In this article, we focus on the analysis of dyed textile fragments uncovered at an early Iron Age (11th-10th centuries BCE) copper smelting site during new excavations in the Timna Valley conducted by the Central Timna Valley (CTV) Project, as well as those found by the Arabah Expedition at the Hathor Temple (Site 200), dated to the Late Bronze/early Iron Ages (13th-11th centuries BCE). Analysis by HPLC-DAD identified two organic dyestuffs, Rubia tinctorum L. and indigotin, from a plant source (probably Isatis tinctoria L.). They are among the earliest plants known in the dyeing craft and cultivated primarily for this purpose. This study provides the earliest evidence of textiles dyed utilizing a chemical dyeing process based on an industrial dyeing plant from the Levant. Moreover, our results shed new light on the society operating the copper mines at the time, suggesting the existence of an elite that was interested in these high quality textiles and invested efforts in procuring them by long-distance trade.
Present day lead pollution is an environmental hazard of global proportions. A correct determination of natural lead levels is very important in order to evaluate anthropogenic lead contributions. In this paper, the anthropogenic signature of early metallurgy in Southern Iberia during the Holocene, more specifically during the Late Prehistory, was assessed by mean of a multiproxy approach: comparison of atmospheric lead pollution, fire regimes, deforestation, mass sediment transport, and archeological data. Although the onset of metallurgy in Southern Iberia is a matter of controversy, here we show the oldest lead pollution record from Western Europe in a continuous paleoenvironmental sequence, which suggests clear lead pollution caused by metallurgical activities since ~3900cal BP (Early Bronze Age). This lead pollution was especially important during Late Bronze and Early Iron ages. At the same time, since ~4000cal BP, an increase in fire activity is observed in this area, which is also coupled with deforestation and increased erosion rates. This study also shows that the lead pollution record locally reached near present-day values many times in the past, suggesting intensive use and manipulation of lead during those periods in this area.
The Flin Flon, Manitoba copper smelter was Canada’s largest point source of mercury emissions until its closure in 2010 after ~80 years of operation. The objective of this study was to understand the variables controlling the local ground-level air mercury concentrations before and after this major point source reduction. Total gaseous mercury (TGM) in air, mercury in precipitation, and other ancillary meteorological and air quality parameters were measured pre and post-smelter closure, and mercury speciation measurements in air were collected post-closure. The results showed that TGM was significantly elevated during the time period when the smelter operated (4.1 ± 3.7 ng m-3), decreased only 20% during the year following its closure, and remained ~2-fold above background levels. Similar trends were observed for mercury concentrations in precipitation. Several lines of evidence indicated that while smelter stack emissions would occasionally mix down to the surface resulting in large spikes in TGM concentrations (up to 61 ng m-3), the largest contributor to elevated TGM concentrations before and after smelter closure was from surface-air fluxes from mercury-enriched soils and/or tailings. These findings highlight the ability of legacy mercury, deposited to local landscapes over decades from industrial activities, to significantly affect local air concentrations via emissions/re-emissions.
Globally, billions of individuals wash their hair in water, which acts as an exogenous metal source. Many studies which measure the metal levels found on human hair specifically aim to remove exogenous materials prior to analysis. While this is needed when using hair analysis to probe the impact of the local environment on endogenous metal levels, it’s not relevant for understanding exactly what is on hair as a result of contact with its daily environment. Understanding these levels are important, as the presence of redox active metals, such as copper and iron, can impact fibre health, either due to UV irradiation, or during the hair colouring process. A global hair sampling study of over 300 individuals from nine countries has been performed, and the combined endogenous and exogenous metals analysed. The levels measured vary widely, even within the narrow geography of each hair sampling location. The levels of calcium, magnesium, copper and iron were not correlated, and within each location there are expected to be individuals with high metal levels. Levels increased from hair root to tip for calcium, magnesium and copper, attributed to hair’s contact with the environment showing the impact of exogenous metals in the overall levels on hair. Levels of redox metals were comparable between individuals who coloured or did not colour their hair, although water hardness ions were statistically significantly higher for hair colouring individuals. Individuals who perceived their hair health as poor had higher metal levels on their hair. Controlling metals on hair, either by preventing their binding during environmental contact, or through controlling their ability to cause hair damage, should lead to improved consumer perceived hair health. © 2013 Society of Cosmetic Scientists and the Société Française de Cosmétologie.
Lead (Pb) concentrations and isotopic compositions from soils, dusts and aerosols from public land and residential lots adjacent to the copper and Pb mine and smelter at Mount Isa, Australia, were examined to understand the sources and risks of environmental Pb exposure. Urban soil samples contain elevated Pb concentrations (mean 1560 mg/kg), of which 45-85% of the Pb is bioaccessible. The Pb isotopic composition of surface soils (0-2 cm), aerosols and dusts ((206)Pb/(207)Pb, (208)Pb/(207)Pb range: 1.049, 2.322-1.069, 2.345) are dominated by Pb derived from the Mount Isa Pb-zinc ore bodies. Underlying soil horizons (10-20 cm) have distinctly different Pb isotopic compositions ((206)Pb/(207)Pb, (208)Pb/(207)Pb range: 1.093, 2.354-1.212, 2.495). Surface soil-, dust- and aerosol-Pb are derived predominantly from smelter emissions and fugitive mining sources and not from in situ weathered bedrock. Remediation strategies should target legacy and ongoing sources of environmental Pb to mitigate the problem of Pb exposure at Mount Isa.
Washing and wet mopping is often advocated as a remedial treatment to limit exposure to lead dust. Here, surface and pre- and post-play wipes were measured to ascertain dust metal exposures (arsenic, cadmium, copper, lead and zinc) following play routines at four playgrounds in the smelter city of Port Pirie, South Australia, which are washed regularly. Although post-play hand wipe metals were 55.9% (95% CI: -0.78, -0.34) lower on wash days, loadings increased ∼5.1% (95% CI: 1.2, 11.7) per hour after washing. Despite washing, post-play hand lead exceeded a conservative value of 800 μg/m(2) within 24 h or sooner, with loadings increasing in proximity to the smelter. Post-play lead loadings were always >1000 μg/m(2) at the playground closest to smelter. Playground washing results in short-lived exposure reduction and effective treatment requires elimination of smelter emissions.
The mining and use of copper by prehistoric people on Michigan’s Keweenaw Peninsula is one of the oldest examples of metalworking. We analyzed the concentration of lead, titanium, magnesium, iron, and organic matter in sediment cores recovered from three lakes located near mine pits to investigate the timing, location, and magnitude of ancient copper mining pollution. Lead concentrations were normalized to lithogenic metals and organic matter to account for processes that can influence natural (or background) lead delivery. Nearly simultaneous lead enrichments occurred at Lake Manganese and Copper Falls Lake ~8000 and 7000 yr BP, indicating that copper extraction occurred concurrently in at least two locations on the peninsula. The poor temporal coherence among the lead enrichments from ~6300 to 5000 yr BP at each lake suggests that the focus of copper mining and annealing shifted through time. In sediment younger that ~5000 yr BP, lead concentrations remain at background levels at all three lakes, excluding historic lead increases starting ~150 yr BP. Our work demonstrates that lead emissions associated with both the historic and Old Copper Complex tradition are detectable and can be used to determine the temporal and geographic pattern of metal pollution.
A long-term disposal of technetium-99 (99Tc) has been considered in a type of cementitious formulation, slag-based grout, at the U.S. Department of Energy, Savannah River Site, Aiken SC, U.S.A. Blast furnace slag, which contains S and Fe electron donors, has been used in a mixture with fly ash, and Portland cement to immobilize 99Tc(VII)O4-(aq) in low level radioactive waste via reductive precipitation reaction. However the long-term stability of Tc(IV) species is not clearly understood as oxygen gradually diffuses into the solid structure. In this study, aging effects of Tc speciation were investigated as a function of depth (<2.5cm) in slag-based grout using X-ray absorption spectroscopy. All of Fe(II) in solids was oxidized to Fe(III) after 117d. However, elemental S, sulfide, and sulfoxide persists at the 0-8mm depths even after 485d, suggesting the presence of a reduced zone below the surface few millimeters. Pertechnetate was successfully reduced to Tc(IV) after 29d. Distorted hydrolyzed Tc(IV) octahedral molecules were partially sulfidized and or polymerized at all depths (0-8mm) and were stable in 485d aged sample. The results of this study suggest that variable S species contribute to stabilize the partially sulfidized Tc(IV) species in aged slag-based grout.
Boiler residue (BR) of thermal power plants is one of the important secondary sources for vanadium production. In this research, the aluminothermic self-propagating high-temperature synthesis (SHS) was used for recovering the transition metals of BR for the first time. The effects of extra aluminum as reducing agent and flux to aluminum ratio (CaO/Al) were studied and the efficiency of recovery and presence of impurities were measured. Aluminothermic reduction of vanadium and other metals was carried out successfully by SHS without any foreign heat source. Vanadium, iron, and nickel principally were reduced and gone into metallic master alloy as SHS product. High levels of efficiency (>80%) were achieved and the results showed that SHS has a great potential to be an industrial process for BR recovery. SHS produced two useful products. Metallic master alloy and fused glass slag that is applicable for ceramic industries. SHS can also neutralize the environmental threats of BR by a one step process.
Co-treatment of flotation waste, neutralization sludge, and arsenic-containing gypsum sludge from copper smelting: solidification/stabilization of arsenic and heavy metals with minimal cement clinker
- Environmental science and pollution research international
- Published 26 days ago
Flotation waste of copper slag (FWCS), neutralization sludge (NS), and arsenic-containing gypsum sludge (GS), both of which are difficult to dispose of, are major solid wastes produced by the copper smelting. This study focused on the co-treatment of FWCS, NS, and GS for solidification/stabilization of arsenic and heavy metals with minimal cement clinker. Firstly, the preparation parameters of binder composed of FWCS, NS, and cement clinker were optimized to be FWCS dosage of 40%, NS dosage of 10%, cement clinker dosage of 50%, mill time of 1.5 h, and water-to-binder ratio of 0.25. On these conditions, the unconfined compressive strength (UCS) of the binder reached 43.24 MPa after hydration of 28 days. Then, the binder was used to solidify/stabilize the As-containing GS. When the mass ratio of binder-to-GS was 5:5, the UCS of matrix can reach 11.06 MPa after hydration of 28 days, meeting the required UCS level of MU10 brick in China. Moreover, arsenic and other heavy metals in FWCS, NS, and GS were effectively solidified or stabilized. The heavy metal concentrations in leachate were much lower than those in the limits of China standard leaching test (CSLT). Therefore, the matrices were potential to be used as bricks in some constructions. XRD analysis shows that the main hydration products of the matrix were portlandite and calcium silicate hydrate. These hydration products may play a significant role in the stabilization/solidification of arsenic and heavy metals.