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R. Cidu

Publications and source records attributed to R. Cidu.

5 recordsLinked to original sources

Isotopic insights into biological regulation of zinc in contaminated systems

Aquatic organisms use a variety of biogeochemical reactions to regulate essential and non-essential trace metals. Many of these mechanisms can lead to isotopic fractionation, thus measurement of metal isotopes may yield insights into the processes by which organisms respond to metal exposure. We illustrate these concepts with two case studies, one involving an intra- and the other an extra-cellular mechanism of Zn sequestration. In the first study, the mayfly Neocloeon triangulifer was grown in the laboratory, and fed a diet of Zn-doped diatoms at Zn levels exceeding the requirements for normal mayfly life functions. The N. triangulifer larvae consumed the diatoms and retained their Zn isotopic signature. Upon metamorphosis, the subimago life stage lost Zn mass either in the exuvia or by excretion, and the Zn retained was isotopically enriched. Thus, Zn uptake is nonfractionating, but Zn regulation favors the lighter isotope. Thus the Zn remaining in the subimago was isotopically heavier. In the second study, Zn was adsorbed on the cell walls and exopolysaccharide secretions of cyanobacteria, which favored the heavier Zn isotope. Continued adsorption eventually resulted in nucleation and biomineralization of hydrozincite {Zn5(CO3)2(OH)6}. These case studies demonstrate the utility of Zn isotopes to provide insights into how aquatic insects respond to metal exposure.

Procedia Earth and Planetary Science

Quantifying biomineralization of zinc in the Rio Naracauli (Sardinia, Italy), using a tracer injection and synoptic sampling

Streams draining mined areas throughout the world commonly have high concentrations of Zn. Because Zn is not easily removed from stream water and because it can be toxic to aquatic organisms, its presence is a persistent problem. The discovery of biomineralization of Zn-bearing solids in the mine drainage of Rio Naracauli, in Sardinia, Italy, provides insights into strategies for removing Zn and improving water quality in streams affected by mine drainage. Until now, the transport and attenuation of Zn has not been quantified in this stream setting. A continuous tracer injection experiment was conducted to quantify the biomineralization process and to identify the loading of constituents that causes a change from precipitation of hydrozincite [Zn 5 (CO 3 ) 2 (OH) 6 ] in the upstream reach to precipitation of a Zn-silicate phase downstream. Based on the mass-load calculations derived from the tracer experiment, about 1.2 kg/day of Zn is sequestered in hydrozincite. This biomineralization represents nearly 90% removal of Zn. Other elements such as Pb and Cd also are sequestered, either in the hydrozincite, or in a separate phase that forms simultaneously. In the lower 600 m of the stream, where the Zn-silicate forms, as much as 0.7 kg/day Zn are sequestered in this solid, but additions of Zn to the stream from groundwater discharge lead to an overall increase in load in that portion of the Rio Naracauli.

Sardinia

Zinc isotope and transition-element dynamics accompanying hydrozincite biomineralization in the Rio Naracauli, Sardinia, Italy

The Rio Naracauli in SW Sardinia drains part of the Ingurtosu Zn–Pb mining district, and contains extreme concentrations of dissolved Zn at near-neutral pH. In the upper reaches of the stream, pH, alkalinity and Zn concentrations are such that hydrozincite [Zn 5 (CO 3 ) 2 (OH) 6 ] precipitates in a biologically mediated process facilitated by a microalga ( Chlorella sp.) and a cyanobacterium ( Scytonema sp.). Values of δ 66 Zn in water and solid samples ranged from − 0.35‰ to + 0.5‰ relative to the JMC 3-0749-Lyon standard, and closely follow a mass-dependent fractionation line. Two composite samples of sphalerite, the primary ore mineral in the Ingurtosu deposits, had an average δ 66 Zn of + 0.15‰, similar to sphalerite measured elsewhere in hydrothermal mineral deposits. Zinc isotope measurements of the stream water and the hydrozincite forming in the stream show a consistent preference for the heavy isotope, 66 Zn, in the hydrozincite relative to 64 Zn. Synthetic hydrozincites produced without added bacteria have δ 66 Zn identical to the dissolved Zn, thus suggesting a biologically mediated mineralization process in Rio Naracauli. The average fractionation, Δ hdz-water , is 0.35‰, the magnitude of which is consistent with other studies, and suggests an extracellular mechanism of the biomineralization process. Zinc concentration and dissolved δ 66 Zn steadily decrease in the reach of the stream where the biomineralization occurs. The biomineralization process also leads to the sequestration of Pb, Cu and Ni in the hydrozincite lattice, and the coeval precipitation of an amorphous CdCO 3 solid, prompting the suggestion that if optimized, the biomineralization process might represent a feasible passive remediation strategy for streams with high Zn and other metals, and with near-neutral pH.

Sardinia

Formation of a low-crystalline Zn-silicate in a stream in SW Sardinia, Italy

n southwestern Sardinia, Italy, the Rio Naracauli drains a catchment that includes several abandoned mines. The drainage from the mines and associated waste rocks has led to extreme concentrations of dissolved Zn, but because of the near-neutral pH, concentrations of other metals remain low. In the reach from approximately 2300 to 3000 m downstream from the headwaters area, an amorphous Zn-silicate precipitates from the water. In this reach, concentrations of both Zn and silica remain nearly constant, but the loads (measured in mass/time) of both increase, suggesting that new Zn and silica are supplied to the stream, likely from emerging groundwater. Zinc isotope signatures of the solid are heavier than the dissolved Zn by about 0.5 permil in 66/64 Zn, suggesting that an extracellular biologically mediated adsorption process may be involved in the formation of the Zn-silicate.

Sardinia

Hydrozincite seasonal precipitation at Naracauli (Sardinia – Italy): Hydrochemical factors and morphological features of the biomineralization process

Hydrozincite [Zn 5 (CO 3 ) 2 (OH) 6 ] precipitation from Naracauli waters (SW Sardinia) is, among other things, promoted by a microbial community made up of a filamentous cyanobacterium ( Scytonema sp.) and a microalgae ( Chlorella sp.). Hydrozincite bioprecipitation is responsible for the natural removal of harmful metals, especially Zn, from the stream waters. Thus, hydrozincite could be used to attenuate metal pollution in mining waters. Information on environmental conditions which promote the biomineralization process is fundamental for the development of remediation strategies. This paper aims to investigate the variables controlling the biomineralization process, and seasonal variation of the hydrochemical factors that affect hydrozincite precipitation. Hydrozincite morphology varies depending on the environmental conditions. Specifically, changes were observed between samples collected in late spring and samples collected in summer, and among samples precipitated under different water flow conditions. According to field observations, correlated with speciation and equilibrium calculation, the maximum intensity in hydrozincite precipitation occurs in the late spring during rainy years. In these conditions, the hydraulic regime in the stream reaches stationary conditions, and saturation index values with respect to hydrozincite reach their highest values. Concomitantly, the Zn 2+ / CO 3 2 - "> CO32- molar ratio reaches values close to 1, indicating that kinetic processes have a role on the hydrozincite biomineralization process.

Sardinia