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Horseshoe Lake, Madison County, Illinois, showing the sites of core 3 from Vermillion et al. (2005) and core 17 analyzed in this study. The stabilization ponds used to treat wastewater from Granite City Steel Co are indicated by shading
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A simple binary mixing model is used to determine the isotopic ratios of lead (Pb) pollution sources to a lake located near a smelter closed because of excessive Pb aerosols (Horseshoe Lake Madison County, Illinois, USA). As a control, we also examine a relatively unpolluted lake in a rural area of Southern Illinois (Horseshoe Lake Alexander County...
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... were located in the American Bottoms to take advantage of the nearby source of coking coal from the Southern Illinois coal fields and favorable freight rates for shipping Pb ore east across the Mississippi River (Theising 2003). In addition, Granite City Steel Co. had already built a large coking plant that could supply the nearby Pb smelters (Fig. 2). In 1902 Markel Lead Co. built a large coke-fired Pb smelter in Granite City, IL. By 1928 the smelter was purchased by NL Industries to refine Pb for use in paint. The smelter also recycled Pb from manufactured products includ- ing vehicle batteries. The smelter operated until 1983 when it was shut down because of continued violations ...
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... Lake (Horseshoe Madison), is a 860 ha (2,150 acres, Hill et al. 1981), 1 m deep oxbow lake located on the American Bottom 7 km from the NL Industries smelter site in Madison County, Illinois and 125 km from the oldest Pb mines in southeast Missouri (Fig. 1). Bordering the floodplain on the East are bluffs composed of Wisconsinan-age loess (Fig. 2). The Lake is located adjacent to Granite City which was established in 1865 when Neidringhaus (now Granite City) Steel Company was built on the shore of Horseshoe Lake. We previously studied the paleolimnological record of heavy metals, and stable isotopes of carbon and nitrogen in the lake using 15 sediment cores ( Brugam et al. ...
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... at both lakes was accomplished manually using polycarbonate tubes attached to steel rods. The coring site at Horseshoe Madison (38.704°N, 90.082°W. Fig. 2) was chosen after a survey that determined the extent of sediment accumulation which showed the potential to retrieve a core with a significant amount of pre-European sediment (Fig. 2). Few of the 15 cores sampled by Vermillion et al. (2005) reached pre-settlement levels. The core used in this study (core 17) was located within 16 m of ...
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... at both lakes was accomplished manually using polycarbonate tubes attached to steel rods. The coring site at Horseshoe Madison (38.704°N, 90.082°W. Fig. 2) was chosen after a survey that determined the extent of sediment accumulation which showed the potential to retrieve a core with a significant amount of pre-European sediment (Fig. 2). Few of the 15 cores sampled by Vermillion et al. (2005) reached pre-settlement levels. The core used in this study (core 17) was located within 16 m of core 3 taken by Vermillion et al. (2005) using a Garmin GPS V (Fig. 2). The proximity of the cores allowed the extrapolation of dates from the earlier core. Water depth at the core ...
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... of sediment accumulation which showed the potential to retrieve a core with a significant amount of pre-European sediment (Fig. 2). Few of the 15 cores sampled by Vermillion et al. (2005) reached pre-settlement levels. The core used in this study (core 17) was located within 16 m of core 3 taken by Vermillion et al. (2005) using a Garmin GPS V (Fig. 2). The proximity of the cores allowed the extrapolation of dates from the earlier core. Water depth at the core site was 3 m and the core was 100 cm long. The core was capped by rubber stoppers at both ends and returned to the lab for ...
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... First of all, we've made a "standard" source apportionment using a binary mixing model (Weiss et al., 2008;Wiederhold, 2015). A negative correlation was found between δ 114/110 Cd values and reciprocal of Cd concentration in soil profiles (Fig. 3), suggesting that binary mixing between two sources (flooding vs parent rock weathering) occurred in this area (Brugam et al., 2012;Wang et al., 2021). Take profile 2 as an example, contributions of flooding-induced Cd input yielded 76%, 55%, and 25% at 10 cm, 40 cm and 90 cm, respectively, in this typical manner (Fig. 3). ...
... Four stable Pb isotopes occur in geologic materials (i.e., ore bodies, coals, and uncontaminated background rocks and soils). 204 Pb is "primordial," or original, in geologic materials, 206 Pb and 207 Pb are the end points in the decay chains of 238 U and 235 U, respectively, and 208 Pb is the end of the decay chain for 232 Th [38,39]. Th and the two U isotopes have different half-lives, so the ratios among the resulting Pb isotopes shift over geologic time scales. ...
... Three-isotope graphs plot two ratios (e.g., 206 Pb/ 207 Pb vs. 206 Pb/ 204 Pb), producing a more useful graph when the Pb concentrations are heterogeneous. In a simple binary system, samples will plot along a mixing line connecting two sources with known isotopic signatures [39,40]. Figure S1 illustrates a general binary mixing line, where samples along the line show the combined influences of two sources of Pb. ...
... Proximity to the sources affects the relative contributions of the sources to each sample. If samples along the mixing line are well correlated, the percent contribution of each source can be estimated mathematically with a mixing model [39,40]. Other, more complex mixing models exist besides simple binary models. ...
Globally, lead (Pb) contamination is one of the top ten chemical exposure issues affecting public health. The identification of specific Pb sources provides valuable information to determine assignment of liability for site cleanup, improve sampling plans and develop remedial strategies. This paper examines Pb concentrations and Pb isotopic data from samples collected at and near the site of a Pb paint production facility with a long operating history. Although high soil Pb concentrations were found at the site, Pb concentrations in surrounding neighborhoods did not simply decline with distance from the site. We evaluated soil concentrations and isotopic mixing lines to explore potential sources of Pb pollution. Three-isotope plots showed overlap of site samples and the surrounding neighborhood, consistent with pollution from the facility affecting offsite soils. A major challenge in separation of potential sources, however, is that the isotopic signatures of other potential Pb sources fall within the range of the soil data. The long operational site history, soil disturbances, the presence of nearby smelters, and other local and remote sources affect identification of lead sources. This analysis demonstrates that source attribution can be confounded by incomplete site and material sourcing information. An integrated approach that includes in-depth site characterization and an evaluation of historical activities (e.g., Pb ores used over time, amounts of Pb emitted by all area smelters, land use changes, and soil disturbances) is important for determining source attribution. This analysis provides insight into future site investigations where soil lead contamination has resulted from a long industrial history in an urban setting.
... The traditional solution to the mixing issue is based on identifying trend lines in scatter plots of isotope ratios and chemical compositions (Brugam et al., 2012;Eshel et al., 2021;Monna et al., 2000;Pernicka, 2020;Pollard and Bray, 2015). However, this method is incapable of dealing with more complex and undetermined mixing situations when the number of potential sources is greater than the number of isotope ratios plus one. ...
Provenance of metals is a major theme in Bronze Age archaeology since it can help to reveal complex cultural and economic entanglements in ancient times. However, where complex societies with diversified trading relationships are concerned, identifying metal provenance has often proved to be challenging due to the frequent mixing of metals from different sources in antiquity. This research addresses this question by developing an innovative method for interpreting lead isotope data of bronze artefacts. Manifold learning and a Bayesian mixing model are combined to reconstruct quantitatively the contribution of metal sources to ancient bronzes. The methodology is employed to resolve the complex metal circulation system in the Zhou period (11th-3rd century BC) of China, and reveals a significant diachronic change of metal resources from North, Central, and South China. The North China metal sources were mainly employed in the Early Western Zhou period (1046-950 BC). In the following ages, the Yangtze River Valley and Qinling Mountains became the major metal sources for Zhou people. The Middle Spring and Autumn period (660 BC-560 BC) witnessed a major shift of dependence between these two sources, demonstrating a fundamental transformation in the metal circulation system. The South China metal sources were exploited throughout the entire Zhou period and probably associated with polymetallic deposits in the Nanling area. This research reveals the long-term patterns of metal exploration and mixing in the Zhou period of China, and also demonstrates the great potential this new methodology promises in addressing the complex metal mixing history in other cultural contexts.
... Pb/ 204 Pb: 18.6336) to model isotope mixing (cf.Brugam et al., 2012), ...
Lead isotope analysis (LIA) can be applied to tin provenance studies when both the U–Th–Pb characteristics of cassiterite and potential Pb contamination are taken into account. As cassiterite (SnO2) contains higher concentrations of U than Pb and negligible Th, radioactive decay increases ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁷Pb/²⁰⁴Pb ratios in cassiterite over time. However, ²⁰⁸Pb/²⁰⁴Pb ratio retains its primary value and can be correlated with LIA databases. A majority of documented Bronze Age tin ingots from Europe have Pb in excess of the 5 ppm maximum that can be derived from Cenozoic to Late Paleozoic cassiterite. A minute mass of galena (PbS) in the ore concentrate is sufficient to mask the cassiterite-derived lead, as would the addition of any lead contaminant introduced in the smelting/casting process. If the galena is cogenetic with the cassiterite, then LIA will be unaffected. The inclusion of uranium-rich minerals in the tin ore concentrate is another potential source of excess lead. In this case, the additional Pb is uranogenic, and so ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁷Pb/²⁰⁴Pb will reflect the age of the uranium minerals, but ²⁰⁸Pb/²⁰⁴Pb will retain its primary value. If the U-minerals are cogenetic or coeval with tin mineralization, then a Pb isochron age will indicate the age of the ore.
Between 1984 and 1994, at least 117 ingots, or roughly one tonne, of tin was raised from the Late Bronze Age Uluburun shipwreck (ca. 1320 B.C.). Over half of the analyzed ingots from this wreck site have high Pb concentrations (>100 ppm), indicative of contamination from non-radiogenic lead associated with lead metal or galena. LIA indicates that the Pb originated from the Pb–Ag-rich Bolkardağ region of the south-central Taurus Mountains. A second group of approximately 28 tin ingots with lower Pb content (<100 ppm) contain additional uranogenic Pb but retain ²⁰⁸Pb/²⁰⁴Pb compositions that overlap with the ca. 300 Ma tin regions of Western Europe and Central Asia, with the most likely source being the Tienshan Mountains in Kyrgyzstan, Tajikistan, and Uzbekistan.
By compensating for previous uncertainty around the use of Pb isotopes for sourcing tin objects, it is now possible to contextualize the Uluburun tin ingots more securely within the metallurgical systems of the Central Taurus-Cilicia-Amanus axis. Recent scholarship has shown that tin production in the South-Central Taurus region had taken place at a scale not previously anticipated. Two parallel production systems appear to have been in place serving elite and common consumption networks via markedly different technologies. The South-Central Taurus and Cilician cities served as important components of maritime and terrestrial metal distribution around the eastern Mediterranean, providing a range of metals from a single geographical region.
... SCIENtIfIC REPoRTs | (2018) 8:6154 | DOI: 10.1038/s41598-018-24474-0 approaches 30,37,38 . For disentangling multiple sources we considered two possible approaches: 1) IsoSource, a mass balance-based multi-source mixing model 46 and 2) MixSIAR 47 , the latest iteration of a series of Bayesian mixing models 48,54 . ...
Lead (Pb) isotopes provide valuable insights into the origin of Pb within a sample, typically allowing for reliable fingerprinting of their source. This is useful for a variety of applications, from tracing sources of pollution-related Pb, to the origins of Pb in archaeological artefacts. However, current approaches investigate source proportions via graphical means, or simple mixing models. As such, an approach, which quantitatively assesses source proportions and fingerprints the signature of analysed Pb, especially for larger numbers of sources, would be valuable. Here we use an advanced Bayesian isotope mixing model for three such applications: tracing dust sources in pre-anthropogenic environmental samples, tracking changing ore exploitation during the Roman period, and identifying the source of Pb in a Roman-age mining artefact. These examples indicate this approach can understand changing Pb sources deposited during both pre-anthropogenic times, when natural cycling of Pb dominated, and the Roman period, one marked by significant anthropogenic pollution. Our archaeometric investigation indicates clear input of Pb from Romanian ores previously speculated, but not proven, to have been the Pb source. Our approach can be applied to a range of disciplines, providing a new method for robustly tracing sources of Pb observed within a variety of environments.
... Studies in which heavy metal isotopes are used in conjunction with their concentration values (e.g., Fig. 6) show far greater interpretational value than either alone (Brännvall et al. 1997, Renberg et al. 2002. The more recent application of binary mixing models to these data are proving very powerful (Brugam et al. 2012) as a tool in source quantification. ...
Since the first studies reporting recent stratigraphic changes of metal concentration in lake sediments, many hundreds of studies have been published in the peer-reviewed literature. It is an impossible task to do justice to all of these works here; instead we: (1) examine recent methodological advances and place these in the context of the historical development of the discipline; and (2) explore the various purposes to which such methods have been applied. Such a historical emphasis may appear in conflict with the needs of a review of new approaches; however, this is not in fact the case for two main reasons. First, most new advances supplement rather than replace traditional methods, such that a thorough understanding of the practical and theoretical issues impacting these is still essential for reliable interpretation of palaeolimnological data. Second, while many of the new methods purport to circumvent problems, they achieve this only under favourable conditions, not dissimilar to the conditions that influence the earlier methods, so the same lesson must be learned anyway. Consequently, we use this historical narrative to address the fundamentals of the discipline.
... This modification has allowed intense industrialization including construction of oil refineries, stock yards, a steel plant and several lead smelters. Thus river modification allows industrialization of flood plains that produces important new pollution effluents (Brugam et al., 2003(Brugam et al., , 2012Colten, 1990). One result is enhanced nutrient inputs to floodplain ecosystems. ...
... Fry's (2006) analysis was an extension of the general two source mixing model for isotopes presented by Faure and Mensing (2005) modified for stable isotopes of nitrogen and carbon. A similar approach has been used by Brugam et al. (2012) using Pb isotopes at Horseshoe Lake. ...
Anthropogenic nitrogen contamination has increased in ecosystems around the world (frequently termed the "nitrogen cascade"). Coke production for steel manufacturing is often overlooked as a source of nitrogen to natural ecosystems. We examined sediment cores from a Horseshoe Lake, a floodplain lake located just East of St. Louis Missouri (USA) to test whether a coking plant effluent could be traced using stable isotopes of nitrogen and diatom microfossils. The distribution of δ(15)N values in surface sediment samples from the lake shows the highest values near the coking plant effluent. Stable isotopes of nitrogen from 4 sediment cores using a mixing model showed three sources of nitrogen since 1688 CE. The first source (active between 1688 and 1920 CE) had a calculated δ(15)N value ranging between -0.4 and 1.1‰ depending on the core. After 1920 a second source with a δ(15)N ranging between 10.6 and 15.4‰ became active. The change in these sources coincides with the construction of a coking plant on the lake shore. A third source with a value approximately 7.0‰ was present at all times and represents background. The diatom microfossil assemblages present from 1688 CE to the late 1800s are dominated by the planktonic species Aulacoseira granulata and periphytic and benthic genera Gomphonema, Cocconeis, and Lyrella. After the late 1800s the diatom assemblages are dominated by Staurosira species indicating a shift of species from high flow riverine environments to epipelic species from a lake environment. Diatom microfossils seem to track the reduction in flooding due to leveeing of the floodplain and the isolation of the lake from the river. Our results show how stable isotopes of nitrogen can be used to track nitrogen inputs from industrial sources. Diatom changes corresponded with changes in connectivity between the Mississippi River and its floodplain.
