Catalytic dechlorination of monochlorobenzene with a new type of nanoscale Ni(B)/Fe(B) bimetallic catalytic reductant

A unique type of nanoscale Ni(B)/Fe(B) bimetallic catalytic reductant was prepared and used for dechlorination of monochlorobenzene (MCB). The sample Ni(B)/Fe(B) was synthesized by an electroless plating method, in which nanoscale Ni(B) was deposited on the surface of nanoscale Fe(B) synthesized by chemical reduction. The results suggest that the nanoscale Ni(B)/Fe(B) bimetallic catalytic reductant has higher dechlorination efficiency than Ni/Fe(B) catalytic reductant prepared by replacing Fe(B) with Ni(2+) in aqueous solution. The Ni content was found to be an important factor in catalytic dechlorination, with the dechlorination rate increasing with Ni content. The electroless plating method improve the efficiency of the Ni(2+) in the solution. Dechlorination takes place with the existence of nanoscale Ni(B)/Fe(B) bimetallic catalytic reductant via a pseudo-first-order reaction.     

Influence of N, P additions on the transfer of nickel from phytoplankton to copepods

We examined the influence of macronutrient (nitrate and phosphate) additions on Ni uptake by phytoplankton (Prorocentrum donghaiense and Skeletonema costatum) and its subsequent transfer to marine copepods (Calanus sinicus and Labidocera euchaeta). Ni uptake by phytoplankton after 24h of exposure was markedly dependent on nutrient conditions, with a higher nutrient quota facilitating Ni accumulation in the algae. Trophic transfer was quantified by measurements of the Ni assimilation efficiency in C. sinicus and L. euchaeta, feeding on the algae under different nutrient treatments. Ni assimilation efficiency generally increased with an increase of nutrient concentration in the algae. A significant positive-correlation was found between the Ni assimilation efficiencies of the copepods and the %intracellular Ni in the algal cells. However, ambient nutritional conditions had little effect on the physiological turnover rate constant of Ni by copepods. Thus, nutrient enrichment may lead to an increase in Ni uptake and transfer in marine plankton.     

Removal of trichloroethylene from water by cellulose acetate supported bimetallic Ni/Fe nanoparticles

In this study, cellulose acetate (CA) supported Ni/Fe nanoparticles were prepared and the ability of these nanoparticles to remove trichloroethylene (TCE) from water was studied. The effects of TCE reduction by the nanoparticles and sorption by the CA support were accounted for separately in the model. CA supported post-coated Ni/Fe nanoparticles were used to investigate the effect of metal particle composition on the observed reduction rate constant. The results show that the metal mass normalized observed reduction rate constant was proportional to the Ni content in the post-coated Ni/Fe nanoparticles in the range of 0-14.3 wt.%. This constant reached a maximum between 14.3 and 21.4 wt.% and decreased with further increase in Ni content. CA supported co-reduced Ni/Fe bimetallic nanoparticles gave poorer performance compared to CA supported post-coated Ni/Fe bimetallic nanoparticles at the same Ni content in Ni/Fe nanoparticles.     

Airborne heavy metal pollution and its effects on foliar elemental composition of Empetrum hermaphroditum and Vaccinium myrtillus in Sør-Varanger, northern Norway

Uptake of Al, Cu, Fe, Mn, Ni, Ca, K, Mg, P, and S in Empetrum nigrum L. ssp. hermaphroditum Hagerup and Vaccinium myrtillus L. from Ni, Cu and SO2 contaminated sites in S?r-Varanger, northern Norway, were investigated. The primary objective was to study the effect of airborne heavy metal pollution on foliar element composition of these two dwarf shrubs. Ni distribution and availability in soils clearly indicate atmospheric deposition of Ni particulates in S?r-Varanger. Foliar Ni concentrations in E. hermaphroditum and V. myrtillus increased in relation to plant available Ni in corresponding soils. Leaves of E. hermaphroditum generally contained higher concentrations of Ni than leaves of V. myrtillus. Emissions influenced some features of leaf elemental composition of the two species in very different ways. In leaves of V. myrtillus, S increased in proportion to Ni and Cu, while levels of Mn decreased. In leaves of E. hermaphroditum, Fe increased in proportion to Ni and Cu, while levels of Ca decreased.     

Food utilization and growth of cutworm Spodoptera litura Fabricius larvae exposed to nickel,and its effect on reproductive potential

Food utilization and growth of the 5th and 6th instar Spodoptera litura Fabricius larvae, and its effect on reproduction potential was evaluated by feeding larvae diets with different doses of Ni for 3 generations. Dose-dependent relationships between Ni levels and food consumption and growth were variable with different larval developmental period and Ni exposure duration. RCR, AD and RGR of the 6th instar larvae were much more affected by Ni exposure than those of 5th instar larvae, and the effects were strongest in the 3rd generation. It was found that RCR was significantly stimulated after 1 and 20 mg kg⁻¹ Ni exposure, while AD was significantly inhibited after 1, 5, 10 and 40 mg kg⁻¹ Ni exposure. However, lower levels of Ni (?5 mg kg⁻¹) significantly increased and higher levels of Ni (?10 mg kg⁻¹) significantly decreased RGR. In 3 successive generations, 10 mg kg⁻¹ Ni significantly increased the ECI and ECD of the 5th instar larvae, and 5 mg kg⁻¹ Ni significantly increased the ECD of the 6th instar larvae. However, ECD were all significantly inhibited with 20 mg kg⁻¹ Ni exposure. Results also revealed that durations of larvae were shortened at low levels of Ni, but extended at high levels of Ni. Fecundity was inhibited by the highest Ni doses in each generation, while improved by low Ni doses in the 3rd generation. Hatching rates in all treatments were significantly decreased in a Ni dose-dependent manner. Study indicated that effects of Ni on these parameters were predominant with the increasing Ni exposure period.     

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.     

Performance of different microalgal species in removing nickel and zinc from industrial wastewater

A series of batch experiments was conducted to compare the ability of 11 microalgal species of the same cell density in removing nickel (Ni) and zinc (Zn) from synthetic wastewater. These included Chlorella vulgaris (commercially available), Chlorella sorokiniana and Scenedesmus quadricauda (isolates from polluted water of Wuhan, China), and eight different isolates from Hong Kong. The Wuhan isolate of Scenedesmus removed most Ni, probably due to its large biomass. Nickel concentration was reduced from an initial 30 to 0.9 mg/l after 5 min (97% Ni removal), and further declined to 0.4 mg/l after 90 min of treatment. In wastewater containing 30 mg/l Ni and 30 mg/l Zn, more than 98%, Ni and Zn were removed simultaneously at the end of 5 min treatment, indicating that the presence of Zn in wastewater did not affect Ni removal by this Scenedesmus isolate. The second most effective species for Ni removal was an isolate, tentatively identified as Chlorella miniata, Ni concentration was reduced to 10 mg/l after 90 min, and was only slightly interfered by the presence of Zn. In terms of metal removal per unit biomass or unit surface area of algal cells, C. miniata was the best species in removing Ni and Zn. At the other extreme, one Hong Kong isolate (Synechocystis sp.) did not remove any Ni and only achieved 40% Zn removal. Performance of the other isolates was comparable with the commercial C. vulgaris, less than 50% Ni was removed after 5 h of treatment and Ni removal was significantly reduced by the presence of Zn. All algae tested were found to be viable, showing these 11 species could tolerate a mixture of 30 mg/l Ni and 30 mg/l Zn in wastewater.     

Accumulation and fraction distribution of Ni(II) in activated sludge treating Ni-laden wastewater

The accumulation and fraction distribution of Ni(II) in sludge was determined, and their effect on the performance of sequencing batch reactor (SBR) systems was evaluated at laboratory scale. The results showed that the removal efficiencies of substrates decreased significantly with increasing feeding concentration of Ni(II) into SBRs. The concentration of Ni(II) fed into the SBRs was significantly positively correlated with the Ni(II) contents accumulated in the sludge, while it was negatively correlated with the biomass in the SBRs. The accumulated Ni(II) in the sludge was distributed mainly in the available fraction, accounting for 75.8–90.0 % of the total Ni(II) content. The accumulated content of Ni(II) in each sludge fraction could be predicted satisfactorily by the feeding Ni(II) concentrations in the solutions. As compared with the total contents and other chemical fractions, Ni(II) in the oxidizable fraction in sludge exhibited more important inhibition effects on sludge microorganisms in the SBRs.     

The influence of organic amendment and nickel pollution on tomato fruit yield and quality

The effects of organic fertilization (sludge application) and/or different levels of Ni pollution on tomato fruit yield, quality, nutrition, and Ni accumulation were investigated. The mass loading of sewage sludge solids used in this study for the amendment of a calcareous soil with low organic matter content was 2% (w/w). A control with no sewage sludge amendment was also included (S). Nickel was added to the sludge amended soil at 0, 60, 120 and 240 mg kg-1 concentrations. Sewage sludge addition to the calcareous soil significantly increased fruit yield but did not adversely affect the quality and nutritional status of the tomato fruit. The results demonstrated that sewage sludge could be successfully used as a horticultural fertilizer. Only the highest addition rate of Ni (240 mg kg-1) to an organic amended calcareous soil had negative effects on fruit yield and quality, and caused a Ni accumulation in fruit that could be considered as a hazard for human health. Thus, no toxic problems will be encountered in tomato fruit due to Ni pollution provided the total Ni (soil Ni plus Ni incorporated with sludge amendment) concentration is kept below the maximum concentration of Ni allowed for agricultural alkaline soils in Spain (112 mg Ni kg-1).     

Nickel tissue residue as a biomarker of sub-toxic exposure and susceptibility in amphibian embryos

Although low level exposure to physicochemical agents is the most common environmental scenario, their effects on living organisms are very controversial. However, there is an increasing need to integrate low level exposures from risk assessment to remediation purposes. This study focus on the possibility to employ Ni tissue residue values as biomarkers of sub-toxic exposure and susceptibility to this metal in a range of almost pristine to sub-toxic concentrations for Rhinella arenarum embryos. For that purpose, three batches of amphibian embryos were pretreated during 10 days with three increasing concentrations of Ni starting in 2, 8 and 20 microg Ni(2+) L(-1) and ending in 16, 64 and 160 microg Ni(2+) L(-1) (in natural fresh waters this value ranges from 2 to 10 microgL(-1); the LC(50)-24h for R. arenarum is 26.2mg Ni(2+) L(-1)). For the experimental conditions, the Ni tissue residue values at 360 h post exposure were 0.5, 2.1 and 3.6 microg Ni g(-1) embryo w/w, respectively, corresponding to BCFs of 31, 33 and 23. The susceptibility to Ni in those experimental embryos was evaluated by means of challenge exposures to three lethal concentrations of this metal (10, 20 and 30 mg Ni(2+) L(-1)), registering survival during the following 10 days of treatment. As a general pattern, the lower, intermediate and higher pretreatments with Ni resulted in enhanced, neutral and adverse effects on embryonic survival, respectively. Thus, sub-toxic exposure to Ni could modify the resistance of the amphibian embryo to this metal and Ni tissue residue values could be considered as biomarkers of both, exposure and susceptibility.     

Colloidal diatomite, radionickel, and humic substance interaction: a combined batch, XPS, and EXAFS investigation

This work determined the influence of humic acid (HA) and fulvic acid (FA) on the interaction mechanism and microstructure of Ni(II) onto diatomite by using batch experiments, X-ray photoelectron spectroscopy (XPS), and extended X-ray absorption fine structure (EXAFS) methods. Macroscopic and spectroscopic experiments have been combined to see the evolution of the interaction mechanism and microstructure of Ni(II) in the presence of HA/FA as compared with that in the absence of HA/FA. The results indicated that the interaction of Ni(II) with diatomite presents the expected solution pH edge at 7.0, which is modified by addition of HA/FA. In the presence of HA/FA, the interaction of Ni(II) with diatomite increased below solution pH 7.0, while Ni(II) interaction decreased above solution pH 7.0. XPS analysis suggested that the enrichment of Ni(II) onto diatomite may be due to the formation of (≡SO)₂Ni. EXAFS results showed that binary surface complexes and ternary surface complexes of Ni(II) can be simultaneously formed in the presence of HA/FA, whereas only binary surface complexes of Ni(II) are formed in the absence of HA/FA, which contribute to the enhanced Ni(II) uptake at low pH values. The results observed in this work are important for the evaluation of Ni(II) and related radionuclide physicochemical behavior in the natural soil and water environment.     

Phytotoxicity of nickel in a range of European soils: influence of soil properties, Ni solubility and speciation

We investigated the influence of soil properties on Ni toxicity to barley root and tomato shoot growth, using 16 European soils. The effective concentration of added Ni causing 50% inhibition (EC(50)) ranged from 52 to 1929mgkg(-1) and from 17 to 920mgkg(-1) for the barley and tomato test, respectively, representing 37- and 54-fold variation among soils. Soil cation exchange capacity was the best single predictor for the EC(50). The EC(50) based on either the Ni concentration or free Ni(2+) activity in soil solution varied less among soils (7-14 fold) than that based on the total added Ni, suggesting that solubility of Ni is a key factor influencing its toxicity to plants. The EC(50) for free Ni(2+) activity from the barley test decreased with increasing pH, indicating a protective effect of protons. The results can be used in the risk assessment of Ni in the terrestrial environment.     

Investigations of chemical fraction of Co and Ni in industrial fly ash and mobility of metals in environmental conditions

The quantitative evaluation of chemical fraction of Co and Ni in the industrial fly ash by methods of five step sequential extraction was carried out in order to characterize metal mobility in environmental conditions. The research involved (i) water-soluble (pH=7), (ii) acid-soluble (pH=5), (iii) oxide, (iv) sulfide and (v) residue metal fractions. It was discovered, that the total extraction of the studied metals from fly ash to solutions take place in the following quantities Co - 35.5 and Ni - 153.0mgkg(-1). The investigations of chemical fractions proved that the subject metals occur mainly in fly ash as: oxide (Co - 7.0, Ni - 28.5mgkg(-1)) and residue (Co - 11.5, Ni - 42.5mgkg(-1)) as well as sulfide (Co - 8.5, Ni - 46.5mgkg(-1)). Low concentrations of metals for water-soluble fraction (Co - 0.7, Ni - 1.2mgkg(-1)) and acid-soluble fraction (Co - 4.5, Ni - 23.5mgkg(-1)) were observed. The fractions of Co and Ni leachable from the ash in environmental conditions contain: 24.0% (Co) and 23.3% (Ni) of metal total amount in the industrial fly ash. The obtained mobility parameter of Co and Ni can be applied to estimate the concentration increase of mobile and hardly mobile forms of these metals in soil polluted with the ash.     

Quantification of bioavailable nickel in sediments and toxic thresholds to Hyalella azteca

Bioaccumulation and chronic toxicity of nickel (Ni) to Hyalella azteca in Ni-spiked sediments was strongly affected by the source of sediment used. The total range in LC50s on a sediment concentration basis ranged over 20 fold. Differences in Ni toxicity generally matched differences in Ni bioaccumulation, and toxicity expressed on a body concentration basis varied less than three fold. Body concentrations, therefore, provide a much more reliable prediction of Ni toxicity in sediments than do concentrations in the sediment. Ni in overlying water was also a reliable predictor of Ni toxicity, but only in tests conducted in Imhoff settling cones with large (67:1) water to sediment ratios. Overlying water LC50s for tests in beakers varied 18 fold. Sediment and body concentrations of Ni tolerated by Hyalella were slightly higher in cones than in beakers. Reproduction was not affected significantly by Ni at concentrations below the LC50 and 10-week EC50s for survival and biomass production (including survival, growth and reproduction) were only marginally lower than 4-week EC50s (survival and growth only).     

The tolerance of Empetrum nigrum to copper and nickel

The Cu and Ni tolerance of 3- to 5-year-old cuttings of crowberry (Empetrum nigrum) were tested in controlled conditions. Six levels of Cu (0.1-100 mg l(-1)), five levels of Ni (0-100 mg l(-1)) and nine levels of Cu+Ni were applied. The elongation of the shoots, new shoot and root dry weights indicated an adverse effect of increasing Cu and Ni concentrations. At low Cu levels the addition of Ni decreased the dry weights more than at high Cu levels. The results show that E. nigrum accumulated high concentrations of Cu and Ni mainly in old stem tissue, which contained a maximum of over 3000 mg kg(-1) Cu and 1000 mg kg(-1) Ni. The concentrations of Cu and Ni in E. nigrum were higher than those measured in plants growing in areas near to Cu-Ni smelters, but the accumulation pattern was similar. The survival of the cuttings was not affected suggesting that E. nigrum possesses an internal heavy metal tolerance.     

CS-Fe和CS-Fe/Ni的制备及其用于去除钴离子

以氯化铁为铁源,硼氢化钠为还原剂,壳聚糖为稳定剂,采用液相还原法制备壳聚糖稳定纳米铁（CS-Fe）;并以氯化铁为铁源,硫酸镍为镍源,硼氢化钠为还原剂,壳聚糖为稳定剂,采用液相还原共沉淀法制备壳聚糖稳定纳米铁镍（CS-Fe/Ni）。通过SEM、EDS、XRD、FT-IR等表征手段,对所制备的CS-Fe和CS-Fe/Ni的形貌及微观结构进行表征,并以Co²⁺为目标去除物评价CS-Fe和CS-Fe/Ni的反应活性。初步研究表明,制成的CS-Fe含有单质纳米铁,颗粒多数以30~90 nm球形颗粒为主;而CS-Fe/Ni材料中含有纳米铁镍,颗粒多数以30~60 nm球形颗粒为主;在相同的实验条件下,反应60 min,CS-Fe/Ni对Co²⁺的去除率高达100%,但是CS-Fe仅为88%,即CS-Fe/Ni对Co²⁺的去除率比CS-Fe高。     

Nickel bioaccumulation in bivalves from the New Caledonia lagoon: seawater and food exposure

The New Caledonian lagoon is submitted to intense heavy metal input from land-based Ni mining. Therefore, the use of sentinel species is strongly recommended in order to develop and implement coastal zone management programmes of the metal contamination. The tropical oysters Isognomon isognomon and Malleus regula and the clam Gafrarium tumidum were previously proposed as such possible sentinel organisms and were thus investigated in this context. The three species were exposed to Ni via seawater or food using radiotracer techniques. Results indicate that uptake and retention efficiencies of Ni are independent of the dissolved Ni concentrations in the surrounding seawater. Hence, for the three species, body concentrations of Ni taken up from the dissolved phase are directly proportional to the ambient dissolved concentrations. Biokinetic patterns indicated that the major part of Ni was rapidly lost from bivalves during the first days of depuration, whereas 7 to 47% of 63Ni were retained in tissues with a biological half-life not significantly different from infinity. Finally, feeding experiments showed that Ni ingested with food (phytoplankton) was assimilated more efficiently in clams (assimilation efficiency, AE = 61%) than in oysters (AE = 17%), and was strongly retained (T(b1/2) > or = 35 d) in the tissues of both bivalves. It is concluded that the investigated species examined are efficient bioaccumulators of Ni from both the surrounding seawater and the food, and that they would be useful bioindicators for monitoring the status of Ni contamination in tropical coastal waters.     

Assessment of the effects of nickel on benthic macroinvertebrates in the field

A field-based evaluation of the biological effects of potential nickel (Ni) exposures was conducted using monitoring data for benthic macroinvertebrates and water chemistry parameters for streams in England and Wales. Observed benthic community metrics were compared to expected community metrics under reference conditions using RIVPACS III+?software. In order to evaluate relationships between Ni concentrations and benthic community metrics, bioavailable Ni concentrations were also calculated for each site. A limiting effect from Ni on the 90th percentile of the maximum achievable ecological quality was derived at “bioavailable Ni” exposures of 10.3 μg l^?1. As snails have been identified as particularly sensitive to nickel exposure, snail abundance in the field in response to nickel exposure, relative to reference conditions, was also analysed. A “low effects” threshold for snail abundance based on an average of spring and autumn data was derived as 3.9 μg l^?1 bioavailable Ni. There was no apparent effect of Ni exposure on the abundance of Ephemeroptera (mayflies), Plecoptera (stoneflies) or Tricoptera (caddisflies) when expressed relative to a reference condition within the range of “bioavailable Ni” exposures observed within the dataset. Nickel exposure concentrations co-vary with the concentrations of other stressors in the dataset, and high concentrations of Ni are also associated with elevated concentrations of other contaminants.     

Bioaccumulation of nickel and vanadium by clams (Meretrix meretrix) living in different salinities along the Saudi coast of the Arabian Gulf

The objective of this study was to investigate bioaccumulation of nickel (Ni) and vanadium (V) in clams living in different salinity regimes along the Saudi coast of the Arabian Gulf. Several hundred clam (Meretrix meretrix), sediment, and seawater samples were collected from 12 locations. Concentrations of Ni and V were determined in these samples using an inductively coupled argon plasma analyzer. Concentrations of Ni and V in the clams varied between 0.35 and 2.61 mg kg(-1) and between 0.13 and 0.35 mg kg(-1) wet tissue, respectively. Analysis of variance of the data revealed significant (P<0.01) inter- and intra-station variations in Ni concentrations in clams. In contrast, the mean concentration of V in clams from all the stations were statistically similar. Correlation between the biometric characteristics of clams and Ni and V concentrations were not statistically significant. Significant (P<0.05) geographical variations in Ni and V concentrations in the sediment samples were found, with relatively higher concentrations in the northern part of the Gulf where there are many oil fields. Ni and V in the sediments were significantly (P<0.05) correlated, suggesting a common contamination source for these elements. Interactions between Ni and V in clams and sediment were poor.     

Biosorption of nickel(II) from aqueous solution by Aspergillus niger: Response surface methodology and isotherm study

In the present study, the effects of biosorbent Aspergillus niger dosage, initial solution pH and initial Ni(II) concentration on the uptake of Ni(II) by NaOH pretreated biomass of A. niger from aqueous solution were investigated. Batch experiments were carried out in order to model and optimize the biosorption process. The influence of three parameters on the uptake of Ni(II) was described using a response surface methodology (RSM) as well as Langmuir and Freundlich isotherm models. Optimum Ni(II) uptake of 4.82 mg Ni(II) g⁻¹ biomass (70.30%) was achieved at pH 6.25, biomass dosage of 2.98 g L⁻¹ and initial Ni(II) concentration of 30.00 mg L⁻¹ Ni(II). Langmuir and Freundlich were able to describe the biosorption isotherm fairly well. However, prediction of Ni(II) biosorption using Langmuir and Freundlich isotherms was relatively poor in comparison with RSM approaches. The biosorption mechanism was also investigated by using Fourier transfer infrared (FT-IR) analysis of untreated, NaOH pretreated, and Ni(II) loaded A. niger biomass.