Silver isotopes: A tool to trace smelter-derived contamination.

Here, for the first time, we report the concentrations and isotopic data of Ag in a variety of ore and metallurgical samples and forest soils that have been polluted due to Ag-Pb smelter emissions. Similar to the Ag concentrations, we identified a large range of δ109Ag values (from -0.8 to +2.4‰), a ∼3‰ spread, within the primary and secondary materials (i.e., galena, fly ash, slag and matte). This phenomenon, however, is evidently unrelated to Ag isotopic fractionation during the smelting process, but it reflects the starting 109Ag/107Ag signal in ore mineral and/or the specific type of ore genesis. The two studied soil profiles differed in Ag isotopic composition, but on the other hand, they consistently showed significantly lighter Ag (≤+0.8‰) of metallurgical origin in the upper horizons compared to the bottom horizons and bedrocks, with low Ag amounts depleted of 107Ag (≤+2.9‰). This isotopic pattern can be attributed to a ternary mixing relationship involving two major anthropogenic Ag components and a minor contribution from geogenic Ag. Accordingly, we did not observe any post-depositional isotopic fractionation in our soils, since Ag was geochemically stable and it was not subjected to leaching. In summary, the Ag isotopes have a potential to trace variations in anthropogenic phases, to monitor specific geochemical processes, and are clearly applicable as anthropogenic Ag source and Ag load proxies.

Tin from Uluburun shipwreck shows small-scale commodity exchange fueled continental tin supply across Late Bronze Age Eurasia.

This paper provides the first comprehensive sourcing analysis of the tin ingots carried by the well-known Late Bronze Age shipwreck found off the Turkish coast at Uluburun (ca. 1320 BCE). Using lead isotope, trace element, and tin isotope analyses, this study demonstrates that ores from Central Asia (Uzbekistan and Tajikistan) were used to produce one-third of the Uluburun tin ingots. The remaining two-thirds were derived from the Taurus Mountains of Turkey, namely, from stream tin and residual low-grade mineralization remaining after extensive exploitation in the Early Bronze Age. The results of our metallurgical analysis, along with archaeological and textual data, illustrate that a culturally diverse, multiregional, and multivector system underpinned Eurasian tin exchange during the Late Bronze Age. The demonstrable scale of this connectivity reveals a vast and disparate network that relied as much on the participation of small regional communities as on supposedly hegemonic institutions of large, centralized states.

Fingerprinting the Cretaceous-Paleogene boundary impact with Zn isotopes.

Numerous geochemical anomalies exist at the K-Pg boundary that indicate the addition of extraterrestrial materials; however, none fingerprint volatilization, a key process that occurs during large bolide impacts. Stable Zn isotopes are an exceptional indicator of volatility-related processes, where partial vaporization of Zn leaves the residuum enriched in its heavy isotopes. Here, we present Zn isotope data for sedimentary rock layers of the K-Pg boundary, which display heavier Zn isotope compositions and lower Zn concentrations relative to surrounding sedimentary rocks, the carbonate platform at the impact site, and most carbonaceous chondrites. Neither volcanic events nor secondary alteration during weathering and diagenesis can explain the Zn concentration and isotope signatures present. The systematically higher Zn isotope values within the boundary layer sediments provide an isotopic fingerprint of partially evaporated material within the K-Pg boundary layer, thus earmarking Zn volatilization during impact and subsequent ejecta transport associated with an impact at the K-Pg.

Tracing Copper Migration in the Tongling Area through Copper Isotope Values in Soils and Waters.

Copper mining in Tongling has occurred since the Bronze Age, and this area is known as one of the first historic places where copper has been, and is currently, extracted. Multiple studies have demonstrated, through concentrated work on soils and waters, the impact of mining in the area. Here we present copper isotope values of 13 ore samples, three tailing samples, 20 water samples (surface and groundwater), and 94 soil samples (15 different profiles ranging in depth from 0⁻2 m) from proximal to distal (up to 10 km) locations radiating from a tailings dam and tailings pile. Oxidation of the copper sulfide minerals results in isotopically heavier oxidized copper. Thus, copper sourced from sulfide minerals has been used to trace copper in mining and environmental applications. At Tongling, higher copper isotope values (greater than 1 per mil, which are interpreted to be derived from copper sulfide weathering) are found both in waters and the upper portions of soils (5⁻100 cm) within 1 km of the source tailings. At greater than 1 km, the soils do not possess heavier copper isotope values; however, the stream water samples that have low copper concentrations have heavier values up to 6.5 km from the source. The data suggest that copper derived from the mining activities remains relatively proximal in the soils but can be traced in the waters at greater distances.

Fingerprinting two metal contaminants in streams with Cu isotopes near the Dexing Mine, China.

Transition metal isotope signatures are becoming useful for fingerprinting sources in surface waters. This study explored the use of Cu isotope values to trace dissolved metal contaminants in stream water throughout a watershed affected by mining by-products of the Dexing Mine, the largest porphyry Cu operation in Asia. Cu isotope values of stream water were compared to potential mineral sources of Cu in the mining operation, and to proximity to the known Cu sources. The first mineral source, chalcopyrite, CuFeS2 has a 'tight' cluster of Cu isotope values (-0.15‰ to +1.65‰; +0.37 ± 0.6‰, 1σ, n=10), and the second mineral source, pyrite (FeS2), has a much larger range of Cu isotope values (-4‰ to +11.9‰; 2.7 ± 4.3‰, 1σ, n=16). Dissolved Cu isotope values of stream water indicated metal derived from either chalcopyrite or pyrite. Above known Cu mineralization, stream waters are approximately +1.5‰ greater than the average chalcopyrite and are interpreted as derived from weathering of chalcopyrite. In contrast, dissolved Cu isotope values in stream water emanating from tailings piles had Cu isotope values similar to or greater than pyrite (>+6‰, a common mineral in the tailings). These values are interpreted as sourced from the tailings, even in solutions that possess significantly lower concentrations of Cu (<0.05 ppm). Elevated Cu isotope values were also found in two soil and two tailings samples (δ(65)Cu ranging between +2 to +5‰). These data point to the mineral pyrite in tailings as the mineral source for the elevated Cu isotope values. Therefore, Cu isotope values of waters emanating from a clearly contaminated drainage possess different Cu isotope values, permitting the discrimination of Cu derived from chalcopyrite and pyrite in solution. Data demonstrate the utility of Cu isotopic values in waters, minerals, and soils to fingerprint metallic contamination for environmental problems.

A reduced astrocyte response to ß-amyloid plaques in the ageing brain associates with cognitive impairment.

AIMS: ß-amyloid (Aß) plaques are a key feature of Alzheimer's disease pathology but correlate poorly with dementia. They are associated with astrocytes which may modulate the effect of Aß-deposition on the neuropil. This study characterised the astrocyte response to Aß plaque subtypes, and investigated their association with cognitive impairment. METHODS: Aß plaque subtypes were identified in the cingulate gyrus using dual labelling immunohistochemistry to Aß and GFAP+ astrocytes, and quantitated in two cortical areas: the area of densest plaque burden and the deep cortex near the white matter border (layer VI). Three subtypes were defined for both diffuse and compact plaques (also known as classical or core-plaques): Aß plaque with (1) no associated astrocytes, (2) focal astrogliosis or (3) circumferential astrogliosis. RESULTS: In the area of densest burden, diffuse plaques with no astrogliosis (ß = -0.05, p = 0.001) and with focal astrogliosis (ß = -0.27, p = 0.009) significantly associated with lower MMSE scores when controlling for sex and age at death. In the deep cortex (layer VI), both diffuse and compact plaques without astrogliosis associated with lower MMSE scores (ß = -0.15, p = 0.017 and ß = -0.81, p = 0.03, respectively). Diffuse plaques with no astrogliosis in layer VI related to dementia status (OR = 1.05, p = 0.025). In the area of densest burden, diffuse plaques with no astrogliosis or with focal astrogliosis associated with increasing Braak stage (ß = 0.01, p<0.001 and ß = 0.07, p<0.001, respectively), and ApoEε4 genotype (OR = 1.02, p = 0.001 and OR = 1.10, p = 0.016, respectively). In layer VI all plaque subtypes associated with Braak stage, and compact amyloid plaques with little and no associated astrogliosis associated with ApoEε4 genotype (OR = 1.50, p = 0.014 and OR = 0.10, p = 0.003, respectively). CONCLUSIONS: Reactive astrocytes in close proximity to either diffuse or compact plaques may have a neuroprotective role in the ageing brain, and possession of at least one copy of the ApoEε4 allele impacts the astroglial response to Aß plaques.