Cu(II), Fe(III) and Mn(II) combinations as environmental stress factors have distinguishing effects on Enterococcus hirae

Pollution by various heavy metals as environmental stress factors might affect bacteria. It was established that iron (Fe(III)), manganese (Mn(II)) and copper (Cu(II)) ion combinations caused effects on Enterococcus hirae that differed from the sum of the effects when the metals were added separately. It was shown that the Cu²⁺-Fe³⁺ combination decreased the growth and ATPase activity of membrane vesicles of wild-type E. hirae ATCC9790 and atpD mutant (with defective F_oF₁-ATPase) MS116. Addition of Mn²⁺-Fe³⁺ combinations within the same concentration range had no effects on growth compared to control (without heavy metals). ATPase activity was increased in the presence of Mn²⁺-Fe³⁺, while together with 0.2 mmol/L N,N'-dicyclohexylcarbodiimide (DCCD), ATPase activity was decreased compared to control (when only 0.2 mmol/L DCCD was present). These results indicate that heavy metals ion combinations probably affect the FOF1-ATPase, leading to conformational changes. Moreover the action may be direct or be mediated by environment redox potential. The effects observed when Fe³⁺ was added separately disappeared in both cases, which might be a result of competing processes between Fe³⁺ and other heavy metals. These findings are novel and improve the understanding of heavy metals ions effects on bacteria, and could be applied for regulation of stress response patterns in the environment.     

Heavy metal availability and impact on activity of soil microorganisms along a Cu/Zn contamination gradient

All the regulations that define a maximum concentration of metals in the receiving soil are based on total soil metal concentration. However, the potential toxicity of a heavy metal in the soil depends on its speciation and availability. We studied the effects of heavy metal speciation and availability on soil microorganism activities along a Cu/Zn contamination gradient. Microbial biomass and enzyme activity of soil contaminated with both Cu and Zn were investigated. The results showed that microbial biomass was negatively affected by the elevated metal levels. The microbial biomass-C （Cmic）/organic C （Corg） ratio was closely correlated to heavy metal stress. There were negative correlations between soil microbial biomass, phosphatase activity and NH4NO3 extractable heavy metals. The soil microorganism activity could be predicted using empirical models with the availability of Cu and Zn. We observed that 72% of the variation in phosphatase activity could be explained by the NH4NO3-extractable and total heavy metal concentration. By considering different monitoring approaches and different viewpoints, this set of methods applied in this study seemed sensitive to site differences and contributed to a better understanding of the effects of heavy metals on the size and activity of microorganisms in soils. The data presented demonstrate the relationship between heavy metals availability and heavy metal toxicity to soil microorganism along a contamination gradient.     

Removal of heavy metals and arsenic from a co-contaminated soil by sieving combined with washing process

Batch experiments were conducted with a heavy metals and arsenic co-contaminated soil from an abandoned mine to evaluate the feasibility of a remediation technology that combines sieving with soil washing.Leaching of the arsenic and heavy metals from the different particle size fractions was found to decrease in the order: 0.1,2–0.1,and 2 mm.With increased contact time,the concentration of heavy metals in the leachate was significantly decreased for small particles,probably because of adsorption by the clay soil component.For the different particle sizes,the removal efficiencies for Pb and Cd were75%–87%,and 61%–77% for Zn and Cu,although the extent of removal was decreased for As and Cr at 45%.The highest efficiency by washing for Pb,Cd,Zn,and As was from the soil particles 2 mm,although good metal removal efficiencies were also achieved in the small particle size fractions.Through SEM-EDS observations and correlation analysis,the leaching regularity of the heavy metals and arsenic was found to be closely related to Fe,Mn,and Ca contents of the soil fractions.The remediation of heavy metal-contaminated soil by sieving combined with soil washing was proven to be efficient,and practical remediation parameters were also recommended.     

The effect of interaction between Bacillus subtilis DBM and soil minerals on Cu(Ⅱ) and Pb(Ⅱ) adsorption

The effects of interaction between Bacillus subtilis DBM and soil minerals on Cu(Ⅱ)and Pb(Ⅱ)adsorption were investigated.After combination with DBM,the Cu(Ⅱ)and Pb(Ⅱ)adsorption capacities of kaolinite and goethite improved compared with the application of the minerals independently.The modeling results of potentiometric titration data proved that the site concentrations of kaolinite and goethite increased by 80%and 30%,respectively after combination with DBM.However,the involvement of functional groups in the DBM/mineral combinations resulted in lower concentrations of observed sites than the theoretical values and led to the enhancement of desorption rates by NH_4NO_3 and EDTA-Na_2.The DBM-mineral complexes might also help to prevent heavy metals from entering DBM cells to improve the survivability of DBM in heavy metal-contaminated environments.During the combination process,the extracellular proteins of DBM provided more binding sites for the minerals to absorb Cu(Ⅱ)and Pb(Ⅱ).In particular,an especially stable complexation site was formed between goethite and phosphodiester bonds from EPS to enhance the Pb(Ⅱ)adsorption capacity.So,we can conclude that the DBM–mineral complexes could improve the Cu(Ⅱ)and Pb(Ⅱ)adsorption capacities of minerals and protect DBM in heavy metal-contaminated environments.     

Speciation and fractionation of heavy metals in soil experimentally contaminated with Pb,Cd, Cu and Zn together and effects on soil negative surface charge

Speciation and fractionation of heavy metals in soil subsamples experimentally loaded with Pb, Cd, Cu and Zn in orthogonal design was investigated by sequential extraction, and operationally defined as water-soluble and exchangeable(SE), weakly specific adsorbed( WSA),Fe and Mn oxides-bound(OX) and organic-bound( ORG). The results showed that fractions of heavy metals in the soil subsamples depended on their speciation. About 90% of Cd and 75% of Zn existed in soil subsamples in the SE fraction. Lead and Cu existed in soil subsamples as SE, WSA and OX fractions simultaneously, although SE was still the major fraction. Organic-bound heavy metals were not clearly apparent in all the soil subsamples. The concentration of some heavy metal fractions in soil subsamples showed the good correlation with ionic impulsion of soil, especially for the SE fraction. Continuous saturation of soil subsamples with 0.20 mol/L NH4CI, which is the first step for determination of the negative surface charge of soil by the ion retention method, resulted in desorption of certain heavy metals from the soil. It was found that the percentage desorption of heavy metals from soil subsamples depended greatly on pH, the composition and original heavy metal content of the soil subsamples. However, most of the heavy metals in the soil subsamples were still be retained after multiple saturation. Compared with the parent soil, the negative surface charge of soil subsamples loaded with heavy metals did not show difference significantly from that of the parent one by statistical analysis. Heavy metals existed in the soil subsamples mainly as exchangeable and precipitated simultaneously.     

Effect of heavy metals and phenol on bacterial decolourisation and COD reduction of sucrose-aspartic acid Maillard product

Melanodins are amino-carbonyl complex, predominantly present in sugarcane molasses based distillery wastewater as major source of colourant. The microbial decolourisation of melanoidin is a challenge due to its binding property with other co-pollutants of distillery waste. Results revealed that the presence of Zn2+ (2.00-20.00 mg/L) in melanoidin solution (1200 mg/L) stimulated the bacterial growth and sucrose-aspartic acid Maillard product (SAA) decolourisation as compared to control, while Fe 3+ and Mn2+ at the same concentration inhibited the process. However, the presence of phenol (100 mg/L) along with Zn2+ , Fe3+ and Mn2+ suppressed the bacterial growth, SAA decolourisation and MnP activity. The shrinkage and reduced number of bacterial cell count at higher concentration of heavy metals in presence of phenol was also observed under scanning electron microscope.     

Remediation of Cu and As contaminated water and soil utilizing biochar supported layered double hydroxide: Mechanisms and soil environment altering

Preparing materials for simultaneous remediation of anionic and cationic heavy metals contamination has always been the focus of research. Herein a biochar supported FeMnMg layered double hydroxide (LDH) composites (LB) for simultaneous remediation of copper and arsenic contamination in water and soil has been assembled by a facile co-precipitation approach. Both adsorption isotherm and kinetics studies of heavy metals removal by LB were applied to look into the adsorption performance of adsorbents in water. Moreover, the adsorption mechanisms of Cu and As by LB were investigated, showing that Cu in aqueous solution was removed by the isomorphic substitution, precipitation and electrostatic adsorption while As was removed by complexation. In addition, the availability of Cu and As in the soil incubation experiments was reduced by 35.54%–63.00% and 8.39%–29.04%, respectively by using LB. Meanwhile, the addition of LB increased the activities of urease and sucrase by 93.78%–374.35% and 84.35%–520.04%, respectively, of which 1% of the dosage was the best. A phenomenon was found that the richness and structure of microbial community became vigorous within 1% dosage of LB, which indirectly enhanced the passivation and stabilization of heavy metals. These results indicated that the soil environment was significantly improved by LB. This research demonstrates that LB would be an imaginably forceful material for the remediation of anionic and cationic heavy metals in contaminated water and soil.     

Effects of cadium, zinc and lead on soil enzyme activities

Heavy metal （HM） is a major hazard to the soil-plant system. This study investigated the combined effects of cadium （Cd）, zinc （Zn） and lead （Pb） on activities of four enzymes in soil, including calatase, urease, invertase and alkalin phosphatase. HM content in tops of canola and four enzymes activities in soil were analyzed at two months after the metal additions to the soil. Pb was not significantly inhibitory than the other heavy metals for the four enzyme activities and was shown to have a protective role on calatase activity in the combined presence of Cd, Zn and Pb; whereas Cd significantly inhibited the four enzyme activities, and Zn only inhibited urease and calatase activities. The inhibiting effect of Cd and Zn on urease and calatase activities can be intensified significantly by the additions of Zn and Cd. There was a negative synergistic inhibitory effect of Cd and Zn on the two enzymes in the presence of Cd, Zn and Pb. The urease activity was inhibited more by the HM combinations than by the metals alone and reduced approximately 20%--40% of urease activity. The intertase and alkaline phosphatase activities significantly decreased only with the increase of Cd concentration in the soil. It was shown that urease was much more sensitive to HM than the other enzymes. There was a obvious negative correlation between the ionic impulsion of HM in soil, the ionic impulsion of HM in canola plants tops and urease activity. It is concluded that the soil urease activity may be a sensitive tool for assessing additive toxic combination effect on soil biochemical parameters.     

Superior activity of iron–manganese supported on kaolin for NO abatement at low temperature

A series of Fe–Mn catalysts was prepared using different supports(kaolin, diatomite, and alumina) and used for NO abatement via low-temperature NH_3-selective catalytic reduction(SCR).The results showed that 12 Fe–10 Mn/Kaolin(with the concentration of Fe and Mn 12 and 10 wt.%, respectively) exhibited the highest activity, and more than 95.8% NO conversion could be obtained within the wide temperature range of 120–300℃.The properties of the catalysts were characterized by inductively coupled plasma-atomic emission spectrometry(ICP-AES), thermogravimetry(TG), Brunner–Emmet–Teller(BET)measurements, X-ray diffraction(XRD), H_2-temperature programmed reduction(H_2-TPR),NH_3-temperature programmed desorption(NH_3-TPD), X-ray photoelectron spectroscopy(XPS), scanning electron microprobe(SEM) and energy dispersive spectroscopy(EDS)techniques.The support effects resulted in significant differences in the components and structures of catalysts.The 12 Fe–10 Mn/Kaolin catalyst exhibited better dispersion of active species, optimum low-temperature reduction behavior, the largest amount of normalized Br?nsted acid sites, and the highest Mn~(4+)/Mn and Fe~(3+)/(Fe~(3+)+ Fe~(2+)), all of which may be major reasons for its superior catalytic activity.     

Leaching of metals on stabilization of metal sludge using cement based materials

Toxicity characteristic leaching procedure(TCLP) of zinc plating sludge was carried out to assess the leaching potential of the sludge and the leachates were analyzed for heavy metals. The concentration of zinc, chromium, and lead in the leachate were 371.5 mg/L, 1.95 mg/L and 1.99 mg/L respectively. Solidification of zinc sludge was carried out using four different binder systems consisting of cement mortar, fly ash, clay and lime and cured for 28 d, The ratio of sludge added varied from 60% to 80% by volume. The solidified products were tested for metal fixing efficiency and physical strength. It was observed that the volume of sludge added that resulted in maximum metal stabilization was 60% for all the combinations, above which the metal fixation efficiency decreased resulting in high values of zinc in the leachate. Addition of 5% sodium silicate enhanced the chemical fixation of metals in all the binder systems. Among the four fixing agents studied, mixture of fly ash: lime, and cement mortar: lime stabilized zinc and other metals in the sludge effectively than other combinations. Addition of lime increased the stabilization of zinc whereas cement mortar increased the strength of the solidified product.     

Heavy metal accumulation by panicled goldenrain tree （Koelreuteria paniculata） and common elaeocarpus （Elaeocarpus decipens） in abandoned mine soils in southern China

Phytoremediation can be used as a sustainable technology for mine spoil remediation to remove heavy metals. This study investigated the concentration of 7 heavy metal contamination in soil and plant samples at an abandoned mine site. We found that, after vegetation remediation at the abandoned mine site, the reduction rates for 7 heavy metals were in the range of 4.2%–86%, where reduction rates over 50% were achieved for four heavy metals (Zn, Mn, Cd, Ni). Transfer coe cients of the panicled goldenrain tree (Koelreuteria paniculata Laxm) and the common elaeocarpus (Elaeocarpus decipens) for Zn, Mn, Ni, and Co were more than 1. Enrichment coe cients of both trees for Mn were higher than 1. Our results suggest that the panicled goldenrain tree and the common elaeocarpus tree may act as accumulators in remediation. Moreover, the woody vegetation remediation in abandoned mining areas play an important role in improving scenery besides removing heavy metal from contaminated soil.     

Enhanced U(Ⅵ) bioreduction by alginate-immobilized uranium-reducing bacteria in the presence of carbon nanotubes and anthraquinone-2,6-disulfonate

Uranium-reducing bacteria were immobilized with sodium alginate, anthraquinone-2,6-disulfonate(AQDS), and carbon nanotubes(CNTs). The effects of different AQDS-CNTs contents, U(Ⅳ) concentrations, and metal ions on U(Ⅳ) reduction by immobilized beads were examined. Over 97.5% U(Ⅵ)(20 mg/L) was removed in 8 hr when the beads were added to 0.7% AQDS-CNTs, which was higher than that without AQDS-CNTs. This result may be attributed to the enhanced electron transfer by AQDS and CNTs. The reduction of U(Ⅵ) occurred at initial U(Ⅵ) concentrations of 10 to 100 mg/L and increased with increasing AQDS-CNT content from 0.1% to 1%. The presence of Fe(Ⅲ), Cu(Ⅱ) and Mn(Ⅱ)slightly increased U(Ⅵ) reduction, whereas Cr(Ⅵ), Ni(Ⅱ), Pb(Ⅱ), and Zn(Ⅱ) significantly inhibited U(Ⅵ) reduction. After eight successive incubation-washing cycles or 8 hr of retention time(HRT) for 48 hr of continuous operation, the removal efficiency of uranium was above 90% and 92%, respectively. The results indicate that the AQDS-CNT/AL/cell beads are suitable for the treatment of uranium-containing wastewaters.     

Phosphorus utilization and microbial community in response to lead/iron addition to a waterlogged soil

Constructed wetlands have emerged as a viable option for helping to solve a wide range of water quality problems. However, heavy metals adsorbed by substrates would decrease the growth of plants, impair the functions of wetlands and eventually result in a failure of contaminant removal. Typha latifolia L., tolerant to heavy metals, has been widely used for phytoremediation of Pb/Zn mine tailings under waterlogged conditions. This study examined e ects of iron as ferrous sulfate (100 and 500 mg/kg) and lead as lead nitrate (0, 100, 500 and 1000 mg/kg) on phosphorus utilization and microbial community structure in a constructed wetland. Wetland plants (T. latifolia) were grown for 8 weeks in rhizobags filled with a paddy soil under waterlogged conditions. The results showed that both the amount of iron plaque on the roots and phosphorus adsorbed on the plaque decreased with the amount of lead addition. When the ratio of added iron to lead was 1:1, phosphorus utilized by plants was the maximum. Total amount of phospholipids fatty acids (PLFAs) was 23%–59% higher in the rhizosphere soil than in bulk soil. The relative abundance of Gram-negative bacteria, aerobic bacteria, and methane oxidizing bacteria was also higher in the rhizosphere soil than in bulk soil, but opposite was observed for other bacteria and fungi. Based on cluster analysis, microbial communities were mostly controlled by the addition of ferrous sulfate and lead nitrate in rhizosphere and bulk soil, respectively.     

Insights into metals in individual fine particles from municipal solid waste using synchrotron radiation-based micro-analytical techniques

Excessive inter-contamination with heavy metals hampers the application of biological treatment products derived from mixed or mechanically-sorted municipal solid waste(MSW). In this study, we investigated fine particles of 2 mm, which are small fractions in MSW but constitute a significant component of the total heavy metal content, using bulk detection techniques. A total of 17 individual fine particles were evaluated using synchrotron radiation-based micro-X-ray fluorescence and micro-X-ray diffraction. We also discussed the association, speciation and source apportionment of heavy metals. Metals were found to exist in a diffuse distribution with heterogeneous intensities and intense hot-spots of 10 μm within the fine particles. Zn–Cu, Pb–Fe and Fe–Mn–Cr had significant correlations in terms of spatial distribution. The overlapped enrichment, spatial association, and the mineral phases of metals revealed the potential sources of fine particles from size-reduced waste fractions(such as scraps of organic wastes or ceramics) or from the importation of other particles. The diverse sources of heavy metal pollutants within the fine particles suggested that separate collection and treatment of the biodegradable waste fraction(such as food waste) is a preferable means of facilitating the beneficial utilization of the stabilized products.     

Volatilization of heavy metals during incineration of municipal solid wastes

Incineration experiments with MSW, which had been impregnated with heavy metals, were presented to obtain information on the volatilization behavior of the elements cadmium (Cd), lead (Pb), and zinc (Zn) under different conditions. Experiments were carried out in a bubbling fluid bed system connected to a customized inductively coupled plasma optical emission spectroscopy(ICP-OES) for analyzing metals in the flue gas. The results indicated that the combustion temperature, the gas atmosphere, and the chlorine content in the flue gas could affect the volatilization behavior of heavy metals. In the fluidized bed combustion, a large surface area was provided by the bed sand particles, and they may act as absorbents for the gaseous ash-forming compound. Comparer with the metals Cd and Pb, the vaporization of Zn was low. The formation of stable compounds such as ZnO.Al2O3 could greatly decrease the metals volatilization. The presence of chlorine would enhance the volatilization of heavy metals by increasing the formation of metal chlorides. However, when the oxygen content was high, the chlorinating reaction was kinetically hindered, which heavy metals release would be delayed.     

Investigation on Fe, Mn, Zn, Cu, Pb and Cd fractions in the natural surface coating samples and surficial sediments in the Songhua River, China

Natural surface coating samples （NSCSs） from the surface of shingles and surficial sediments （SSs） in the Songhua River, China were employed to investigate the relationship between NSCSs and SSs in fractions of heavy metals （Fe, Mn, Zn, Cu, Pb, and Cd） using the modified sequential extraction procedure （MSEP）. The results show that the differences between NSCSs and SSs in Fe fi＇actions were insignificant and Fe was dominantly present as residual phase （76.22% for NSCSs and 80.88% for SSs） and Fe-oxides phase （20.33% for NSCSs and 16.15% for SSs）. Significant variation of Mn distribution patterns between NSCSs and SSs was observed with Mn in NSCSs mainly present in Mn-oxides phase （48.27%） and that in SSs present as residual phase （45.44%）. Zn, Cu, Pb and Cd were found dominantly in residual fractions （〉48%）, and next in solid oxides/hydroxides for Zn, Pb and Cd and in easily oxidizable solids/compounds form for Cu, respectively. The heavy metal distribution patterns implied that Fe/Mn oxides both in NSCSs and SSs were more important sinks for binding and adsorption of Zn, Pb and Cd than organic matter （OM）, and inversely, higher affinity of Cu to OM than Fe/Mn oxides in NSCSs and SSs was obtained. Meanwhile, it was found that the distributions of heavy metals in NSCSs and SSs were similar to each other and the pseudo-total concentrations of Zn, Cu, Pb and Cd in NSCSs were greater than those in SSs, highlighting the more importance for NSCSs than SSs in controlling behaviours of heavy metals in aquatic environments.     

Heavy metal concentrations in redeveloping soil of mine spoil under plantations of certain native woody species in dry tropical environment, India

Total concentration of heavy metals(Cd, Cr, Cu, Fe, Pb, Ni, Mn and Zn) was estimated in the redeveloping soil of mine spoil under 5-yr old plantations of four woody species namely: Albizia lebbeck, Albizia procera, Tectona grandis and Dendrocalamus strictus.The data recorded in the present study were compared with other unplanted coal mine spoil colliery, which was around to the study site and adjoining area of dry tropical forest. Among all the heavy metals, the maximum concentration was found for Fe and minimum for Cd.However, among all four species, total concentrations of these heavy metals were recorded maximally in the plantation plots of T. grandis except for Fe, while minimally in A. lebbeck except for Zn, whereas, the maximum concentration of Fe and Zn was in the plantation plots of D. strictus and A. procera. Statistical analysis revealed significant differences due to species for all the heavy metals except Cu.Among four species, A. lebbeck, A. procera and D. strictus showed more efficient for reducing heavy metal concentrations whereas T. grandis was not more effective to reduce heavy metal concentrations in redeveloping soil of mine spoil.     

Evaluation of phytoextracting cadmium and lead by sunflower, ricinus, alfalfa and mustard in hydroponic culture

Soil contaminated with heavy metals cadmium(Cd)and lead(Pb)is hard to be remediated.Phytoremediation may be a feasible method to remove toxic metals from soil,but there are few suitable plants which can hyperaccumulate metals.In this study,Cd and Pb accumulation by four plants including sunflower(Helianthus annuus L.),mustard(Brassica juncea L.),alfalfa(Medicago sativa L.), ricinus(Ricinus communis L.)in hydroponic cultures was compared.Results showed that these plants could phytocxtract heavy metals, the ability of accumulation differed with species,concentrations and categories of heavy metals.Values of BCF(bioconcentration factor)and TF(translocation factor)indicated that four species had dissimilar abilities of phytoextraction and transportation of heavy metals.Changes on the biomass of plants,pH and Eh at different treatments revealed that these four plants had distinct responses to Cd and Pb in cultures.Measurements should be taken to improve the phytoremediation of sites contaminated with heavy metals,such as pH and Eh regulations,and so forth.     

Response of ammonia-oxidizing archaea to heavy metal contamination in freshwater sediment

It has been well-documented that the distribution of ammonia-oxidizing bacteria(AOB) and archaea(AOA) in soils can be affected by heavy metal contamination, whereas information about the impact of heavy metal on these ammonia-oxidizing microorganisms in freshwater sediment is still lacking. The present study explored the change of sediment ammonia-oxidizing microorganisms in a freshwater reservoir after being accidentally contaminated by industrial discharge containing high levels of metals. Bacterial amoA gene was found to be below the quantitative PCR detection and was not successfully amplified by conventional PCR. The number of archaeal amoA gene in reservoir sediments were 9.62 × 10~2–1.35 × 10~7 copies per gram dry sediment. AOA abundance continuously decreased, and AOA richness, diversity and community structure also considerably varied with time. Therefore, heavy metal pollution could have a profound impact on freshwater sediment AOA community. This work could expand our knowledge of the effect of heavy metal contamination on nitrification in natural ecosystems.