Effects of synthesis methods on catalytic activities of CoOx–TiO2 for low-temperature NH3-SCR of NO

A series of cobalt doped TiO_2(Co-TiO_2) and Co Oxloaded TiO_2(Co/TiO_2) catalysts prepared by sol–gel and impregnation methods respectively were investigated on selective catalytic reduction with NH_3(NH_3-SCR) of NO. It was found that Co-TiO_2 catalyst showed more preferable catalytic activity at low temperature range. From characterization results of XRD,TEM, Raman and FT-IR, Co species were proved to be doped into TiO_2 lattice by replaced Ti atoms. After being characterized and analyzed by NH_3-TPD, PL, XPS, EPR and DRIFTS, it was found that the better NH_3-SCR activities of Co-TiO_2 catalysts, compared with Co/TiO_2 catalyst, were ascribed to the formation of more oxygen vacancies which further promoted the production of more superoxide ions(O-2). The superoxide ions were crucial for the formation of low temperature SCR reaction intermediates(NO-3) by reacting with adsorbed NO molecule. Therefore, these aspects were responsible for the higher low temperature NH_3-SCR activity of Co-TiO_2 catalysts.     

Synthesis,crystal structure,photodegradation kinetics and photocatalytic activity of novel photocatalyst ZnBiYO4

ZnBiYO₄ was synthesized by a solid-state reaction method for the first time. The structural and photocatalytic properties of ZnBiYO₄ were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and UV–Vis diffuse reflectance. ZnBiYO₄ crystallized with a tetragonal spinel structure with space group I41/A. The lattice parameters for ZnBiYO₄ were a = b = 11.176479 Å and c = 10.014323 Å. The band gap of ZnBiYO₄ was estimated to be 1.58 eV. The photocatalytic activity of ZnBiYO₄ was assessed by photodegradation of methyl orange under visible light irradiation. The results showed that ZnBiYO₄ had higher catalytic activity compared with N-doped TiO₂ under the same experimental conditions using visible light irradiation. The photocatalytic degradation of methyl orange with ZnBiYO₄ or N-doped TiO₂ as catalyst followed first-order reaction kinetics, and the first-order rate constant was 0.01575 and 0.00416 min^− 1 for ZnBiYO₄ and N-doped TiO₂, respectively. After visible light irradiation for 220 min with ZnBiYO₄ as catalyst, complete removal and mineralization of methyl orange were observed. The reduction of total organic carbon, formation of inorganic products, SO₄^2 − and NO₃⁻, and evolution of CO₂ revealed the continuous mineralization of methyl orange during the photocatalytic process. The intermediate products were identified using liquid chromatography–mass spectrometry. The ZnBiYO₄/(visible light) photocatalysis system was found to be suitable for textile industry wastewater treatment and could be used to solve other environmental chemical pollution problems.     

Enhanced dechlorination of 2,4-dichlorophenol by recoverable Ni/Fe–Fe3O4 nanocomposites

Ni/Fe-Fe_3O_4 nanocomposites were synthesized for dechlorination of 2,4-dichlorophenol(2,4-DCP). The effects of the Ni content in Ni/Fe-Fe_3O_4 nanocomposites, solution pH, and common dissolved ions on the dechlorination efficiency were investigated, in addition to the reusability of the nanocomposites. The results showed that increasing content of Ni in Ni/Fe–Fe_3O_4 nanocomposites, from 1 to 5 wt.%, greatly increased the dechlorination efficiency; the Ni/Fe–Fe_3O_4 nanocomposites had much higher dechlorination efficiency than bare Ni/Fe nanoparticles. Ni content of 5 wt.% and initial p H below 6.0 was found to be the optimal conditions for the catalytic dechlorination of 2,4-DCP. Both 2,4-DCP and the intermediate product 2-chlorophenol(2-CP) were completely removed, and the concentration of the final product phenol was close to the theoretical phenol production from complete dechlorination of 20 mg/L of 2,4-DCP, after 3 hr reaction at initial p H value of 6.0,3 g/L Ni/Fe-Fe_3O_4 , 5 wt.% Ni content in the composite, and temperature of 22℃. 2,4-DCP dechlorination was enhanced by Cl-and inhibited by NO3-and SO_4~(2-). The nanocomposites were easily separated from the solution by an applied magnetic field. When the catalyst was reused, the removal efficiency of 2,4-DCP was almost 100% for the first seven uses, and gradually decreased to 75% in cycles 8–10. Therefore, the Ni/Fe–Fe_3O_4 nanocomposites can be considered as a potentially effective tool for remediation of pollution by 2,4-DCP.     

Enhanced photoelectrocatalytic degradation of ammonia by in situ photoelectrogenerated active chlorine on TiO2 nanotube electrodes

TiO_2 nanotube(Ti NT) electrodes anodized in fluorinated organic solutions were successfully prepared on Ti sheets. Field-emission scanning electron microscopy(FE-SEM) and X-ray diffraction(XRD) were performed to characterize the TiNT electrodes. The linear voltammetry results under irradiation showed that the TiNT electrode annealed at 450°C presented the highest photoelectrochemical activity. By combining photocatalytic with electrochemical process, a significantly synergetic effect on ammonia degradation was observed with Na_2SO_4 as supporting electrolyte at pH 10.7. Furthermore, the photoelectrocatalytic efficiency on the ammonia degradation was greatly enhanced in presence of chloride ions without the limitation of pH. The degradation rate was improved by 14.8 times reaching 4.98 × 10~(-2) min~(-1) at pH 10.7 and a faster degradation rate of 6.34 × 10~(-2) min~(-1)was obtained at pH 3.01. The in situ photoelectrocatalytic generated active chlorine was proposed to be responsible for the improved efficiency. On the other hand, an enhanced degradation of ammonia using TiNT electrode fabricated in fluorinated organic solution was also confirmed compared to TiNT electrode anodized in fluorinated water solution and TiO_2 film electrode fabricated by sol–gel method. Finally, the effect of chloride concentration was also discussed.     

Enhanced catalytic complete oxidation of 1,2-dichloroethane over mesoporous transition metal-doped γ-Al2O3

High-surface-area mesoprous powders of γ-Al₂O₃ doped with Cu^2 +, Cr^3 +, and V^3 + ions were prepared via a modified sol–gel method and were investigated as catalysts for the oxidation of chlorinated organic compounds. The composites retained high surface areas and pore volumes comparable with those of undoped γ-Al₂O₃ and the presence of the transition metal ions enhanced their surface acidic properties. The catalytic activity of the prepared catalysts in the oxidation of 1,2-dichloroethane (DCE) was studied in the temperature range of 250–400°C. The catalytic activity and product selectivity were strongly dependent on the presence and the type of dopant ion. While Cu^2 +- and Cr^3 +-containing catalysts showed 100% conversion at 300°C and 350°C, V^3 +-containing catalyst showed considerably lower conversion. Furthermore, while the major products of the reactions over γ-alumina were vinyl chloride (C₂H₃Cl) and hydrogen chloride (HCl) at all temperatures, Cu- and Cr-doped catalysts showed significantly stronger capability for deep oxidation to CO₂.     

The selective catalytic reduction of NO over Ce0.3TiOx-supported metal oxide catalysts

A Ce_(0.3)TiO_xoxide carrier was synthesized via a sol–gel process,and Ce_(0.3)TiO_xsupported metal(M=Cd,Mn,Fe,W,Mo)oxide catalysts were prepared by the method of incipient-wetness impregnation.The catalysts were characterized by means of X-ray diffraction(XRD),Brunauer–Emmett–Teller(BET)analysis,scanning electron microscopy(SEM),transmission electron microscopy(TEM),Fourier transform infrared(FT–IR)spectroscopy,UV–Visdiffusereflectancespectroscopy(UV–VisDRS),and Temperature-programmed reduction with H_2(H_2-TPR).The catalytic activities for de-NO_(x )were evaluated by the NH_3-SCR reaction.Among all the catalysts tested,the 2 wt.%Cd/Ce_(0.3)TiO_xcatalyst exhibited the best NH_3-SCR performance,with a wide temperature window of 250–450°C for NO conversion above 90%.Moreover,the catalyst showed N_2 selectivity greater than 99%from 200 to 450°C.     

Removal of formaldehyde over MnxCe1-xO2 catalysts: Thermal catalytic oxidation versus ozone catalytic oxidation

MnxCe1- xO2（x： 0.3–0.9） prepared by Pechini method was used as a catalyst for the thermal catalytic oxidation of formaldehyde（HCHO）. At x = 0.3 and 0.5, most of the manganese was incorporated in the fluorite structure of Ce O2 to form a solid solution. The catalytic activity was best at x = 0.5, at which the temperature of 100% removal rate is the lowest（270°C）. The temperature for 100% removal of HCHO oxidation is reduced by approximately 40°C by loading 5 wt.% Cu Oxinto Mn0.5Ce0.5O2. With ozone catalytic oxidation, HCHO（61 ppm） in gas stream was completely oxidized by adding 506 ppm O3 over Mn0.5Ce0.5O2 catalyst with a GHSV（gas hourly space velocity） of 10,000 hr-1at 25°C. The effect of the molar ratio of O3 to HCHO was also investigated. As O3/HCHO ratio was increased from 3 to 8, the removal efficiency of HCHO was increased from 83.3% to 100%. With O3/HCHO ratio of 8, the mineralization efficiency of HCHO to CO2 was 86.1%. At 25°C, the p-type oxide semiconductor（Mn0.5Ce0.5O2） exhibited an excellent ozone decomposition efficiency of 99.2%,which significantly exceeded that of n-type oxide semiconductors such as Ti O2, which had a low ozone decomposition efficiency（9.81%）. At a GHSV of 10,000 hr-1, [O3]/[HCHO] = 3 and temperature of 25°C, a high HCHO removal efficiency（≥ 81.2%） was maintained throughout the durability test of 80 hr, indicating the long-term stability of the catalyst for HCHO removal.     

Phosphate recovery from anaerobic digester effluents using CaMg(OH)4

Dolomite lime(DL)(CaMg(OH)_4) was used as an economical source of Mg~(2+)for the removal and recovery of phosphate from an anaerobic digester effluent of a municipal wastewater treatment plant(MWWTP) wastewater. Batch precipitation results determined that phosphate was effectively reduced from 87 to less than 4 mg-P/L when the effluent water was mixed with 0.3 g/L of DL. The competitive precipitation mechanisms of different solids in the treatment system consisting of Ca~(2+)–Mg~(2+)–NH_4~+–PO_4~(3-)CO_3~(2-)were determined by comparing model predictions with experimental results. Thermodynamic model calculations indicated that hydroxyapatite(Ca_(10)(PO_4)_6(OH)_2), Ca_4H(PO_4)_3?3H_2O, Ca_3(PO_4)_2(beta), and Ca_3(PO_4)_2(am2)were more stable than struvite(MgNH_4PO_3?6H_2O) and calcite(CaCO_3). However, X-ray diffraction(XRD) analysis determined the formation of struvite and calcite minerals in the treated effluent. Kinetic experimental results showed that most of the phosphate was removed from synthetic effluent containing NH_4~+within 2 hr, while only 20% of the PO_4~(3-)was removed in the absence of NH_4~+after 24 hr of treatment. The formation of struvite in the DL-treated effluent was due to the rapid precipitation rate of the mineral. The final pH of the DL-treated effluent significantly influenced the mass ratio of struvite to calcite in the precipitates. Because more calcite was formed when the p H increased from 8.4 to 9.6, a p H range of 8.0–8.5 should be used to produce solid with high PO_4~(3-)content. This study demonstrated that DL could be used for effective removal of phosphate from the effluent and that resultant precipitates contained high content of phosphate and ammonium.     

Remarkable promotion effect of trace sulfation on OMS-2 nanorod catalysts for the catalytic combustion of ethanol

OMS-2 nanorod catalysts were synthesized by a hydrothermal redox reaction method using MnSO₄ (OMS-2-SO₄) and Mn(CH₃COO)₂ (OMS-2-AC) as precursors. SO₄^2 −-doped OMS-2-AC catalysts with different SO₄^2 − concentrations were prepared next by adding (NH₄)₂SO₄ solution into OMS-2-AC samples to investigate the effect of the anion SO₄^2 − on the OMS-2-AC catalyst. All catalysts were then tested for the catalytic oxidation of ethanol. The OMS-2-SO₄ catalyst synthesized demonstrated much better activity than OMS-2-AC. The SO₄^2 − doping greatly influenced the activity of the OMS-2-AC catalyst, with a dramatic promotion of activity for suitable concentration of SO₄^2 − (SO₄/catalyst = 0.5% W/W). The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma optical emission spectroscopy (ICP-OES), NH₃-TPD and H₂-TPR techniques. The results showed that the presence of a suitable amount of SO₄^2 − species in the OMS-2-AC catalyst could decrease the Mn–O bond strength and also enhance the lattice oxygen and acid site concentrations, which then effectively promoted the catalytic activity of OMS-2-AC toward ethanol oxidation. Thus it was confirmed that the better catalytic performance of OMS-2-SO₄ compared to OMS-2-AC is due to the presence of some residual SO₄^2 − species in OMS-2-SO₄ samples.     

Assessing the effects of surface-bound humic acid on the phototoxicity of anatase and rutile TiO2 nanoparticles in vitro

In this study,the cytotoxicity of two different crystal phases of TiO₂ nanoparticles,with surface modification by humic acid（HA）,to Escherichia coli,was assessed.The physicochemical properties of TiO₂ nanoparticles were thoroughly characterized.Three different initial concentrations,namely 50,100,and 200 ppm,of HA were used for synthesis of HA coated TiO₂ nanoparticles（denoted as A/RHA50,A/RHA100,and A/RHA200,respectively）.Results indicate that rutile（LC50（concentration that causes 50%mortality compared the control group）=6.5）was more toxic than anatase（LC₅0=278.8）under simulated sunlight（SSL）irradiation,possibly due to an extremely narrow band gap.It is noted that HA coating increased the toxicity of anatase,but decreased that of rutile.Additionally,AHA50 and RHA50had the biggest differences compared to uncoated anatase and rutile with LC₅0of 201.9 and21.6,respectively.We then investigated the formation of reactive oxygen species（ROS）by TiO₂ nanoparticles in terms of hydroxyl radicals（OH）and superoxide anions（O₂^-）.Data suggested that O₂^- was the main ROS that accounted for the higher toxicity of rutile upon SSL irradiation.We also observed that HA coating decreased the generation of OH and O₂^- on rutile,but increased O₂^- formation on anatase.Results from TEM analysis also indicated that HA coated rutile tended to be attached to the surface of E.coli more than anatase.     

Remediation of saline–sodic soil with flue gas desulfurization gypsum in a reclaimed tidal flat of southeast China

Salinization and sodicity are obstacles for vegetation reconstruction of coastal tidal flat soils. A study was conducted with flue gas desulfurization(FGD)-gypsum applied at rates of 0, 15, 30, 45 and 60 Mg/ha to remediate tidal flat soils of the Yangtze River estuary.Exchangeable sodium percentage(ESP), exchangeable sodium(ExNa), p H, soluble salt concentration, and composition of soluble salts were measured in 10 cm increments from the surface to 30 cm depth after 6 and 18 months. The results indicated that the effect of FGD-gypsum is greatest in the 0–10 cm mixing soil layer and 60 Mg/ha was the optimal rate that can reduce the ESP to below 6% and decrease soil p H to neutral(7.0). The improvement effect was reached after 6 months, and remained after 18 months. The composition of soluble salts was transformed from sodic salt ions mainly containing Na~+, HCO_3~-+ CO_3~(2-)and Cl-to neutral salt ions mainly containing Ca~(2+)and SO_4~(2-). Non-halophyte plants were survived at 90%. The study demonstrates that the use of FGD-gypsum for remediating tidal flat soils is promising.     

Photocatalytic parameters and kinetic study for degradation of dichlorophenol-indophenol (DCPIP) dye using highly active mesoporous TiO2 nanoparticles

Highly active mesoporous TiO_2 of about 6 nm crystal size and 280.7 m~2/g specific surface areas has been successfully synthesized via controlled hydrolysis of titanium butoxide at acidic medium. It was characterized by means of XRD(X-ray diffraction), SEM(scanning electron microscopy), TEM(transmission electron microscopy), FT-IR(Fourier transform infrared spectroscopy), TGA(thermogravimetric analysis), DSC(differential scanning calorimetry) and BET(Brunauer–Emmett–Teller) surface area. The degradation of dichlorophenol-indophenol(DCPIP) under ultraviolet(UV) light was studied to evaluate the photocatalytic activity of samples. The effects of different parameters and kinetics were investigated. Accordingly, a complete degradation of DCPIP dye was achieved by applying the optimal operational conditions of 1 g/L of catalyst, 10 mg/L of DCPIP, pH of 3 and the temperature at 25 ± 3°C after 3 min under UV irradiation. Meanwhile, the Langmuir–Hinshelwood kinetic model described the variations in pure photocatalytic branch in consistent with a first order power law model.The results proved that the prepared TiO_2 nanoparticle has a photocatalytic activity significantly better than Degussa P-25.     

N/Ce doped graphene supported Pt nanoparticles for the catalytic oxidation of formaldehyde at room temperature

Pt catalysts with nitrogen-doped graphene oxide (GO) as support and CeO₂ as promoter were prepared by impregnation method,and their catalytic oxidation of formaldehyde (HCHO) at room temperature was tested.The Pt-CeO₂/N-rGO (reduced GO) with a mass fraction of 0.7% Pt and 0.8%CeO₂ exhibited an excellent catalytic performance with the 100% conversion of HCHO at room temperature.Physicochemical characterization demonstrated that nitrogendoping greatly increased the...     

Comparison between UV and VUV photolysis for the pre- and post-treatment of coking wastewater

In this study, ultraviolet (UV) and vacuum ultraviolet (VUV) photolysis were investigated for the pre-treatment and post-treatment of coking wastewater. First, 6-fold diluted raw coking wastewater was irradiated by UV and VUV. It was found that 15.9%–35.4% total organic carbon (TOC) was removed after 24 hr irradiation. The irradiated effluent could be degraded by the acclimated activated sludge. Even though the VUV photolysis removed more chemical oxygen demand (COD) than UV, the UV-irradiated effluent demonstrated better biodegradability. After 4 hr UV irradiation, the biological oxygen demand BOD₅/COD ratio of irradiated coking wastewater increased from 0.163 to 0.224, and its toxicity decreased to the greatest extent. Second, the biologically treated coking wastewater was irradiated by UV and VUV. Both of them were able to remove 37%–47% TOC within 8 hr irradiation. Compared to UV, VUV photolysis could significantly improve the transparency of the bio-treated effluent. VUV also reduced 7% more ammonia nitrogen (NH₄⁺–N), 17% more nitrite nitrogen (NO₂⁻–N), and 18% more total nitrogen (TN) than UV, producing 35% less nitrite nitrogen (NO₃⁻–N) as a result. In conclusion, UV irradiation was better in improving the biodegradability of coking wastewater, while VUV was more effective at photolyzing the residual organic compounds and inorganic N-species in the bio-treated effluent.     

Particulate matter assessment of a wetland in Beijing

To increase the knowledge on the particulate matter of a wetland in Beijing, an experimental study on the concentration and composition of PM₁₀ and PM_2.5 was implemented in Beijing Olympic Forest Park from 2013 to 2014. This study analyzed the meteorological factors and deposition fluxes at different heights and in different periods in the wetlands. The results showed that the mean mass concentrations of PM₁₀ and PM_2.5 were the highest at 06:00–09:00 and the lowest at 15:00–18:00. And the annual concentration of PM₁₀ and PM_2.5 in the wetland followed the order of dry period (winter) > normal water period (spring and autumn) > wet period (summer), with the concentration in the dry period significantly higher than that in the normal water and wet periods. The chemical composition of PM_2.5 in the wetlands included NH₄⁺, K⁺, Na⁺, Mg^2 +, SO₄^2 −, NO₃⁻, and Cl⁻, which respectively accounted for 12.7%, 1.0%, 0.8%, 0.7%, 46.6%, 33.2%, and 5.1% of the average annual composition. The concentration of PM₁₀ and PM_2.5 in the wetlands had a significant positive correlation with relative humidity, a negative correlation with wind speed, and an insignificant negative correlation with temperature and radiation. The daily average dry deposition amount of PM₁₀ in the different periods followed the order of dry period > normal water period > wet period, and the daily average dry deposition amount of PM_2.5 in the different periods was dry period > wet period > normal water period.     

TiO2光催化氧化苯酚动力学研究

以中压汞灯为光源,研究了苯酚在ＴｉＯ２水悬浮液中降解动力学,考察了苯酚在起始浓度,气相氧浓度,催化剂投加量（ＴｉＯ２）光强度以及催化剂煅烧温度对苯酚光解速率的影响,揭示了苯酚多相光催化氧化反应的特点,反应过程符合表现一级动力学规律,气相氧的影响为一级,苯酚初始浓度的影响为负一级,在一定光强度下,催化剂的投加量存在一最值值,说明有效光强度,气相氧以及催化剂投加量是光催化氧化反应的关键因素,适当地热处     

The effect of salinity on waste activated sludge alkaline fermentation and kinetic analysis

The effect of salinity on sludge alkaline fermentation at low temperature(20°C) was investigated, and a kinetic analysis was performed. Different doses of sodium chloride(Na Cl, 0–25 g/L) were added into the fermentation system. The batch-mode results showed that the soluble chemical oxygen demand(SCOD) increased with salinity. The hydrolysate(soluble protein, polysaccharide) and the acidification products(short chain fatty acids(SCFAs), NH+4–N, and PO_4~(3-)–P) increased with salinity initially, but slightly declined respectively at higher level salinity(20 g/L or 20–25 g/L). However, the hydrolytic acidification performance increased in the presence of salt compared to that without salt.Furthermore, the results of Haldane inhibition kinetics analysis showed that the salt enhanced the hydrolysis rate of particulate organic matter from sludge particulate and the specific utilization of hydrolysate, and decreased the specific utilization of SCFAs. Pearson correlation coefficient analysis indicated that the importance of polysaccharide on the accumulation of SCFAs was reduced with salt addition, but the importance of protein and NH+4–N on SCFA accumulation was increased.     

Effect of organic matter on phosphorus recovery from sewage sludge subjected to microwave hybrid pretreatment

Microwave (MW) hybrid processes are able to disrupt the flocculent structure of complex waste activated sludge, and help promote the recovery of phosphorus as struvite. In this study, to optimize struvite yield, (1) the characteristics of matter released in MW-hybrid treatments were compared, including MW, MW-acid, MW-alkali, MW-H₂O₂, and MW-H₂O₂-alkali. The results showed that selective release of carbon, nitrogen, phosphorus, Ca^2 +, and Mg^2 + achieved by sludge pretreatment using MW-hybrid processes. MW-H₂O₂ is the recommended sludge pretreatment process for phosphorus recovery in the form of struvite. The ratio of Mg^2 +:NH₄⁺-N:PO₄^3 −-P was 1.2:2.9:1 in the supernatant. (2) To clarify the effects of organic matter on struvite recovery, the composition and molecular weight distribution of organic matters were analyzed. Low molecular weight COD was found to facilitate the removal rate of NH₄⁺-N and PO₄³-P via crystallization, and the amorphous struvite crystals (< 1 kDa) from the filtered solutions had high purity. Therefore, the present study reveals the necessity of taking into consideration the interference effect of high molecular weight organic matters during struvite crystallization from sewage sludge.     

Potential ammonia emission from flag leaves of paddy rice (Oryza sativa L. cv. Koshihikari)

The present study aimed to investigate the potential ammonia (NH₃) emission from flag leaves of paddy rice (Oryza sativa L. cv. Koshihikari). The study was conducted at a paddy field in central Japan that was designed as a free-air CO₂ enrichment (FACE) facility for paddy rice. A dynamic chamber method was used to measure the potential NH₃ emissions. The air concentrations of NH₃ at two heights (2 and 6 m from the ground surface) were measured using a filter-pack method, and the exchange fluxes of NH₃ of the whole paddy field were calculated using a gradient method. The flag leaves showed potential NH₃ emissions of 25-38 ng N cm⁻² h⁻¹ in the daytime from the heading to the maturity stages, and they showed potentials of approximately 22 ng N cm⁻² h⁻¹, even in the nighttime, at the heading and mid-ripening stages. The exchange fluxes of NH₃ of the whole paddy field in the daytime were net emissions of 0.9-3.9 g N ha⁻¹ h⁻¹ whereas the exchange fluxes of NH₃ in the nighttime were approximately zero.     

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 Cu^2 +–Fe^3 + 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 Mn^2 +–Fe^3 + 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 Mn^2 +–Fe^3 +, 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 F_OF₁-ATPase, leading to conformational changes. Moreover the action may be direct or be mediated by environment redox potential. The effects observed when Fe^3 + was added separately disappeared in both cases, which might be a result of competing processes between Fe^3 + 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.