Free Ni Ion Research Articles

Highly efficient nickel recovery from industrial wastewater via synergistic electrodeposition and electrocatalytic oxidation technique

This study was conducted to address water pollution concerns entwined with electroless nickel plating (ENP) industry. Its principal endeavor centers on the development and application of an innovative single-compartment technique to proficiently treat spent ENP baths. The research demonstrated the recovery of Nickel (Ni) from wastewater through synergistic interactions between electrocatalytic oxidation and electrodeposition processes. Electrochemical tests used a direct current power supply in constant current mode, with the positive pole on IrO2/Ti mesh and negative pole on stainless steel. Zero-valent nickel recovered on the electrodes was conclusively identified via SEM, XRD, and EDS analyses. This work carefully examined the impact of initial pH, initial Ni ion concentration, and current density (CD) on electrochemical recovery efficiency. The findings suggest that higher current densities positively influence the Ni recovery ratio. Additionally, through meticulous experiments, the viability of this approach for treating spent ENP baths has been confirmed. An impressive 98.88% recovery of Ni was achieved under specific conditions: CD 4.5 mA cm−2, experimental time 180 min, pH 4.5, electrodes spacing 1.5 cm, temperature 55 °C, and a dilution factor 10 times. The study demonstrated the process for Ni recovering from ENP wastewater through direct oxidation and subsequent decomposition, leading to liberation of free Ni ions. The recovered substance, identified as zero-valent nickel, adheres to the electrodes. The method employed in this research is described by its cost-effectiveness, user-friendliness, and low energy consumption. As a result, this study makes valuable contributions to both wastewater remediation and the sustainable utilization of Ni resources.

Associations of Community Structure and Functions of Benthic Invertebrates with Nickel Concentrations: Analyses from Field Surveys.

Field surveys provide valuable empirical information about the effects of heavy metals on the biological integrity of river ecosystems. To evaluate the effect of nickel (Ni) on aquatic organisms, we conducted field surveys of benthic invertebrates and Ni concentrations at 45 sites in 19 rivers in Japan. We examined the relationships between 11 structural or functional measures of benthic invertebrate communities and free Ni ion concentrations with a 90th quantile regression model. Among the measures, Ephemeroptera, Plecoptera, and Trichoptera (EPT) richness, total wet biomass of all invertebrates, and total abundance of filter feeders were negatively associated with free Ni ion concentrations. The total abundance of mud burrowers and their percentage contribution to the abundance of all invertebrates as well as the total abundances of collector-gatherers and predators were positively associated with the Ni ion concentrations. The free ion concentrations of Ni associated with a 5% reduction of one of the 3 measures from its 90th quantile value at reference sites (EC5) were estimated to be 0.2 to 7.6 µg/L. The point estimates of EC5 were similar in order of magnitude to the environmental quality standard for Ni in the European Union. However, the usefulness of simple point estimates of effective concentrations based on quantile regression lines should be carefully examined because the uncertainties in our EC5 values were large. Environ Toxicol Chem 2019;38:1728-1737. © 2019 SETAC.

Time-dependent uptake and toxicity of nickel to Enchytraeus crypticus in the presence of humic acid and fulvic acid.

The present study aimed to investigate the influence of different fractions of dissolved organic carbon (DOC) on the uptake and toxicity of nickel (Ni) in the soil invertebrate Enchytraeus crypticus after different exposure times. The addition of DOC as humic acid or fulvic acid significantly reduced Ni uptake by E. crypticus in the soil-solution test system. Median lethal effect concentrations were calculated based on total dissolved Ni concentrations (LC50[Ni]), free Ni ion activity (LC50{Ni2+ }), and Ni body concentrations (LC50Body-Ni ). The LC50[Ni] values increased with increasing DOC levels and decreased with exposure time (4, 7, and 10 d). Humic acid exerted a greater protective effect on Ni toxicity than fulvic acid, but the protective effects decreased with prolonged exposure time. The LC50{Ni2+ } values also decreased with exposure time but were almost constant with variation in DOC levels, indicating that the protective effect of DOC is mainly through complexation with free Ni ions to reduce Ni bioavailability. The LC50Body-Ni value was independent of DOC concentration and exposure time, with an estimated overall value of 22.1 µg/g dry weight. The present study shows that body concentration could serve as an effective indicator for predicting Ni toxicity with variations in the exposure environment (e.g., DOC) and exposure time. Environ Toxicol Chem 2017;36:3019-3027. © 2017 SETAC.

Differential Toxicities of Nickel Salts to the Nematode Caenorhabditis elegans.

This study focused on assessing whether nickel (Ni) toxicity to the nematode Caenorhabditis elegans was affected by the molecular structure of the Ni salt used. Nematodes were exposed to seven Ni salts [Ni sulfate hexahydrate (NiSO4·6H2O), Ni chloride hexahydrate (NiCl2·6H2O), Ni acetate tetrahydrate (Ni(OCOCH3)2·4H2O), Ni nitrate hexahydrate (N2NiO6·6H2O), anhydrous Ni iodide (NiI2), Ni sulfamate hydrate (Ni(SO3NH2)2·H2O), and Ni fluoride tetrahydrate (NiF2·4H2O)] in an aquatic medium for 24h, and lethality curves were generated and analyzed. Ni fluoride, Ni iodide, and Ni chloride were most toxic to C. elegans, followed by Ni nitrate, Ni sulfamate, Ni acetate, and Ni sulfate. The LC50 values of the halogen-containing salts were statistically different from the corresponding value of the least toxic salt, Ni sulfate. This finding is consistent with the expected high bioavailability of free Ni ions in halide solutions. We recommend that the halide salts be used in future Ni testing involving aquatic invertebrates.

Effect of major cations (Ca2+, Mg2+, Na+, K+) and anions (SO, Cl−, NO) on Ni accumulation and toxicity in aquatic plant (Lemna minor L.): Implications For Ni risk assessment

The effect of major cation activity (Ca(2+) , Mg(2+) , Na(+) , K(+) ) on Ni toxicity, with dose expressed as exposure (total dissolved Ni concentration NiTot ) or free Ni ion activity (in solution Ni(2+) ), or as tissue residue (Ni concentration in plant tissue NiTiss ) to the aquatic plant Lemna minor L. was examined. In addition, Ni accumulation kinetics was explored to provide mechanistic insight into current approaches of toxicity modeling, such as the tissue residue approach and the biotic ligand model (BLM), and the implications for plant Ni risk assessment. Major cations did not inhibit Ni accumulation via competitive inhibition as expected by the BLM framework. For example, Ca(2+) and Mg(2+) (sulfate as counter-anion) had an anticompetitive effect on Ni accumulation, suggesting that Ca or Mg forms a ternary complex with Ni-biotic ligand. The counter-anion of the added Ca (sulfate, chloride, or nitrate) affected plant response (percentage of root growth inhibition) to Ni. Generally, sulfate and chloride influenced plant response while nitrate did not, even when compared within the same range of Ca(2+) , which suggests that the anion dominated the observed plant response. Overall, although an effect of major cations on Ni toxicity to L. minor L. was observed at a physiological level, Ni(2+) or NiTot alone modeled plant response, generally within a span of twofold, over a wide range of water chemistry. Thus, consideration of major cation competition for improving Ni toxicity predictions in risk assessment for aquatic plants may not be necessary.

Studies on the Growth Mechanism of Hydrothermal Synthesis of α-Ni(OH)2Nanowires

4 SO ions and OH ions play important roles in hydrothermal synthesis of Ni(OH)2 nanostructures with only inorganic nickel salt and NaOH. The whole process could be divided into 2 parts, the preparation of Ni(OH)2 gel and its hydrothermal reaction. According to our analysis, the former one is an ionic-reaction which produces amorphous Ni(OH)2. It is the later one when Ni(OH)2 gel crystallizes that dominates the polymorph and morphology of final products. The influence of OHon morphologies of Ni(OH)2 has been studied by changing the ratio of n( 4 SO )/n(OH -). To discuss the effect of 2 4 SO ions in hydrothermal system on crystal growth, we wash the gel which is prepared by NiCl2 and NaOH with the mixture solution of Na2SO4 and NiSO4 for different times, so that Cl ions in the gel solution could be replaced by 4 SO ions in varying degrees. Then the nanosized Ni(OH)2 products is prepared by hydrothermal treatment. Also, the samples were characterized by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). TEM results show that there will be 2 main nanostructures in different hydrothermal conditions: nanowires and nanosheets. XRD and FTIR results reveals that the nanowires is Ni(SO4)0.3(OH)1.4, one kind of α-Ni(OH)2, and the nanosheet is β-Ni(OH)2. We finally got a conclusion that low amount of OH and pure 4 SO environment is advantageous to synthesis of α-Ni(OH)2 nanowires. Since α-Ni(OH)2 is hydroxyl-deficient and consists of stacked Ni(OH)2-x layers toward which the 4 SO ion has a higher affinity than other ions such as Cl and 3 NO , the 4 SO ion is able to enter its interlayers. The structure is stabilized due to the strong coordination bonds between 4 SO and Ni + in Ni(OH)2-x layers. Also, free Ni ions in solution would be linked to intercalated 4 SO through coordination bonds, so that new Ni(OH)2-x layers could form constantly and stack along the c-axis. As a result, there will be a preferential growth in the [001] direction. However, this process is not likely to continue when there is high amount of OH-, which may cause high Coulomb repulsion along the [001] direction.

Effect of pH and environmental ligands on accumulation and toxicity of Ni2+ to Lemna minor

Environmental context Predicting metal toxicity is an important tool for effective and efficient risk assessment and regulation of metal pollution in the environment. The present study aims to provide scientific support for the development of a predictive Ni toxicity model for aquatic plants that is particularly applicable to mining-affected natural waters. We show that the effects of pH and natural organic ligands on Ni accumulation and toxicity can be modelled, but further research is required to understand the effects of flotation ligands used in the mining industry. Abstract Effects of water chemistry and metal speciation on metal uptake and toxicity to aquatic plants such as Lemna minor are not fully understood. The present study examined the effect of pH and environmental ligands (dissolved organic carbon (DOC) and mining related flotation ligands diethylenetriamine (DETA), triethylenetetramine (TETA), sodium isopropyl xanthate), on Ni toxicity to L. minor. Exposure and tissue residue toxicity thresholds were assessed to validate the use of a Biotic Ligand Model (BLM) or a Tissue Residue Approach (TRA) as a framework for predicting Ni toxicity. An increase in the activity of H+ non-linearly decreased the toxicity of free Ni ion activity, whereas Ni accumulation kinetics indicated that the mechanism of Ni2+ and H+ interaction was not competitive inhibition as expected by the BLM framework. The effect of DOC on the toxicity of total Ni concentration was relatively small (toxicity decreased by less than a factor of 2) and was explained solely by the complexation of Ni2+ by DOC. Alternatively, the protective effect of flotation ligands (DETA and TETA) was much less than expected based on estimated Ni complexation. Overall, a TRA model was directly applicable in the presence of organic ligands but not to varying pH, whereas a BLM-type model was applicable with changes in pH and DOC but not in the presence of the lesser studied flotation ligands. Such mechanistic information is essential for the development of reliable Ni toxicity models that would aid in risk assessment and regulation of Ni in the environment, particularly in mining-affected regions.

Nickel speciation in the presence of different sources and fractions of dissolved organic matter

This study evaluated nickel (Ni) speciation in the presence of different fractions (humic acid (HA), fulvic acid (FA)) and sources (natural sediment, Suwannee River, peat moss) of dissolved organic matter (DOM) at Ni concentrations toxicologically relevant to the freshwater amphipod, Hyalella azteca. The free Ni ion, Ni 2+, was measured in reconstituted water (with or without DOM) using a miniaturized ion-exchange technique (IET). Ni speciation from these experiments was compared to calculated results obtained from equilibrium modelling (WHAM, Model VI). While it is known that Ni will complex with DOM, it was found that under acutely toxic Ni exposure concentrations ([Ni Total]=5 mg/L, or 85.1 μM) representative surface-water DOC concentrations (∼10 mg/L) played little or no role in Ni speciation. Conversely, at sublethal Ni exposure concentrations ([Ni Total]=0.2 and 0.5 μg/L, or 3.4 and 8.51 μM, respectively) DOM significantly affected Ni speciation with [Ni 2+] decreasing with increasing concentration of DOM. It was found that for similar concentrations of DOC (same fraction, different sources), the measured Ni 2+ concentrations were reduced (relative to the control), but similar to one another. Conversely, at similar DOC concentrations, the HA fraction reduced Ni 2+ levels to a greater extent than the associated FA fraction. Overall, this study provides proof of principle that Suwannee River and peat humic substances are suitable analogues for natural sediment pore-water DOM when evaluating Ni bioavailability in freshwater.