[Removal of Fe(⠡), Mn(⠡), and NH4+-N by Using δ-MnO2 Coated Zeolite].

δ-MnO2/zeolite nanocomposites were prepared with natural zeolite, potassium permanganate, and manganese sulfate by oxidation-reduction precipitation, which were used to simultaneously remove Fe2+, Mn2+, and NH4+-N from groundwater. To investigate the performance and mechanism of Fe2+, Mn2+, and NH4+-N removal from groundwater by δ-MnO2/zeolite nanocomposites, static batch experiments were conducted under different environmental conditions in a zero-oxygen atmosphere using SEM, TEM, Zeta potential, FTIR, and XPS techniques. The experimental results showed that the manganese-oxide-coated natural zeolite was δ-MnO2, and Fe2+, Mn2+, and NH4+-N adsorption on the δ-MnO2/zeolite nanocomposites could be best described with the pseudo-second-order kinetic model and the Langmuir model. In addition, the maximum adsorption capacities of Fe2+, Mn2+, and NH4+-N were calculated to be 215.1, 23.6, and 7.64 mg·g-1, respectively. The removal mechanism of NH4+-N from the solutions by zeolite was via the action of ion exchange, and the adsorption and oxidation catalysis of δ-MnO2-coated zeolite were responsible for the removal of Fe2+ and Mn2+. This research indicates that δ-MnO2/zeolite nanocomposites could be used as highly efficient adsorbents to simultaneously remove Fe2+, Mn2+, and NH4+-N from water.

[Transformation of Ammonia in Wetland Sediments for Treatment of Mining Wastewater].

Nitrogen elements play an important role in the biogeochemical cycle of artificial wetlands. In this study, we investigated the anaerobic transformation of ammonia nitrogen and its main pathways in sediment in an artificial wetland. Results showed that the anaerobic ammonia oxidation (ANAMMOX) process and iron reduction occurred in wetland sediment, coupled with anaerobic ammonia oxidation (Feammox). Feammox used Fe(Ⅲ) to oxidize ammonia nitrogen to produce nitrogen; intermediate products were nitrate, nitrite, and N2O. Addition of ferrihydrite promoted the Feammox process and ammonia nitrogen loss caused by Feammox was enhanced from 1.69 to 2.72 mg·(kg·d)-1. When ferrihydrite was added, a loss of 28% of total nitrogen (TN) in the wetland occurred, associated with Feammox, increasing to 42%. Anaerobic ammonia oxidation was significantly inhibited with addition of ferrihydrite and TN loss in the system decreased by about 25%. Results showed that the formation of goethite by mineralization of ferrihydrite inhibited the ANAMMOX process, promoting Feammox to lead to competing electronic donors for the S-ANAMMOX process, causing inhibition of the S-ANAMMOX process. This achieves the purpose of reducing TN loss in the wetland system. In addition, this may have some significance for further understanding the interaction between iron reduction and the nitrogen cycle in the wetland.

Simultaneous chemical oxygen demand removal, methane production and heavy metal precipitation in the biological treatment of landfill leachate using acid mine drainage as sulfate resource.

Biological treatment played an important role in the treatment of landfill leachate. In the current study, acid mine drainage (AMD) was used as a source of sulfate to strengthen the anaerobic treatment of landfill leachate. Effects of chemical oxygen demand (COD) and SO42- mass concentration ratio on the decomposition of organic matter, methane production and sulfate reduction were investigated and the microbial community was analyzed using the high throughout methods. Results showed that high removal efficiency of COD, methane production and heavy metal removal was achieved when the initial COD/SO42- ratio (based on mass) was set at 3.0. The relative abundance of anaerobic hydrogen-producing bacteria (Candidatus Cloacamonas) in the experimental group with the addition of AMD was significantly increased compared to the control. Abundance of hydrogenotrophic methanogens of Methanosarcina and Methanomassiliicoccus was increased. Results confirmed that AMD could be used as sulfate resource to strengthen the biological treatment of landfill leachate.

[Effects of Goethite, Magnetite and Gypsum on the Anaerobic Degradation of 2,4-Dichlorophenol].

2,4-dichlorophenol(2,4-DCP), a highly toxic and refractory organic compound, was commonly used in pesticide production and thus widely distributed in water and soil. Goethite, magnetite and gypsum were added into the anaerobic system which simulated the natural anaerobic process to evaluate their effects on the anaerobic degradation of 2,4-DCP. It indicated that goethite, magnetite and gypsum had no appreciable adsorption ability toward 2,4-DCP under anaerobic condition. Mass balance analysis showed that only the transformation of 2,4-DCP to 4-chlorophenol(4-CP) occurred in all experimental groups. The addition of sodium acetate doubled the reductive dechlorination rate of 2,4-DCP in comparison with the groups without exogenous carbon source. The reductive dechlorination rate of 2,4-DCP was enhanced by the addition of goethite and magnetite, which was caused by the improved metabolic activity of dechlorination bacteria that played an important role in the anaerobic degradation of 2,4-DCP. Gypsum greatly inhibited or even stopped the degradation process of 2,4-DCP through restraining the growth and activity of dechlorination bacteria. This study will shed light on the migration and degradation of refractory chlorinated organic contaminants in anaerobic sedimentary environment, and the treatment of such matters in environmental technology.

[Preparation of Magnetic Biomass Carbon by Thermal Decomposition of Siderite Driven by Wheat Straw and Its Adsorption on Cadmium].

C-Fe3O4 composite material [magnetic biomass char (MBC)] was prepared by pyrolysis of a mixture of wheat straw and siderite at 500℃. The MBC was characterized by XRF, FTIR, XRD, SEM, XPS, and a magnetic susceptibility device. The effect of contact time, pH value, initial Cd2+ concentration, and ionic strength on the adsorption capacity of the MBC to Cd2+ was investigated. The results showed that the BET surface areas of the MBC and biomass char (BC) were 23.38 m2·g-1 and 7.20 m2·g-1, respectively, total pore volumes were 1.04×10-1 cm3·g-1 and 2.23×10-2 cm3·g-1, and average pore diameters were 17.74 nm and 12.38 nm. The magnetic susceptibility of the MBC was 42900×10-8 m3·kg-1. FTIR showed that phenolic hydroxyl and carboxyl functional groups bound metal ions on the surface of the MBC and BC. The kinetic data of the MBC were described well by the pseudo-second-order model. Isothermal adsorption of Cd2+ by MBC and BC was fitted well by the Freundlich equation. The adsorption velocity increased with an increase of pH in the region 3-6 and then stabilized in the region 6-9. The adsorption capacity of Cd2+ decreased slightly when ionic strength increased from 1 mmol·L-1 to 100 mmol·L-1, whereas the desorption rate increased from 0.51% to 8.5%. The adsorption properties and characterization results illustrated that the removal mechanism of Cd2+ likely was through adsorption and ion exchange on the surface of the MBC with a high amount of functional groups. In addition, magnetic adsorbents offered a significant advantage compared to other adsorbents in the aspect of separation from aqueous solution.

Identification and determination of the contribution of iron-steel manufacturing industry to sediment-associated polycyclic aromatic hydrocarbons (PAHs) in a large shallow lake of eastern China.

Seventeen polycyclic aromatic hydrocarbon (PAH) compounds were determined in surface sediments collected from the Chaohu Lake (a large shallow lake in eastern China) and its tributaries. Both diagnostic ratios and a receptor model (positive matrix factorization, PMF) were applied to identify and determine the contribution of a local iron-steel manufacturing plant located in the Nanfei River (NFR) to the Chaohu Lake basin. The results show that sites located in the downstream of the steel plant contained concentrations of 17 PAH (Σ17PAH) approximately two orders of magnitudes higher than those from other sites. Five factors were identified by the PMF model, including industrial waste, wood/biomass burning, diagenetic origin, domestic coal combustion, and industrial combustion. Our findings suggest that sediments in the downstream of the plant and in the western part of the Chaohu Lake were predominantly affected by industrial coal combustion. A mixture of pyrolytic origins impacted urban sediments in the upstream of the plant, whereas diagenetic origins along with coal and biomass burning were suggested to influence the eastern part and rural tributaries of the lake. To assess the potential ecological risk and toxicity caused by the iron-steel plant, sediment toxicity was evaluated by the PMF model, sediment quality guideline, and toxic equivalent factors. All of the three approaches suggested PAH accumulation in the NFR sediments could produce significant adverse ecological effects and half of the sediment toxicity in the NFR may be attributed to the emissions from the iron-steel plant. Some rural locations also exhibited PAH concentrations above probable effects, most likely contributed by wood/biomass burning.

Influence of Different Electron Acceptors on the Anaerobic Degradation of Curly-Leaf Pondweed.

Curly-leaf pondweed (Potamogeton crispus) was utilized as the representative to investigate the biodecomposition process of aquatic plants under different reducible conditions. Results showed that the methane production was inhibited when different electron acceptors (Fe(III), and ) were available. The methane production was decreased by 57% when Fe(III) and or were both available compared to the control. The degradation efficiency of hemicellulose and lignin with Fe(III) and were increased significantly. This provided a theoretical basis for slowing down the emissions of methane.

Occurrence, compositional distribution, and toxicity assessment of pyrethroid insecticides in sediments from the fluvial systems of Chaohu Lake, Eastern China.

Surface sediment-associated synthetic pyrethroid insecticides (SPs) are known to pose high risks to the benthic organisms in Chaohu Lake, a shallow lake of Eastern China. However, the pollution status of the lake's tributaries and estuaries is still unknown. The present study was conducted to investigate the occurrence, compositional distribution, and toxicity of 12 currently used SPs in the surface sediments from four important tributaries, as well as in the sediment cores at their estuaries, using GC-MS for quantification. All SPs selected were detectable, with cypermethrin, es/fenvalerate, and permethrin dominant in both surface and core sediments, suggesting that these compounds were extensively applied. Urban samples contained the highest summed concentrations of the 12 SPs analyzed (Σ12SP) in both surface and core sediments compared with rural samples, suggesting that urban areas near aquatic environments posed high risks for SPs. The mean concentration of Σ12SP in surface sediments of each river was generally higher than that found in core sediments from its corresponding estuary, perhaps implying recent increases in SP usage. Surface sediments were significantly dominated by cypermethrin and permethrin, whereas core sediments were dominated by permethrin and es/fenvalerate. The compositional distributions demonstrated a spatial variation for surface sediments because urban sediments generally contained greater percentages of permethrin and cypermethrin, but rural sediments had significant levels of es/fenvalerate and cypermethrin. In all sediment cores, the percentage of permethrin gradually increased, whereas es/fenvalerate tended to decrease, from the bottom sediments to the top, indicating that the former represented fresh input, whereas the latter represented historical residue. Most urban samples would be expected to be highly toxic to benthic organisms due to the residue of SPs based on a calculation of toxic units (TUs) using toxicity data of the amphipod Hyalella azteca. However, low TU values were found for the samples from rural areas. These results indicate that the bottom sediments were exposed to high risk largely by the residual SPs from urban areas. The summed TUs were mostly attributable to cypermethrin, followed by λ-cyhalothrin and es/fenvalerate. Despite permethrin contributing ∼28.7 % of the Σ12SP concentration, it only represented 6.34 % of the summed TUs. Therefore, our results suggest that high levels of urbanization can increase the accumulation of SPs in aquatic environments.

Occurrence, source identification and ecological risk evaluation of metal elements in surface sediment: toward a comprehensive understanding of heavy metal pollution in Chaohu Lake, Eastern China.

In the present study, surface sediment samples from 48 sites covering the whole water area and three main estuaries of Chaohu Lake were collected to determine the concentrations of 25 metal elements using microwave-assisted digestion combined with ICP-MS. Spatial variation, source appointments, and contamination evaluation were examined using multivariate statistical techniques and pollution indices. The results show that for the elements Cd, Pb, Zr, Hf, U, Sr, Zn, Th, Rb, Sn, Cs, Tl, Bi, and Ba, which had higher coefficients of variation (CV), the concentrations were significantly higher in the eastern lake than in the western lake, but other elements with low CV values did not show spatial differences. The accumulation of Cu, Zn, Rb, Sr, Zr, Cd, Sn, Cs, Ba, Hf, Ta, Tl, Pb, Bi, U, and Th in the surface sediments was inferred as long-term agricultural cultivation impact, but that of Ti, V, Cr, Mn, Co, and Ni may have been a natural occurrence. The contribution from industrial and municipal impact was negligible, despite the rapid urbanization around the studied area. Principal component analysis-multiple linear regression (PCA-MLR) predicted the contribution from agricultural activities to range from 0.45 ± 1.31% for Co to 92.7 ± 17.7% for Cd. The results of the pollution indices indicate that Chaohu Lake was weakly to moderately affected by Ti, V, Cr, Mn, Co, and Ni but was severely contaminated by Hf and Cd. The overall pollution level in the eastern lake was higher than that in the western lake with respect to the pollution level index (PLI). Therefore, our results can help comprehensively understand the sediment contamination by metals in Chaohu Lake.

[Preparation of γ-Fe2O3 Catalyst by Heat Treatment of Natural Limonite for Selective Catalytic Reduction of NO by NH3].

Natural limonite was used as a precursor to prepare γ-Fe2O3 via thermal treatment. The influences of reaction temperature, manganese oxides existing in limonite and coexisting SO2 and H2O on the catalytic reduction activity of the preparedγ-Fe2O3 were evaluated, and the activity of SCR was compared with that of α-Fe2O3, by means of XRD, XRF, XPS, NH3-TPD, FT-IR and so on. The results showed that because the surface acidity of γ-Fe2O3 is stronger, the SCR temperature window of γ-Fe2O3 was 200-350℃ being broader than that of α-Fe2O3 (200-300℃), and in the active temperature window, the NO removal reached over 99%. The existence of MnO2 in the newly formed γ-Fe2O3 slightly decreased the SCR reactivity at lower temperature (100-200℃), while it decreased the SCR reactivity at higher temperature (400-450℃). The existence of SO2 led to the shifting of temperature window by 100℃ from 200-350℃ to 300-450℃, and the volume fraction of 5%H2O only had a tiny negative effect on the SCR reactivity of γ-Fe2O3. However, the coexisting SO2 and H2O, especially when the volume fraction of SO2 reached 0.12%, significantly decreased the SCR reactivity due to the generation of ammonium sulfate. Besides, although the magnetic susceptibility of reacted γ-Fe2O3 experienced a slight decrease compared with the newly prepared γ-Fe2O3, the catalysts could still be used repeatedly by magnetic recycling.

[Modeling the Environmental Behaviors and Ecological Risks of Permethrin in Chaohu Lake].

Environmental pollution caused by synthetic pyrethroid insecticides has received a great deal of attention with the increase in usage recently.To understand the occurrence, environmental processes, fate and ecological impact of permethrin in Chaohu Lake, fugacity based multimedia fate model combining species sensitivities model (SSD) were employed.The concentration distribution, and transfer fluxes were predicted under nonequilibrium steady-state condition, and the effect of input parameter on the outputs was evaluated by sensitive and uncertainty analysis.Furthermore, SSD model of aquatic organisms was constructed for permethrin to assess the potential ecological risk and to determine the maximum annual input amount of permethrin for the purpose of protecting 95% of species.The results showed that the predicted concentrations of permethrin in air, water and sediment were 3.99×10-16, 5.63×10-11, 1.95×10-5mol·m-3, and sediment was the largest sink.Most permethrin was transported from water to air via volatilization, but elimination from air was mostly by particle dry deposition.Permethrin in water was predominately from advection, and was removed by deposition of suspended particulate matter.Sediment associated permethrin was generally derived from suspended particulate matter deposition, and was eliminated by resuspension and sediment burial.The results of SSD model suggested HC5 value was at 0.97 ng·L-1, which was much higher than the predicted environmental concentration of permethrin in water.Only 0.77% of species was possibly impacted by exposure to permethrin.In order to protect 95% of species in Chaohu Lake, the maximum annual input amount of permethrin should be controlled below 78.2 t·a-1.

Component analysis and heavy metal adsorption ability of extracellular polymeric substances (EPS) from sulfate reducing bacteria.

Extracellular polymeric substances (EPS) play an important role in the treatment of acid mine drainage (AMD) by sulfate-reducing bacteria (SRB). In this paper, Desulfovibrio desulfuricans was used as the test strain to explore the effect of heavy metals on the components and adsorption ability of EPS. Fourier-transform infrared (FTIR) spectroscopy analysis results showed that heavy metals did not influence the type of functional groups of EPS. Potentiometric titration results indicated that the acidic constants (pKa) of the EPS fell into three ranges of 3.5-4.0, 5.9-6.7, and 8.9-9.8. The adsorption site concentrations of the surface functional groups also increased. Adsorption results suggested that EPS had a specific binding affinity for the dosed heavy metal, and that EPS extracted from the Zn(2+)-dosed system had a higher binding affinity for all heavy metals. Additionally, Zn(2+) decreased the inhibitory effects of Cd(2+) and Cu(2+) on the SRB.

Comparison of hematite-facilitated anaerobic digestion of acetate and beef extract.

The effect of hematite with different specific surface areas (SSA) on anaerobic methanogenic process was investigated in this study using two different carbon sources (acetate or beef extract). Comparative analyses showed that methane generation rate, microbial growth and the starting-up duration were all significantly enhanced by hematite. The reduction rate of high SSA hematite was 2.5-3.5 times greater than that of low SSA hematite. This work indicated that low SSA hematite was superior to high SSA hematite in facilitating methanogenesis which was partially attributed to the lower affinity for the iron-reduction bacteria.

[Photocatalytic Degradation of Gaseous Toluene by a Photo-Fenton Reaction].

In this study, the performance of photo-Fenton reaction on decomposition of toluene was investigated by a flowing column using toluene as a representative of volatile organic pollutants (VOCs). The effects of initial pH, H2O2 concentration, Fe2+ concentration, initial concentration of toluene on degradation of toluene by photo-Fenton reaction were evaluated. Mass spectrometry and gas chromatograph were utilized to detect the products. The results showed that the introduction of UV greatly enhanced the Fenton reaction by improving the generation of hydroxyl radicals. When the initial concentration of toluene was 260 mg x m(-3), the toluene removal can achieve 98% under the following experimental conditions: initial pH = 3.0, H2O2 20 mmol x L(-1), Fe2+ 0.3 mmol x L(-1). Furthermore, no other intermediate except CO2 was detected in the reaction that photocatalytic degradation of toluene in waste gas by the photo-Fenton, which indicates all the degraded toluene was mineralized into CO2.

PAHs in sediment cores at main river estuaries of Chaohu Lake: implication for the change of local anthropogenic activities.

In the present study, 28 polycyclic aromatic hydrocarbons (PAHs) were investigated in four sediment cores collected from the main river estuaries of Chaohu Lake, one of the severely polluted lakes in China. The results indicate that elevated concentrations of total PAHs (Σ28PAH) were found in the samples from the estuary of Nanfei River (ENF), considering BaP-based total toxicity equivalent (TEQ-BaP) and toxic unit (TU) results; there are potential adverse environmental implications. The total organic carbon (TOC) played an important role on the accumulation of PAHs at ENF and the estuary of Tongyang River (ETY). The predominant PAHs are high molecular weight (HMW) homologous for all samples; as a result, industrial wastewater from a steel company is expectedly the key source of PAHs in ENF, while coke consumption would be the important source of PAHs at other three sampling sites. Vertical distribution of PAHs in the sediment cores could be explained by the local social and economic activities. Furthermore, a minor variation of PAH composition in the sediment core could be justified by the stable structure of energy consumption in the Anhui Province. These results justify the need for further enhancement of industrial wastewater treatment and development of renewable energies which are the key factors on the control of PAH pollution in China.

[Influence of goethite on anaerobic fermentation of organic fraction of municipal solid waste (OFMSW)].

Effects of goethite on the anaerobic fermentation process of organic fraction of municipal solid wastes, including the biogas production and characteristics of leachate, were investigated in the anaerobic digesters constructed by PVC. The results showed that the addition of goethite promoted hydrolysis and acidogenesis efficiency of solid wastes and gas production rate. The total gas volume was 163.4 L,which increased by 20% compared to the blank. The intermediate products of Fe2+ , NH+4 -N, NO-3 -N, COD and organic acids in the leachate were analyzed. Results showed that the addition of goethite reduced the system ORP to - 124 mV which could improve the activity of the anaerobic microorganism. Addition of goethite could also promote the utilization of organic acids which decreased the inhibition effects of organic acids on the anaerobic microorganism.

Competitive adsorption of heavy metal by extracellular polymeric substances (EPS) extracted from sulfate reducing bacteria.

Competitive adsorption of heavy metals by extracellular polymeric substances (EPS) extracted from Desulfovibrio desulfuricans was investigated. Chemical analysis showed that different EPS compositions had different capacities for the adsorption of heavy metals which was investigated using Cu(2+) and Zn(2+). Batch adsorption tests indicated that EPS had a higher combined ability with Zn(2+) than Cu(2+). This was confirmed and explained by Fourier transform infrared (FTIR) and excitation-emission matrix (EEM) spectroscopy analysis. FTIR analysis showed that both polysaccharides and protein combined with Zn(2+) while only protein combined with Cu(2+). EEM spectra further revealed that tryptophan-like substances were the main compositions reacted with the heavy metals. Moreover, Zn(2+) had a higher fluorescence quenching ability than Cu(2+).

Synthetic effect between iron oxide and sulfate mineral on the anaerobic transformation of organic substance.

Synthetic effect between sulfate minerals (gypsum) and iron oxide (hematite) on the anaerobic transformation of organic substance was investigated in the current study. The results showed that gypsum was completely decomposed while hematite was partially reduced. The mineral phase analysis results showed that FeS and CaCO3 was the major mineralization product. Methane generation process was inhibited and inorganic carbon contents in the precipitates were enhanced compared to the control without hematite and gypsum. The inorganic carbon content increased with the increasing of hematite dosages. Co-addition of sulfate minerals and iron oxide would have a potential application prospect in the carbon sequestration area and reduction of the greenhouse gas release. The results would also reveal the role of inorganic mineral in the global carbon cycle.

[Effect of the interaction of microorganisms and iron oxides on arsenic releasing into groundwater in Chinese Loess].

A large part of groundwater in the Chinese Loess Plateau area is characterized by high arsenic concentration. Anaerobic bacteria have been considered to play key roles in promoting arsenic releasing from loess to groundwater. However, this hypothesis remains unconfirmed. Based on modeling experiments, this study investigated the speciation of arsenic in loess, and then determined the release rates and quantities of arsenic with the mediation of anaerobic bacteria. The results showed that arsenic contents in loess were between 23 mg.kg-1 and 30 mg.kg-1. No obvious arsenic content difference among loess samples was observed. The ratios for specific adsorbed, iron oxides co-precipitated and silicate co-precipitated arsenic were 37.76% , 36. 15% and 25. 69% , respectively. Indigenous microorganisms, dissimilatory iron reducing bacteria (DIRB) and sulfate reducing bacteria (SRB) could all promote the release of arsenic from loess. Organic matters highly affected the release rates. More than 100 mg.L-1 sodium lactate was required for all bacterial experiments to facilitate obvious arsenic release. Considering the redox condition in loess, the contribution of SRB to arsenic release in loess area was less feasible than that of DIRB and indigenous microorganisms.

PAHs in the Chinese environment: levels, inventory mass, source and toxic potency assessment.

This paper presents a systematic but preliminary study on the levels, inventory mass, emission sources and risk of exposure to PAHs in China by examining 14 polycyclic aromatic hydrocarbons (from the 16 priority PAHs listed by the U.S. EPA, excluding naphthalene and acenaphthylene) in four main environmental media (air, water, soil and sediment). The concentration of individual PAHs in the air, soil, freshwater, seawater, freshwater sediment and marine sediment of China was compared with the global concentration range (GCR) of PAHs from a large number of studies. The PAH levels were found at the high end of the GCR in the air, at the upper middle of the GCR in the water body, and at the middle of the GCR in the soil and sediment. These indicate that PAHs still are emitted heavily in China. About 530 000 tons of Σ14PAH was estimated to be distributed into these four media in China. Soil possesses the highest proportion of the PAHs (60%), and the air has the lowest proportion (<0.5%). Therefore, the soil and sediment play an important role in the storage of PAHs. More than 10 thousand tons of PAHs are emitted from all kinds of sources. Firewood, straw, domestic and coking were considered as the main emissions of PAHs in the energy supply. A benzo[a]pyrene (BaP) based hazard quotient (HQ) was introduced to assess the potential toxic risk of exposure. The terrestrial water environment was found to have a high BaP exposure. The HQ value was more than 1 for 58% of freshwater and 39% of freshwater sediment samples. Urban and developed sites were considered to have high BaP exposure risk.