Field evidence of decreased extractability of copper and nickel added to soils in 6-year field experiments

The phytotoxicity of added copper (Cu) and nickel (Ni) is influenced by soil properties and field aging. However, the differences in the chemical behavior between Cu and Ni are still unclear. Therefore, this study was conducted to investigate the extractability of added Cu and Ni in 6-year field experiments, as well as the link with their phytotoxicity. The results showed that the extractability of added Cu decreased by 6.63% (5.10%–7.90%), 22.5% (20.6%–23.9%), and 6.87% (0%–17.9%) on average for acidic, neutral, and alkaline soil from 1 to 6 years, although the phytotoxicity of added Cu and Ni did not change significantly from 1 to 6 years in the long term field experiment. Because of dissolution of Cu, when the pH decreased below 7.0, the extractability of Cu in alkaline soil by EDTA at pH 4.0 could not reflect the effects of aging. For Ni, the extractability decreased by 18.1% (10.1%–33.0%), 63.0% (59.2%–68.8%), and 22.0% (12.4%–31.8%) from 1 to 6 years in acidic, neutral, and alkaline soils, respectively, indicating the effects of aging on Ni were greater than on Cu. The sum of ten sequential extractions of Cu and Ni showed that added Cu was more extractable than Ni in neutral and alkaline soil, but similar in acidic soil.

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Enzymatic and cellular level effects of nickel∗

The effects of Ni on hepatic enzymes of tilapia, viz. acid‐ and alkaline phosphatases, catalase and glucose‐6‐phosphatase, both under in vivo and in vitro conditions reflected the following tendencies. In vivo conditions indicated maximal increase in activity for acid phosphatase at 3.00 ppm, equivalent to 28.5%, followed by a slight decrease and increase thereafter. As for alkaline phosphatase, gradual increase in activity was observed with maximal activity at 9 ppm of Ni, equivalent to 16.8%. Catalase demonstrated similar tendencies with maximal activity at 9.0 ppm, equivalent to 101.2%. In the case of glucose‐6‐phosphatase, the tendency was the reverse with maximal inhibition at 9.00 ppm, i.e. 41.9%. In contrast to in vivo conditions, in vitro systems indicated that all investigated enzymes were inhibited in the region of 4–10% except for catalase which demonstrated a slight increase by 5–6% in activity between concentrations of 10–15 ppm of Ni but thereafter continuous inhibitory effects prevailed.

At cellular level, exposure of tilapia to a lethal dose of 9 ppm of Ni indicated not much of an adverse effect except for a slight depletion in fat and glycogen content. In the case of mitochondria, they were normal and a few large secondary lysosomes were observed. In relation to the cell membrane no dramatic change was detected.     

Influence of iron,nickel and cobalt on biogas production during the anaerobic fermentation of fresh residual biomass

We have investigated the dependence of the rate of the production of biogas upon the concentration of nickel, cobalt and iron at sub-toxic concentration and monitored its composition as amount of hydrogen, methane and carbon dioxide. The distribution of the added metals between the liquid and solid phase has also been monitored.

The results of our investigations show that the addition of any of the listed metals to the sludge may cause the production of a higher amount of biogas and influence the methane or carbon dioxide percentage. Conversely, the effect on the hydrogen production depends upon the metal added, the age of the active sludge used, and its adaptation to the susbtrate. As a general feature, during the acidogenesis phase, nickel reduces, while iron increases, the percentage of dihydrogen in the biogas, while cobalt has no influence.     

水环境中镍毒性的机制研究：有害结局路径(AOP)分析

目前对镍(Ni)生态风险评估和水质法规采用了基于机制的预测工具，如生物配体模型(BLMs)。然而，尽管有许多具体细致的研究，Ni对水生生物毒性的精确机制仍然难以确定。对Ni行为机制的不确定性导致了大家在一些管理设置中应用像BLM这样的工具时，有所顾虑。为了解决这一认知差距，作者使用了有害结局路径(AOP)分析，也是第一个用于金属的AOP分析，来确定Ni毒性的多种潜在机制以及它们与淡水水生生物的相互作用。在金属的分子起始事件(molecular initiating events)在分类群中可能存在的前提下，在许多不同种水生和陆生生物数据的基础上，考虑建立一种潜在的行为机制。通过分析，作者识别了Ni可能对水生生物产生毒性的5个潜在的分子起始事件：Ca²⁺体内平衡的破坏，Mg²⁺体内平衡的破坏，Fe²⁺/³⁺体内平衡的破坏，活性氧类物质引起的氧化损伤，以及呼吸上皮细胞的过敏反应。在生物组织的器官水平，这5个潜在的分子起始事件会分解成3个可能的途径：支持外骨骼、外壳和骨骼生长的Ca²⁺减少；呼吸受损；细胞毒性和肿瘤形成。在整个生物体的水平，器官水平的反应将可能导致生长、繁殖的降低和/或能量代谢的改变，并且在每个通路之间有几个潜在的反馈回路。总体来说，目前的AOP分析可指导Ni的毒性机制研究，并为其他金属开发AOPs提供了有效的参考。
精选自Brix, K. V., Schlekat, C. E. and Garman, E. R. (2017), The mechanisms of nickel toxicity in aquatic environments: An adverse outcome pathway analysis. Environmental Toxicology and Chemistry, 36: 1128–1137. doi: 10.1002/etc.3706
详情请见http://onlinelibrary.wiley.com/wol1/doi/10.1002/etc.3706/full
     

Enhanced solar-light-driven photocatalytic properties of novel Z-scheme binary BiPO4 nanorods anchored onto NiFe2O4 nanoplates: Efficient removal of toxic organic pollutants

Global environmental problems have been increasing with the growth of the world economy and have become a crucial issue. To replace fossil fuels, sustainable and eco-friendly catalysts are required for the removal of organic pollutants. In this study, nickel ferrite (NiFe₂O₄) was prepared using a simple wet-chemical synthesis, followed by calcination; bismuth phosphate (BiPO₄) was also prepared using a hydrothermal method. Further, NiFe₂O₄/BiPO₄ nanocomposites were prepared using a hydrothermal technique. Numerous characterization studies, such as structural, morphology, surface area, optical, photoluminescence, and photoelectrochemical investigations, were used to analyze NiFe₂O₄/BiPO₄ nanocomposites. The morphology analysis indicated a successful decoration of BiPO₄ nanorods on the surface of NiFe₂O₄ nanoplate. Further, the bandgap of the NiFe₂O₄/BiPO₄ nanocomposites was modified owing to the formation of a heterostructure. The as-prepared NiFe₂O₄/BiPO₄ nanocomposite exhibited promising properties to be used as a novel heterostructure for tetracycline (TC) and Rhodamine B (RhB) removal. The NiFe₂O₄/BiPO₄ nanocomposite degrades TC (98%) and RhB (99%) pollutants upon solar-light irradiation within 100 and 60 min, respectively. Moreover, the trapping experiments confirmed the Z-scheme approach of the prepared nanocomposites. The efficient separation and transfer of photogenerated electron-hole pairs rendered by the heterostructure were confirmed by utilizing electrochemical impedance spectroscopy, photocurrent experiments, and photoluminescence. Mott–Schottky measurements were used determine the positions of the conduction and valence bands of the samples, and the detailed mechanism of photocatalytic degradation of toxic pollutants was projected and discussed.     

The synergistic interaction of Nickel(II) with dna damaging agents

In this report we present several examples in which nickel(II) in combination with DNA damaging agents caused an enhanced or synergistic biological response using several different endpoints. These examples of Ni(II) toxicity represent several approaches designed to understand the genotoxicity of Ni(II) as well as several other metal ions. They are discussed in this report as a partial basis for our hypothesis that Ni(II) may alter the cellular processing of DNA damage at some common point in the pathway for DNA repair of several different agents. In cultured Chinese hamster cells DNA damage by Ni(II) ions was not readily demonstrated by the method of alkaline elution, but pretreatment of cells with Ni(II) before X‐irradiation produced an enhanced amount of strand breaks compared to the amount produced by X‐rays alone. A synergistic enhancement of cell transformation of Syrian hamster embryo cells was observed for combined treatments of Ni(II) and benzo(a)pyrene. The nickel enhancement of mutagenesis by ultraviolet light was demonstrated for the bacterial gene gpt stably integrated into the Chinese hamster V79 genome.     

The effect of calcium and pH on nickel accumulation in and rhizotoxicity to pea (Pisum sativum L.) root-empirical relationships and modeling

The accumulation and rhizotoxicity of Ni to pea were investigated. Calcium, H, and Ni competed for root-binding sites with high pH and low Ca favoring more Ni accumulation. At low pH, Ca accumulation is the key factor determining root growth, while at medium to high pH, root elongation is more sensitive to Ni concentration. The tissue concentration of Ni and Ca ([Ni]t or [Ca]t, μmol g⁻¹ dry root) can be predicted from total dissolved Ni ([Ni]_T, μM), pH, and total dissolved Ca ([Ca]_T, mM) by two approaches. Approach 1 is the empirical equations [Ni]t = (0.361 pH-0.695[Ca]_T)*[Ni]_T and [Ca]t = 8.29 pH + 10.8 [Ca]_T. The second approach involves a two-step model. The surface-bound Ni and Ca are estimated from a surface adsorption model with binding constants derived from independent ion adsorption experiments. Then transfer functions are used to predict internal root Ni and Ca accumulation.     

Soft and sour: The challenge of setting environmental quality standards for bioavailable metal concentration in Fennoscandinavian freshwaters

The European Union Water Framework Directive (WFD) requires member states to ensure that all inland and coastal waters achieve ‘good’ water quality status. To this end, the WFD has set environmental quality standards (EQS) or Water quality criteria (WQC) for priority pollutants that include the four metals Cd, Ni, Pb and Hg. Many states have also chosen to set EQS for Cu and Zn. The use of bioavailability models to set EQS, paves the way for accepting higher local metal concentrations in waters where metal bioavailability is deemed low. The Biotic Ligand Model (BLM) concept has been proposed as a tool for estimating metal bioavailability and for calculating local EQS in the EU guidance document. The BLM estimates metal bioavailability based on the dissolved metal concentration and key ancillary water chemistry parameters (acidity, hardness and organic carbon content). The BLMs developed so far, have only been validated for water chemistry input parameters typical of Central Europe. However, the pH, alkalinity and dissolved organic carbon levels of a significant fraction of Fennoscandinavian (Finland, Norway and Sweden) freshwaters are outside the calibration range of currently available BLMs. The levels of Ca²⁺, alkalinity and pH in 75%, 29% and 22%, respectively, of the ca. 2500 Fennoscandinavian freshwater bodies investigated in this survey were outside the calibration range of tested BLMs. Moreover, a comparison of the ability of the tested BLMs to predict the acute and chronic copper toxicity to Daphnia magna and Rainbow trout indicated that the BLMs should be used with caution outside their current validation range. We conclude that more work is needed to extend the application of BLMs in the practical risk assessment to encompass a broader range of European freshwater bodies.