Microbial community dynamics in uranium contaminated subsurface sediments under biostimulated conditions with high nitrate and nickel pressure

BACKGROUND, AIM, AND SCOPE: The subsurface at the Oak Ridge Field Research Center represents an extreme and diverse geochemical environment that places different stresses on the endogenous microbial communities, including low pH, elevated nitrate concentrations, and the occurrence of heavy metals and radionuclides, including hexavalent uranium [U(VI)]. The in situ immobilization of U(VI) in the aquifer can be achieved through microbial reduction to relatively insoluble U(IV). However, a high redox potential due to the presence of nitrate and the toxicity of heavy metals will impede this process. Our aim is to test biostimulation of the endogenous microbial communities to improve nitrate reduction and subsequent U(VI) reduction under conditions of elevated heavy metals. MATERIALS AND METHODS: Column experiments were used to test the possibility of using biostimulation via the addition of ethanol as a carbon source to improve nitrate reduction in the presence of elevated aqueous nickel. We subsequently analyzed the composition of the microbial communities that became established and their potential for U(VI) reduction and its in situ immobilization. RESULTS: Phylogenetic analysis revealed that the microbial population changed from heavy metal sensitive members of the actinobacteria, alpha- and gamma-proteobacteria to a community dominated by heavy metal resistant (nickel, cadmium, zinc, and cobalt resistant), nitrate reducing beta- and gamma-proteobacteria, and sulfate reducing Clostridiaceae. Coincidentally, synchrotron X-ray absorption spectroscopy analyses indicated that the resulting redox conditions favored U(VI) reduction transformation to insoluble U(IV) species associated with soil minerals and biomass. DISCUSSION: This study shows that the necessary genetic information to adapt to the implemented nickel stress resides in the endogenous microbial population present at the Oak Ridge FRC site, which changed from a community generally found under oligotrophic conditions to a community able to withstand the stress imposed by heavy metals, while efficiently reducing nitrate as electron donor. Once nitrate was reduced efficient reduction and in situ immobilization of uranium was observed. CONCLUSIONS: This study provides evidence that stimulating the metabolism of the endogenous bacterial population at the Oak Ridge FRC site by adding ethanol, a suitable carbon source, results in efficient nitrate reduction under conditions of elevated nickel, and a decrease of the redox potential such that sulfate and iron reducing bacteria are able to thrive and create conditions favorable for the reduction and in situ immobilization of uranium. Since we have found that the remediation potential resides within the endogenous microbial community, we believe it will be feasible to conduct field tests. RECOMMENDATIONS AND PERSPECTIVES: Biostimulation of endogenous bacteria provides an efficient tool for the successful in situ remediation of mixed-waste sites, particularly those co-contaminated with heavy metals, nitrate and radionuclides, as found in the United States and other countries as environmental legacies of the nuclear age.     

A study of the extraction of vanadium and nickel in oil-fired fly ash

Annual production of oil-fired fly ash in Taiwan is approximately 43 000 tons, of this approximately 13 000 tons is electrostatically precipitated, the rest is cyclonically collected. Structurewise, both consist of porous unburned carbon, vanadium and nickel oxide, and water-soluble sulfate. Electrostatically precipitated fly ash contains large amounts of ammonium sulfate. If these ashes are not properly disposed of, they become environmental problems, such as dusting, leakage of acid liquids, and pollution with heavy metals. This paper discusses the experimental extraction of vanadium and nickel from oil-fired fly ash. The results indicated that leaching of oil-fired fly ash in 0.5 N of sulfuric acid led to an extraction of 65% vanadium, 60% nickel, and 42% iron, along with an increase in the concentration of sulfuric acid. When leached in 2 N sodium hydroxide solution, the extraction of vanadium was 80%, and the extraction of nickel was negligible. If leached in an ammonia water, the extraction of nickel increased, along with an increase in the concentration of ammonia in water. When leached with 4 N ammonia water, the extraction of nickel was 60%, the extraction of vanadium was less than that obtainable from leaching in sulfuric acid solution or in sodium hydroxide solution. If electrostatically precipitated fly ash was leached in a solution of 0.25 N ammonia water and 2 N ammonium sulfate, it would yield an extraction of 60% nickel and 8% vanadium—leading to a selective extraction of nickel. This study has established an extraction flowsheet in which fly ash was first leached in an ammoniacal solution containing ammonium sulfate to recover nickel. The leached residues were then leached in an alkaline solution to recover vanadium.     

Catalytic ozonation treatment of papermaking wastewater by Ag-doped NiFe2O4: Performance and mechanism

The catalytic ozonation treatment of secondary biochemical effluent for papermaking wastewater by Ag-doped nickel ferrite was investigated. Ag-doped catalysts prepared by sol-gel method were characterized, illustrating that Ag entirely entered the crystalline of NiFe₂O₄ and changed the surface properties. The addition of catalyst enhanced the removal efficiency of chemical oxygen demand and total organic carbon. The results of gas chromatography-mass spectrometer, ultraviolet light absorbance at 254 nm and three-dimensional fluorescence excitation-emission matrix suggested that aromatic compounds were efficiently degraded and toxic substances, such as dibutyl phthalate. In addition, the radical scavenging experiments confirmed the hydroxyl radicals acted as the main reactive oxygen species and the surface properties of catalysts played an important role in the reaction. Overall, this work validated potential applications of Ag-doped NiFe₂O₄ catalyzed ozonation process of biologically recalcitrant wastewater.     

镍对蔬菜毒害临界值的研究

采用水培＋土培的方法研究了镍对蔬菜的毒害临界值。先采用水培法从18种福建常见蔬菜中筛选出对镍毒害的高敏感蔬菜,再通过土培试验确定土壤镍对高敏感蔬菜的毒害临界值。结果表明,在水培条件下镍对蔬菜生长存在低浓度的刺激效应和高浓度的抑制效应。综合表观症状和蔬菜地上部生物量降低20％的效应浓度值（EC20）确定清江白（Brassica chinensis L．）和蕹菜（Lpomoea aquatica Forsk．）为镍毒害的高敏感蔬菜。以蕹菜为指示作物的土培试验表明,随着镍添加量的增加,蕹菜地上部生物量显著下降。以土培条件下蕹菜地上部生物量降低10％为依据,确定土壤有效镍毒害临界值为2．21mg·kg^-1（DTPA提取）;根据野外采集的菜园土壤DTPA提取镍和全镍的回归关系,求得土壤全镍毒害临界值为43．67mg·kg^-1。     

铜、镍、铅、锌4种重金属对水田土壤藻类的综合效应

为确定污水、污泥的农田施用标准,使用正交试验表L₉（3⁴）研究了4种重金属铜、镍、铅和锌在低、中、高3种浓度下对土壤藻类的数量和种类的影响。混合重金属使土壤藻类的种群结构发生改变,使蓝藻数量减少,硅藻数量或减少或增加,视条件而定,裸藻成为优势种。在土壤－藻类体系中重金属临界值铜为50mg/kg,镍为50mg/kg,铅为150mg/kg,锌为300mg/kg。     

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.     

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.     

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.     

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。     

电催化还原技术处理丙烯酸盐废水的研究

采用电催化还原技术处理高浓度丙烯酸盐废水,考察了离子交换隔膜、阴极材料等对丙烯酸盐转化的影响.结果表明,电催化还原技术可将废水中的丙烯酸盐高效还原为丙酸盐;反应器中加入阳离子交换隔膜有利于提高催化还原的电流效率;阴极极板材料对丙烯酸盐还原有很大影响.其中钯/泡沫镍电极（Pd/Nickel foam）的平均电流效率最高,...