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.     

废旧镍镉电池的生物沥滤处理——沥滤停留时间的影响研究

用污泥加硫酸化液沥滤镍镉电池中的重金属是一种全新的工艺,该工艺主要由生物酸化反应器和金属沥滤反应器两个反应器组成.生物酸化反应器中产生的酸液就是沥滤电池中重金属的反应液.研究表明,酸化液在沥滤反应池的停留时间对沥滤的效果有显著影响.在1、4、7、12 d 4个停留时间中,4 d的效果是最好的,对金属Cd和Ni都用40 d左右基本实现了全部滤除;1d略微慢一些,Cd用了40 d,Ni用了45 d;7 d和12 d的沥滤时间都长于50 d.4 d产生的金属废液量是1 d的1/4,考虑到后续处理金属沥滤废液的工作量,选择4d的停留时间要优于1d.     

Effect of iron ion configurations on Ni2+ removal in electrocoagulation

Electrocoagulation (EC) has been widely used to treat the heavy metal wastewater in industry. A novel process of sinusoidal alternating current electrocoagulation (SACC) is adopted to remove Ni²⁺ in wastewater in this study. The morphology of precipitates and the distribution of the main functional iron configurations were investigated. Ferron timed complex spectroscopy can identify the monomeric iron configurations [Fe(a)], oligomeric iron configurations [Fe(b)] and polymeric iron configurations [Fe(c)]. The optimal operating conditions of SACC process were determined through single-factor experiments. The maximum Ni²⁺ removal efficiency [Re(Ni²⁺)] was achieved under the conditions of pH₀=7, current density (j) = 7 A/m², electrolysis time (t) = 25 min, c₀(Ni²⁺) = 100 mg/L. At pH=7, the proportion of Fe(b) and Fe(c) in the system was 50.4 at.% and 23.1 at.%, respectively. In the SACC process, Fe(b) and Fe(c) are the main iron configurations in solution, while Fe(c) are the vast majority of the iron configurations in the direct current electrocoagulation (DCC) process. Re(Ni²⁺) is 99.56% for SACC and 98.75% for DCC under the same optimum conditions, respectively. The precipitates produced by SACC have a high proportion of Fe(b) configurations with spherical α-FeOOH and γ-FeOOH structures which contain abundant hydroxyl groups. Moreover, it is demonstrated that Fe(b) has better adsorption capacity than Fe(c) through adsorption experiments of methyl orange (MO) dye. Fe(a) configurations in the homogeneous solution had no effect on the removal of nickel.     

Nickel recovery from electronic waste II Electrodeposition of Ni and Ni–Fe alloys from diluted sulfate solutions

This study focuses on the electrodeposition of Ni and Ni–Fe alloys from synthetic solutions similar to those obtained by the dissolution of electron gun (an electrical component of cathode ray tubes) waste. The influence of various parameters (pH, electrolyte composition, Ni²⁺/Fe²⁺ ratio, current density) on the electrodeposition process was investigated. Scanning electron microscopy (SEM) and X-ray fluorescence analysis (XRFA) were used to provide information about the obtained deposits’ thickness, morphology, and elemental composition. By controlling the experimental parameters, the composition of the Ni–Fe alloys can be tailored towards specific applications. Complementarily, the differences in the nucleation mechanisms for Ni, Fe and Ni–Fe deposition from sulfate solutions have been evaluated and discussed using cyclic voltammetry and potential step chronoamperometry. The obtained results suggest a progressive nucleation mechanism for Ni, while for Fe and Ni–Fe, the obtained data points are best fitted to an instantaneous nucleation model.     

石墨炉原子吸收法测定水中微量镍的研究

研究了石墨炉原子吸收光谱法测定生活饮用水中微量镍的方法,对基体改进剂和最佳加热程序进行了探讨。结果表明,本方法不需添加基体改进剂,灰化温度为1 200℃、原子化温度2 300℃,加标回收率为93.7%~1 03.0%,RSD<5.2%,该方法的检测下限为5.0μg/L。方法简便、准确,适用于生活饮用水中镍的测定。     

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.     

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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Bioavailability of trace metals in brownfield soils in an urban area in the UK

Thirty-two brownfield sites from the city of Wolverhampton were selected from those with a former industrial use, wasteland or areas adjacent to industrial processes. Samples (<2 mm powdered soil fraction) were analysed, using inductively coupled plasma–atomic emission spectrometry (ICP–AES) for 20 elements. Loss on ignition and pH were also determined. A five-step chemical sequential extraction technique was carried out. Single leach extraction with 0.12 M hydrochloric acid of Pb, Cu and Zn in soil was determined as a first approximation of the bioavailability in the human stomach. Some of the sites were found to have high concentrations of the potentially toxic elements Pb, Zn, Cu and Ni. The partitioning of metals showed a high variability, however a number of trends were determined. The majority of Zn was partitioned into the least chemically stable phases (steps 1, 2 and 3). The majority of Cu was associated with the organic phase (step 4) and the majority of Ni was fractionated into the residue phase (step 5). The majority of Pb was associated with the residue fraction (step 5) followed by Fe–Mn oxide fraction (step 3). The variability reflects the heterogeneous and complex nature of metal speciation in urban soils with varied historic histories. There was a strong inverse linear relationship between the metals Ni, Zn and Pb in the readily exchangeable phase (step 1) and soil pH, significant at P < 0.01 level. There was a significant increase (P < 0.05) in the partitioning of Cu, Ni and Zn into step 4 (the organic phase) in soils with a higher organic carbon content (estimated by loss on ignition). Copper was highly partitioned into step 4 as it has a strong association with organics in soil but this phase was not important for the partitioning of Ni or Zn. The fractionation of Ni, Cu and Zn increased significantly in step 3 when the total metal concentration increases (P < 0.01). The Fe–Mn oxide fraction becomes more important in soils elevated in these metals, possibly due to the scavenging of metals by oxides. Cu and Pb extracted by HCl was statistically similar to the sum of the metals in steps 1 to 4 (P < 0.01) and HCl available Zn was statistically similar to the sum of Zn in steps 1 to 3 (P < 0.01). Step 4 (the organic phase) was not an important phase for Zn, so it was concluded that any Cu, Zn and Pb present in soil in a nonresidue phase would be potentially available for uptake into the human system once soil has been ingested.     

Embryo toxicity of pesticides and heavy metals to the ramshorn snail, Marisa cornuarietis (Prosobranchia)

An invertebrate embryo toxicity test with the ampullariid snail, Marisa cornuarietis, to assess the toxicity of pesticides and heavy metals recently was established. Snail embryos were treated with atrazine (100, 1000, 10 000, and 30 000 μg/L), imidacloprid (10 000, 25 000, and 50 000 μg/L), Ni²⁺ (0.1, 1, 10, and 100 μg/L) or Zn²⁺ (100, 200, 500, 1000, 2000, and 5000 μg/L). The effect of these substances was examined by monitoring the following endpoints: mortality, formation of tentacles and eyes, heart rate, hatching, and weight after hatching. Effects in term of a significant delay on the formation of both tentacles and eyes were found after treatment with 100 μg/L Ni²⁺ or 200 μg/L Zn²⁺. The heart rate was shown to significantly decrease at 25 000 μg/L imidacloprid or 1000 μg/L Zn²⁺. At 100 μg/L atrazine, 10 μg/L Ni²⁺, or 1000 μg/L Zn²⁺ a significant delay in hatching became visible. No significant mortality was observed for the tested concentrations of atrazine, imidacloprid, or Ni²⁺, while 5000 μg/L Zn²⁺ resulted in 100% mortality after 10 d. The weight of freshly hatched individuals remained unaffected in all treatments. On the basis of the lowest observed effect concentrations (LOECs) recorded, we could show the M. cornuarietis embryo toxicity test (MariETT) to react up to three orders of magnitude more sensitive (for metals) and at least one order of magnitude more sensitive (for the tested organics) than the established Danio rerio embryo test.