Traceability and dispersion of highly toxic soluble phases from historical mine tailings: insights from Pb isotope systematics.

Dispersion of potentially toxic elements associated with efflorescent crusts and mine tailings materials from historical mine sites threaten the environment and human health. Limited research has been done on traceability from historical mining sites in arid and semi-arid regions. Pb isotope systematics was applied to decipher the importance of identifying the mixing of lead sources involved in forming efflorescent salts and the repercussions on traceability. This research assessed mine waste (sulfide-rich and oxide-rich tailings material and efflorescent salts) and street dust from surrounding settlements at a historical mining site in northwestern Mexico, focusing on Pb isotope composition. The isotope data of tailings materials defined a trending line (R2 = 0.9); the sulfide-rich tailings materials and respective efflorescent salts yielded less radiogenic Pb composition, whereas the oxide-rich tailings and respective efflorescent salts yielded relatively more radiogenic compositions, similar to the geogenic component. The isotope composition of street dust suggests the dispersion of tailings materials into the surroundings. This investigation found that the variability of Pb isotope composition in tailings materials because of the geochemical heterogeneity, ranging from less radiogenic to more radiogenic, can add complexity during environmental assessments because the composition of oxidized materials and efflorescent salts can mask the geogenic component, potentially underestimating the influence on the environmental media.

Paracyclops chiltoni inhabiting water highly contaminated with arsenic: Water chemistry, population structure, and arsenic distribution within the organism.

We investigated population structure and arsenic bioaccumulation and distribution in zooplankton inhabiting highly contaminated freshwater with arsenic. We collected water and zooplankton samples over a 4 year period, determined environmental temperature as well as water temperature, pH, electrical conductivity (EC), total dissolved solids (TDS), oxidation-reduction potential (ORP), dissolved oxygen (DO), major cations and anions and total arsenic concentration. We identified zooplankton species and determined their abundance, length, sex ratios, and arsenic bioaccumulation and distribution in exposed organisms. At the study site, an extremophile, Paracyclops chiltoni, was found to survive in an environment with high concentration of arsenic, sulfate and fluoride in freshwater as a well-adapted organism. Results showed that the average arsenic concentration in freshwater was 53.64 ± 10.58 mg/L. Exposed organisms of Paracyclops chiltoni showed arsenic accumulation (up to 9.6 ± 5.4 mgAs/kg) in its body, likely in the digestive tract as well as typical abundance and length, which showed a relationship to environmental temperature and oxic conditions in freshwater. Metallotolerant copepods might help to better understand if arsenic methylation processes occur in freshwater aquatic organisms.

Water resources affected by potentially toxic elements in an area under current and historical mining in northwestern Mexico.

Rio Sonora watershed and its aquifer-located in northwest Mexico-have been influenced by mining operations for 140 years, possibly causing emissions of potentially toxic elements (PTE) and affecting health of exposed populations. On the basis of available data from governmental surveys (2014-2017) and recent sampling (2018), this study constructed reliable PTE total concentration database that allowed us to report temporal/spatial variations in surface and groundwater and their associated health risks to the population living in the central part of the Rio Sonora basin. The data clearly showed that a mining spill that took place in 2014 has had an adverse impact on total PTE concentrations in surface water. They also indicated the presence of different PTE point source locations that have continued to cause contamination of surface water at levels of health concern. Data also suggested slight impacts of the spill event on groundwater possibly related to soil neutralizing potential. Two metal groups were detected for surface waters (Pb-Cd-As-Ni-Cr and of Zn-Al-Cr) and groundwaters (Cr-As-Cu-Cd and Zn-Al), which suggest that they have different sources or are being released by different processes. The potential health impacts of PTE concentrations were associated with specific age groups, dates, and areas. The results indicate that in this complex semi-arid rural system, current and historical mining activities, as well as contrasting hydrological conditions, have impacted surface and groundwater quality with important ecological and human health risks.

Barriers for plant establishment in the abandoned tailings of Nacozari, Sonora, Mexico: the influence of compost addition on seedling performance and tailing properties.

Past mining activities have left a legacy of abandoned mine tailing deposits whose metal contaminants poses serious risks to ecosystems and human health. While the development of a vegetated cover in mine tailings can help in mitigating these risks, the local factors limiting plant establishment in these sites are not well understood, restricting phytostabilization efforts. Here, we explore some of the barriers that limit seedling establishment of two species (Vachellia farnesiana and Prosopis velutina) in a mine tailing deposit located in Nacozari, Sonora, Mexico, and assess whether compost addition can help in overcoming these barriers in pot and field experiments. Our field observations found 20 times more carbon and at least 4 times more nitrogen concentration in areas under vegetated patches than in non-vegetated areas, while a previous study found no difference in metal concentrations and other physicochemical parameters. This suggests that organic matter and nutrients are a major limitation for plant establishment. In agreement with this, species failed to establish without compost addition in the field experiment. Compost addition also had a positive effect on biomass accumulation, pH and microbial activity, but increased the substrate soluble concentration of As, Cu, and Zn. Nonetheless, only Cu, K, and Mo in P. velutina accumulated in tissues at levels considered toxic for animal consumption. Our study documents that compost addition facilitated plant establishment for the phytostabilization of mine tailings and help to prevent the dispersion of most metal contaminants via animal consumption. We encourage the use of complementary strategies to minimize the risk of dispersion of metal contaminants.

Mobility and accessibility of Zn, Pb, and As in abandoned mine tailings of northwestern Mexico.

Generation, storage, and management of waste coming from industrial processes are a growing worldwide problem. One of the main contributors is the mining industry, in particular tailings generated by historical mining, which are barely maintained, especially in developing countries. Assessing the impact of a mining site to surrounding soils and ecosystems can be complex, especially when determining mobility and accessibility of the contaminants is required to perform ecological and human health risk assessment. As an effort to obtain information regarding mobility and accessibility of some potentially toxic elements (Zn, Pb, and As) from an historical mining site of northwestern Mexico, the abandoned mine tailings of San Felipe de Jesús in central Sonora and adjacent agricultural soils were investigated. Mobility and accessibility were assessed by means of sequential extraction procedures and using simulated physiological media. Additionally, an assessment of accidental oral intake was calculated considering the bioaccessible fractions. Results show that higher concentrations of contaminants were found in sulfide-rich tailings (Zn = 92,540; Pb = 21,288; As = 19,740 mg kg-1) compared with oxide-rich tailings (Zn = 43,240; Pb = 14,763; As = 13,401 mg kg-1). Concentrations in agricultural soils were on average Zn = 4755, Pb = 2840, and As = 103 mg kg-1. Zinc was mainly recovered from labile fractions in oxide-rich tailings (~ 60%) and in a lower amount from sulfide-rich tailings (~ 30%). Pb and As were mainly associated with residual fractions (80-95%) in both types of tailings. The percentage of mobile fractions (sum of water-soluble, exchangeable, and bound to carbonate fractions) in agricultural soils was as follows: Zn ~ 60%, Pb ~ 15%, and As ~ 70%. Regarding the phytoaccessible fraction, the studied elements in mine tailings and agricultural soil samples exceeded the threshold limits, except for As in agricultural soils. According to data obtained, toxic effects were also calculated. As for daily oral intake for non-carcinogenic effects in adults and children, only Pb and As exceeded reference dose values, especially in children exposed to sulfide-rich tailings and agricultural soils. Regarding carcinogenic effects of Pb and As, most of the samples were above acceptable risk values.

Arsenic removal and activity of a sulfate reducing bacteria-enriched anaerobic sludge using zero valent iron as electron donor.

Arsenic (As) removal from water, subject to sulfate-reducing conditions has been shown to result in safe As levels. We evaluated sulfate-reducing activity and arsenic removal by an anaerobic sludge enriched with sulfate-reducing bacteria (SRB), using zero valent iron (ZVI) as electron donor and different concentrations of AsV or AsIII (up to 5 mg/L). Sulfate and As removal were monitored in aqueous samples of batch assays. Likewise, precipitates resulting from As removal were characterized in solids. Sulfate-reducing activity on the part of anaerobic sludge was slightly decreased by AsIII and it was 50% decreased, particularly at 5 mg/L AsV, for which arsenic removal equaled 98%. At all other As concentrations assayed, 100% As was removed. The co-existence of S, As and Fe in solids from assays with As, was demonstrated by scanning electron microscopy (SEM-EDS) and by micro-X-ray fluorescence, corroborating the possible formation of Fe-As-S type minerals for As precipitation. Pharmacosiderite and scorodite minerals were identified by micro-X-ray absorption near edge structure and confirmed by extended X-ray adsorption fine structure, and these were related to the oxidation of arsenopyrite during analysis. Results indicate the suitability of the anaerobic sludge for bioremediating arsenic-contaminated groundwater under sulfidogenic conditions with ZVI as electron donor.

The nature of ancient Egyptian copper-containing carbon inks is revealed by synchrotron radiation based X-ray microscopy.

For the first time it is shown that carbon black inks on ancient Egyptian papyri from different time periods and geographical regions contain copper. The inks have been investigated using synchrotron-based micro X-ray fluorescence (XRF) and micro X-ray absorption near-edge structure spectroscopy (XANES) at the European Synchrotron Radiation Facility (ESRF). The composition of the copper-containing carbon inks showed no significant differences that could be related to time periods or the geographical locations. This renders it probable that the same technology for ink production was used throughout Egypt for a period spanning at least 300 years. It is argued that the black pigment material (soot) for these inks was obtained as by-products of technical metallurgy. The copper (Cu) can be correlated with the following three main components: cuprite (Cu2O), azurite (Cu3[CO3]2[OH]2) and malachite (Cu2CO3[OH]2).

Weathering in soil increases nanoparticle CuO bioaccumulation within a terrestrial food chain.

This study evaluates the bioaccumulation of unweathered (U) and weathered (W) CuO in NP, bulk and ionic form (0-400 mg/kg) by lettuce exposed for 70 d in soil co-contaminated with field incurred chlordane. To evaluate CuO trophic transfer, leaves were fed to crickets (Acheta domestica) for 15 d, followed by insect feeding to lizards (Anolis carolinensis). Upon weathering, the root Cu content of the NP treatment increased 214% (327 ± 59.1 mg/kg) over unaged treatment. Cu root content decreased in bulk and ionic treatments from 70-130 mg/kg to 13-26 mg/kg upon aging in soil. Micro X-ray fluorescence (µ-XRF) analysis of W-NP-exposed roots showed a homogenous distribution of Cu (and Ca) in the tissues. Additionally, micro X-ray absorption near-edge (µ-XANES) analysis of W-NP-exposed roots showed near complete transformation of CuO to Cu (I)-sulfur and oxide complexes in the tissues, whereas in unweathered treatment, most root Cu remained as CuO. The expression level of nine genes involved in Cu transport shows that the mechanisms of CuO NPs (and bulk) response/accumulation are different than ionic Cu. The chlordane accumulation by lettuce upon co-exposure to CuO NPs significantly increased upon weathering. Conversely, bulk and ionic exposures decreased pesticide accumulation by plant upon weathering. The Cu cricket fecal content from U-NP-exposed insects was significantly greater than the bulk or ion treatments, suggesting a higher initial NP accumulation followed by significantly greater elimination during depuration. In the lizard, Cu content in the intestine, body and head did not differ as a function of weathering. This study demonstrates that CuO NPs may undergo transformation processes in soil upon weathering that subsequently impact NPs availability in terrestrial food chains.

Removal and accumulation of As, Cd and Cr by Typha latifolia.

The removal from the solution and the accumulation of As, Cd and Cr by Typha latifolia was studied. Small plants of T. latifolia, collected from a non-contaminated site, were exposed to individual concentrations of As, Cd and Cr for 10 days. The ability of T. latifolia for the removal of toxic elements ranged from 23% to 54% for As, 43%-55% for Cd and 28%-73% for Cr. The accumulation of toxic elements in T. latifolia occurred mainly in the roots. The results suggest that T. latifolia can be considered as an interesting alternative for treating aquatic effluents polluted with toxic trace elements.