[42]
Browning CAL12Shotgun pellet1.15292.0991---0.4132-Spain[5]
EleyShotgun pellet1.15502.1190----UKUK[39]
EleyShotgun pellet1.15202.0980----UKUK[39]
EleyShotgun pellet1.15302.1200----UKUK[39]
EleyShotgun pellet1.14702.1300----UKUK[39]
GameboreShotgun pellet1.13202.1340----UKUK[39]
GameboreShotgun pellet1.14102.1150----UKUK[39]
GameboreShotgun pellet1.14202.1270----UKUK[39]
GameboreShotgun pellet1.13902.1160----UKUK[39]
GameboreShotgun pellet1.14102.1140----UKUK[39]
GameboreShotgun pellet1.13802.1270----UKUK[39]
HullShotgun pellet1.15602.1060----UKUK[39]
HullShotgun pellet1.15802.1110----UKUK[39]
HullShotgun pellet1.15402.1000----UKUK[39]
Lyalvale ExpressShotgun pellet1.15202.1250----UKUK[39]
Lyalvale ExpressShotgun pellet1.15902.1140----UKUK[39]
Lyalvale ExpressShotgun pellet1.15302.1170----UKUK[39]
Lyalvale ExpressShotgun pellet1.15002.1260----UKUK[39]
R.C. (Italy)Shotgun pellet1.14502.1230----ItalyUK[39]
-Shotgun pellet1.1800----- [43]
-Shotgun pellet1.17652.0700-----Japan[44]
-Shotgun pellet1.14942.1400-----Japan[45]
-Shotgun pellet1.15102.1290-18.1610 0.4083 Poland[46]
-Shotgun pellet1.16992.0885---0.4093 Spain[33]
-Shotgun pellet
(hunting use)
1.15482.1073-----Ecuador[17]
-Shotgun pellet
(hunting use)
1.15482.1010-----Ecuador[17]
-Shotgun pellet
(hunting use)
1.15512.0966-----Ecuador[17]
-Shotgun pellet
(hunting use)
1.16222.0960-----Ecuador[17]
-Shotgun pellet
(hunting use)
1.16522.0962-----Ecuador[17]
HumassonShotgun Pellets1.2200-----CanadaCanada[46]
ChallengerShotgun Pellets1.1600-----CanadaCanada[46]
CIL “Canuck”Shotgun Pellets1.0800-----CanadaCanada[46]
RemingtonShotgun Pellets1.2300-----USACanada[46]
WinchesterShotgun Pellets1.1500-----USACanada[46]
Kent USAShotgun Pellets1.1000-----USACanada[46]
FederalShotgun Pellets1.2300-----USACanada[46]
EleyShotgun Pellets1.0800-----UKCanada[46]
VeeShotgun Pellets1.1500-----SpainCanada[46]
Sellier & BellotShotgun Pellets1.1700-----Czech RepublicCanada[46]
DouillerieShotgun Pellets1.1600-----FranceCanada[46]
PD OlympieShotgun Pellets1.1600-----PolandCanada[46]
MondialShotgun Pellets1.1700-----HungaryCanada[46]
“-” not indicated.
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Rodríguez-Seijo, A.; Sjåstad, K.E.; Chrastný, V. Can Isotopes Be Used as Lead Tracers in Shooting-Range Soils? Appl. Sci. 2022, 12, 8803. https://0-doi-org.brum.beds.ac.uk/10.3390/app12178803

AMA Style

Rodríguez-Seijo A, Sjåstad KE, Chrastný V. Can Isotopes Be Used as Lead Tracers in Shooting-Range Soils? Applied Sciences. 2022; 12(17):8803. https://0-doi-org.brum.beds.ac.uk/10.3390/app12178803

Chicago/Turabian Style

Rodríguez-Seijo, Andrés, Knut Endre Sjåstad, and Vladislav Chrastný. 2022. "Can Isotopes Be Used as Lead Tracers in Shooting-Range Soils?" Applied Sciences 12, no. 17: 8803. https://0-doi-org.brum.beds.ac.uk/10.3390/app12178803

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