Changes in zinc and cadmium concentrations in Greenland ice during the past 7760 years

doi:10.1016/S1352-2310(97)00029-0

Atmospheric Environment

Volume 31, Issue 15, August 1997, Pages 2235-2242

https://doi.org/10.1016/S1352-2310(97)00029-0 Get rights and content

Abstract

Analysis of Zn and Cd in Greenland Holocene ice dated from 7760 to 471 yr ago shows no significant changes during the Greek, Roman and medieval times. It indicates that emissions from early mining and smelting operations were not intense enough for these two metals to have left detectable signals in Greenland ice above natural background, contrary to what was previously observed for Pb and Cu. Zn was especially used during Antiquity to make brass, the important binary CuZn alloy which was probably produced as early as ∼4000 yr ago. Rock and soil dust and continental biogenic sources are found to be important contributors to natural Zn and Cd in Holocene Greenland ice. During periods without major volcanic events, contribution from volcanoes was probably insignificant for Zn but could be important for Cd.

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The effect of metal production and utilization on humans during the Roman and medieval periods has been widely attested, along with a considerable increase in environmental pollution of toxic metals (e.g., Murozumi et al., 1969; Hong et al., 1994; 1996; Shotyk et al., 1998; Renberg et al., 1994; Alfonso et al., 2001; Mart’ınez Cortizas et al., 2002; Le Roux et al., 2003; 2004; Borsos et al., 2003; Durali-Müller, 2005; Delile et al., 2017). There is, however, ample evidence that global pollution by metals started long before the Roman period (perhaps as early as the 3rd millennium BCE; e.g., Settle and Patterson, 1980; Hong et al., 1997; Shotyk et al., 1998; Martínez Cortizas et al., 2002; Mighall et al., 2002). Large-scale pollution during the Levantine Iron Age (~1200–586 BCE) is evident in metal production centers, such as Faynan (e.g., Grattan et al., 2007; Hunt and el-Rishi, 2010; Beherec et al., 2016).
The extent of pollution and human mobility in the Iron Age in the southern Levant is estimated in this study through lead (Pb) and strontium (Sr) concentrations and isotopic compositions in human tooth enamel. The concentrations of Pb and other trace metals (Cu, Co, Cd, Zn) and Pb/Ca along with Ba/Ca ratios are used to determine background levels of metals and exposure to metal pollution. Strontium isotopic ratios are used to trace individuals’ residence as children and young adults, and Pb isotopic ratios are used for determining sources of in-vivo pollution. Seven teeth from the Natufian to the Pre-pottery Neolithic periods were used to establish metal-concentration baselines, and their Pb concentrations were compared with previous results. Forty-one additional samples (31 individuals) were selected from secure archaeological contexts, mostly urban sites, from the Iron Age (~1200 ‒ 586 BCE; 28 individuals) and from the Persian Period (~586–332 BCE; 3 individuals). Based on their Pb/Ca ratios, five individuals were found to be in-vivo polluted, and four additional individuals were possibly polluted, all dating to the Iron Age, suggesting that just under a third of the sampled Iron Age individuals were exposed to heavy metals to some extent. All individuals except one (from the coastal site of Dor) plot within the ⁸⁷Sr/⁸⁶Sr range of local, bioavailable Sr in soils (0.7058–0.7102). The unpolluted and possibly polluted individuals from coastal sites have a different ⁸⁷Sr/⁸⁶Sr range (0.7081–0.7112) than the inland unpolluted individuals (⁸⁷Sr/⁸⁶Sr = 0.7079–0.7084), suggesting that the former have more coastal/marine contribution in their diet. This Sr isotopic distribution pattern reflects a generally non-mobile population in both coastal and inland sites. Polluted Iron Age individuals, on the other hand, from both inland and coastal sites, have ⁸⁷Sr/⁸⁶Sr values which fall in a narrow range (0.7083–0.7086), possibly affected to some extent by coastal/marine sediments. Lead isotopic composition of four out of five individuals clearly deviate from local soil values, indicating an external contribution of Pb, some of which possibly originated from lead-rich Cu-ores in the Arabah. We thus propose a correlation between pollution and mobility in the Iron Age southern Levant. A possible explanation might be that polluted individuals had interactions with the coast or the marine environments, where they came into contact with metals, as a result of exposure to metalworking, use and/or trade.
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There is plenty of archaeological evidence for Roman copper alloys in northern Britain (Dungworth, 1997, 2002) but copper concentrations and EF also remain low. After the fall of the Roman Empire, zinc production probably declined at least until the 10th century AD (Hong et al., 1997). Natural zinc can originate from rocks and soil dust, volcanoes and biogenic sources.
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The synthesis presented in columns 1–3 of Table 1 is used to make the predictions of the possible nature and intensity of past anthropogenic metal pollution in the area (column 4). The flux of anthropogenic copper through the atmosphere to the Greenland icesheet during the Roman-Byzantine period was substantial and estimated by Hong et al. [67–69] to be in the region of 2300 t/year. These authors proposed that the economic rise of “Athenian Civilisation”, the development around the Mediterranean of a copper-based coinage, and the rise and decline of “Roman-Byzantine” mining and metallurgy were responsible for the distinctive heavy metal-pollution record detected in the Greenland ice cores.
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Changes in zinc and cadmium concentrations in Greenland ice during the past 7760 years

Abstract

Spectrochim. Acta

Analytica Chim. Acta

Atmospheric Environment

Sci. Total Envir.

J. Archeological Sci.

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