Precise measurement of Fe isotopes in marine and biological samples by pseudo-high-resolution multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS).

This paper introduces an enhanced technique for analyzing iron isotopes in complex marine and biological samples. A dedicated iron purification method for biological marine matrices, utilizing three ion exchange columns, is validated. The MC-ICPMS in pseudo-high-resolution mode determines precise iron isotopic ratios, with sensitivity improved through the DSN-100 desolvating nebulizer system and Apex-IR. Only 2 µg of iron on DSN versus 1 µg on Apex is needed for six replicates (30-60 times improvement) while 10 to 20 µg is required for a single measurement on a wet system considering the resolution power (Rp) is maintained at 11,000-13,000. The Ni-doping method with a Fe/Ni ratio of 1 yields more accurate isotopic ratios than standard-sample bracketing alone. Measurement reproducibility of triplicate samples from marine biological experiments on MC-ICPMS is ± 0.03‰ (2SD) for δ56Fe and ± 0.07‰ for δ57Fe (2SD). This study introduces a novel iron purification process specifically designed for marine and biological samples, enhancing sensitivity and enabling more reliable measurements with smaller sample sizes and reduced uncertainties. It proposes iron isotopic compositions for biological reference materials, offering a valuable reference dataset in diverse scientific disciplines.

Evaluation on chemical stability of lead blast furnace (LBF) and imperial smelting furnace (ISF) slags.

The leaching behavior of Pb and Zn from lead blast furnace (LBF) and imperial smelting furnace (ISF) slags sampled in the North of France was studied as a function of pHs and under two atmospheres (open air and nitrogen). The leaching of major elements from the slags was monitored as a function of pH (4, 5.5, 7, 8.5 and 10) under both atmospheres for different slag-water interaction times (1 day and 9 days). The leaching results were coupled with a geochemical model; Visual MINTEQ version 3.0, and a detailed morphological and mineralogical analysis was performed on the leached slags by scanning and transmission electron microscopy (SEM and TEM). Significant amounts of Ca, Fe and Zn were released under acidic conditions (pH 4) with a decrease towards the neutral to alkaline conditions (pH 7 and 10) for both LBF and ISF slags. On the other hand, Fe leachability was limited at neutral to alkaline pH for both slags. The concentrations of all elements increased gradually after 216 h compared to initial 24 h of leaching period. The presence of oxygen under open-air atmosphere not only enhanced oxidative weathering but also encouraged formation of secondary oxide and carbonate phases. Formation of carbonates and clay minerals was suggested by Visual MINTEQ which was further confirmed by SEM & TEM. The hydration and partial dissolution of hardystonite, as well as the destabilization of amorphous glassy matrix mainly contributed to the release of major elements, whereas the spinel related oxides were resistant against pH changes and atmospheres within the time frame concerned for both LBF and ISF slags. The total amount of Pb leached out at pH 7 under both atmospheres suggested that both LBF and ISF slags are prone to weathering even at neutral environmental conditions.

Bio-alteration of metallurgical wastes by Pseudomonas aeruginosa in a semi flow-through reactor.

Metallurgical activities can generate a huge amount of partially vitrified waste products which are either landfilled or recycled. Lead Blast Furnace (LBF) slags are often disposed of in the vicinity of metallurgical plants, and are prone to weathering, releasing potentially toxic chemical components into the local environment. To simulate natural weathering in a slag heap, bioweathering of these LBF slags was studied in the presence of a pure heterotrophic bacterial strain (Pseudomonas aeruginosa) and in a semi-flow through reactor with intermittent leachate renewal. The evolution of water chemistry, slag composition and texture were monitored during the experiments. The cumulative bulk release of dissolved Fe, Si, Ca and Mg doubled in the presence of bacteria, probably due to the release of soluble complexing organic molecules (e.g. siderophores). In addition, bacterial biomass served as the bioadsorbent for Pb, Fe and Zn as 70-80% of Pb and Fe, 40-60% of Zn released are attached to and immobilized by the bacterial biomass.

Iron isotopic fractionation driven by low-temperature biogeochemical processes.

Iron is geologically important and biochemically crucial for all microorganisms, plants and animals due to its redox exchange, the involvement in electron transport and metabolic processes. Despite the abundance of iron in the earth crust, its bioavailability is very limited in nature due to its occurrence as ferrihydrite, goethite, and hematite where they are thermodynamically stable with low dissolution kinetics in neutral or alkaline environments. Organisms such as bacteria, fungi, and plants have evolved iron acquisition mechanisms to increase its bioavailability in such environments, thereby, contributing largely to the iron cycle in the environment. Biogeochemical cycling of metals including Fe in natural systems usually results in stable isotope fractionation; the extent of fractionation depends on processes involved. Our review suggests that significant fractionation of iron isotopes occurs in low-temperature environments, where the extent of fractionation is greatly governed by several biogeochemical processes such as redox reaction, alteration, complexation, adsorption, oxidation and reduction, with or without the influence of microorganisms. This paper includes relevant data sets on the theoretical calculations, experimental prediction, as well as laboratory studies on stable iron isotopes fractionation induced by different biogeochemical processes.

Zn isotopes fractionation during slags' weathering: One source of contamination, multiple isotopic signatures.

During the chemical weathering of lead blast furnace (LBF) and imperial smelting furnace (ISF) slags, possible Zn isotopes fractionation was studied as a function of pH, atmosphere (open air vs nitrogen), and time. Bulk LBF and ISF displayed heavier signatures compared to Johnson Matthey Company (JMC) Zn standard solution (i.e. 0.13 ±â€¯0.06‰ and 0.78 ±â€¯0.13‰ for LBF and ISF, resp). The Zn signatures vary greatly by changes in solution pH; heavier signatures at low pH and lighter signature at high pH. Smithsonite (ZnCO3) formation could induce a big delta Δ66ZnNitro-Open.atm of 1.13‰ at pH 10 and rapid zinc hydroxide precipitation could induce Δ66ZnNitro-Open.atm of 0.13-0.2‰ at pH 8.5. In addition, slags contain many mineral phases: ∼80-84% of amorphous glassy phase (in v/v) and ∼16-20% of many other crystalline phases. Zn isotope signatures in primary mineral phases can be extrapolated where the signature of the amorphous glassy phase lies between -0.35‰ and -0.42‰, and that of the overall crystalline phases was estimated to be 2.12‰ for LBF and 5.74‰ for ISF. Therefore, un-weathered slags with many mineral phases can host distinct Zn isotope signatures, which further evolve significantly during chemical weathering. One should thus carefully consider the heterogeneity of slags and the low-temperature chemical processes which lead to diverse Zn isotopic signature in the end, when using Zn isotopes as tracer of smelter's contamination.

Co-disposal of electronic waste with municipal solid waste in bioreactor landfills.

Three pilot scale lysimeters were adopted to evaluate the stability pattern and leaching potential of heavy metals from MSW landfills under the E-waste co-disposed condition. One lysimeter served as control and solely filled with MSW, whereas the other two lysimeters were provided with 10% and 25% of E-waste scraps (% by weight), respectively. The reactors were monitored over a period of 280 days at ambient settings with continuous leachate recirculation. Stabilization pattern of carbon appears to be more than 50% in all the three lysimeters with irrespective of their operating conditions. Iron and zinc concentrations were high in leachate during bioreactor landfill operation and correlating with the TCLP leachability test results. In contrast, Pb concentration was around <0.6 mg/L, but which showed maximum leaching potential under TCLP test conditions. But, no heavy metal accumulation was found with leachate recirculation practices in lysimeters. Mobility of the metal content from the E-waste was found to be amplified with the long term disposal or stabilization within landfills. The results showed that the TCLP test cannot be completely reliable tool for measuring long-term leachability of toxic substances under landfill condition; rather landfill lysimeter studies are necessary to get the real scenario.