The Ti-modified sepiolite (Ti-Sep)-supported Mn-Cu mixed oxide (yMn5Cu/Ti-Sep) catalysts were synthesized using the co-precipitation method. The materials were characterized by the X-ray diffraction scanning electron microscope, N2 adsorption-desorption, H2-TPR, O2-TPD, and XPS techniques, and their catalytic activities for CO oxidation were evaluated. It was found that the catalytic activities of yMn5Cu/Ti-Sep were higher than those of 5Cu/Ti-Sep and 30Mn/Ti-Sep, and the Mn/Cu molar ratio had a distinct influence on catalytic activity of the sample. Among the yMn5Cu/Ti- Sep samples, the 30Mn5Cu/Ti-Sep catalyst showed the best activity (which also outperformed the 30Mn5Cu/Sep catalyst), giving the highest reaction rate of 0.875 × 10–3 mmol·g–1·s–1 and the lowest T50% and T100% of 56°C and 86°C, respectively. Moreover, the 30Mn5Cu/Ti-Sep possessed the best low-temperature reducibility, the lowest O2 desorption temperature, and the highest surface Mn3+/Mn4+ atomic ratio. It is concluded that factors, such as the strong interaction between the copper or manganese oxides and the Ti-Sep support, good low-temperature reducibility, and good mobility of chemisorbed oxygen species, were responsible for the excellent catalytic activity of 30Mn5Cu/Ti-Sep.
The relationship between the improvement of sludge dewaterability and variation of organic matters has been studied in the process of sludge pre-conditioning with modified cinder, especially for extracellular polymeric substances (EPS) in the sludge. During the conditioning process, the decreases of total organic carbon (TOC) and soluble chemical oxygen demand (SCOD) were obviously in the supernatant especially for the acid modified cinder (ACMC), which could be attributed to the processes of adsorption and sweeping. The reduction of polysaccharide and protein in supernatant indicated that ACMC might adsorb EPS so that the tightly bound EPS (TB-EPS) decreased in sludge. In the case of ACMC addition with 24 g·L–1, SRF of the sludge decreased from 7.85 × 1012 m·kg–1 to 2.06 × 1012 m·kg–1, and the filter cake moisture decreased from 85% to 60%. The reconstruction of “floc mass” was confirmed as the main sludge conditioning mechanism. ACMC promoted the dewatering performance through the charge neutralization and adsorption bridging with the negative EPS, and provided firm and dense structure for sludge floc as skeleton builder. The passages for water quick transmitting were built to avoid collapsing during the high-pressure process.
Denitrifying biofilter (DNBF) is widely used for advanced nitrogen removal in the reclaimed wastewater treatment plants (RWWTPs). Manual control of DNBF easily led to unstable process performance and high cost. Consequently, there is a need to automatic control of two decisive operational processes, carbon dosage and backwash, in DNBF. In this study, online control of DNBF was investigated in the pilot-scale DNBF (600 m3·d–1), and then applied in the full-scale DNBF (10 × 104 m3·d–1). A novel simple online control strategy for carbon dosage with the effluent nitrate as the sole control parameter was designed and tested in the pilot-scale DNBF. Backwash operation was optimized based on the backwash control strategy using turbidity as control parameter. Using the integrated control strategy, in the pilot-scale DNBF, highly efficient nitrate removal with effluent TN lower than 3 mg·L–1 was achieved and DNBF was not clogged any more. The online control strategy for carbon dosage was successfully applied in a RWWTP. Using the online control strategy, the effluent nitrate concentration was controlled relatively stable and carbon dosage was saved for 18%.
It is common that 2,4,6-trichlorophenol (TCP) coexists with nitrate or nitrite in industrial wastewaters. In this work, simultaneous reductive dechlorination of TCP and denitrification of nitrate or nitrite competed for electron donor, which led to their mutual inhibition. All inhibitions could be relieved to a certain degree by augmenting an organic electron donor, but the impact of the added electron donor was strongest for TCP. For simultaneous reduction of TCP together with nitrate, TCP’s removal rate value increased 75% and 150%, respectively, when added glucose was increased from 0.4 mmol?L–1 to 0.5 mmol?L–1 and to 0.76 mmol?L–1. For comparison, the removal rate for nitrate increased by only 25% and 114% for the same added glucose. The relationship between their initial biodegradation rates versus their initial concentrations could be represented well with the Monod model, which quantified their half-maximum-rate concentration (KS value), and KS values for TCP, nitrate, and nitrite were larger with simultaneous reduction than independent reduction. The increases in KS are further evidence that competition for the electron donor led to mutual inhibition. For bioremediation of wastewater containing TCP and oxidized nitrogen, both reduction reactions should proceed more rapidly if the oxidized nitrogen is nitrite instead of nitrate and if readily biodegradable electron acceptor is augmented.
A novel microorganism embedding material was prepared to enhance the biological nitrogen removal through simultaneous nitrification and denitrification. Polyvinyl alcohol (PVA), sodium alginate (SA) and cyclodextrin (CD) were used to compose gel bead with embedded activated sludge. The effects of temperature, CD addition and concentrations of PVA and SA on nitrogen removal were evaluated. Results show that the gel bead with CD addition at 30°C contributed to the highest nitrogen removal efficiency and nitrogen removal rate of 85.4% and 2.08 mgL·(L·h)–1, respectively. Meanwhile, negligible NO3– and NO2– were observed, proving the occurrence of simultaneous nitrification and denitrification. The High-Throughput Sequencing confirms that the microbial community mainly contained Comamonadaceae in the proportion of 61.3%. Overall, CD increased gel bead’s porosity and resulted in the high specific endogenous respiration rate and high nitrogen removal efficiency, which is a favorable additional agent to the traditional embedding material.
This paper studied the biofilm properties and corrosion behavior of sulfate reducing bacteria (SRB) on stainless steel 316L (SS316L) surface in circulating cooling water system with and without additives including hydroxy ethyl fork phosphonic acid (HEDP), dodecyl dimethyl benzyl ammonium chlotide (1227) and NaClO. Biochemical technique, electrochemical technology, X-ray photoelectron spectroscopy (XPS) and scanning electron microscope (SEM) were used. The results show that the extracellular polymeric substance (EPS) in biofilm attached on the SS316L surface mainly contain proteins and polysaccharides, the contents are 98 ug·cm-2 and 635ug·cm-2, respectively. The polysaccharides were cut by 1227 about 80%, while 55% by NaClO. The proteins were reduced by NaClO about 53%, while only 30% by 1227. The potentiodynamic polarization shows that the corrosion potential of SS316L was enhanced from -0.495 V to -0.390 V by the chemical additives, delaying the occurrence of the corrosion. And the corrosion rate was also reduced from 5.19 × 10-3 mm·a-1 to 2.42 × 10-3 mm·a-1. But NaClO still caused pitting corrosion after sterilizing the bacteria, while 1227 can form a protective film on the surface of SS316L. Though HEDP contribute to the bacteria activity, it can enhance the breakdown potential. XPS results confirmed that 1227 can change the value of C:O in the biofilm attached on metal surface, and NaClO can eliminate the existence of amidogen. This study would provide some recommendations for the selection of chemical additives in the thermal power plant.
Currently, increasing amounts of end-of-life (EoL) electronic products are being generated due to their reduced life spans and the unavailability of suitable recycling technologies. In particular, waste printed circuit boards (PCBs) have become of global concern with regard to environmental issues because of their high metal and toxic material contents, which are pollutants. There are many environmental threats owed to the disposal of electronic waste; off-gasses, such as dioxins, furans, polybrominated organic pollutants, and polycyclic aromatic hydrocarbons, can be generated during thermal treatments, which can cause serious health problems if effective off-gas cleaning systems are not developed and improved. Moreover, heavy metals will dissolve, and release into the ground water from the landfill sites. Such waste PCBs contain precious metals which are of monetary value. Therefore, it is beneficial to recover the metal content and protect the environment from pollution. Hydrometallurgy is a successful technique used worldwide for the recovery of precious metals (especially gold and silver) from ores, concentrates, and waste materials. It is generally preferred over other methods because it can offer high recovery rates at a relatively low cost. This article reviews the recent trends and developments with regard to the recycling of precious metals from waste PCBs through hydrometallurgical techniques, such as leaching and recovery.
Exploration of heavy metals and organic pollutants, their leaching capacity along with health and environmental risks in contaminated industrial construction and demolition waste (ICDW) within a pesticide manufacturing plant were investigated. A maximum content of 90.8 mg?kg–1 Cd was found present in the wastes, which might originate from phosphorus rocks and industrial sulfuric acid used in pesticide production processes. An average concentration of 979.8 mg?kg–1 dichlorovos and other 11 organophosphorus pesticide were also detected. Relatively high leaching rates of around 4.14‰were obtained from laboratory simulated ICDW using both glacial acetic acid-sodium hydroxide and deionized water. Pesticide pollutants had the strongest tendency to retaining on dry bricks (leaching rate 1.68‰) compared to mortar-coatings, etc. due to their different physical characteristics and octanol-water partioning coefficient. Mobility of pesticide from on-site ICDW by water was spatially correlated to waste types, process sections and human activities, with a flux of leaching rate between 5.9‰ to 27.4%. Risk-based corrective action (RBCA) model was used to simulate the risk of contaminated ICDW debris randomly scattered. Oral and dermal ingestion amount by local workers was 9.8 × 10–3 and 1.9 × 10–2 mg?(kg?d)–1, respectively. Potential leaching risk to aquatic systems exceeded the limit for nearly 75% waste. Environmental and health risk exceedance was found in most ICDW, while the risk value of the most severely contaminated brick waste was 660 times beyond critical level. Implications for waste management involving construction and deconstruction work, waste transferring and regulation supplying were also provided.
The gene for the catalytic domain of thermostable endo-β-1,3-glucanase (laminarinase) LamA was cloned from Thermotoga maritima MSB8 and heterologously expressed in a bioengineered Synechococcus sp. PCC 7002. The mutant strain was cultured in a photobioreactor to assess biomass yield, recombinant laminarinase activity, and CO2 uptake. The maximum enzyme activity was observed at a pH of 8.0 and a temperature of 70°C. At a CO2 concentration of 5%, we obtained a maximum specific growth rate of 0.083 h–1, a biomass productivity of 0.42 g?L–1?d–1, a biomass concentration of 3.697 g?L–1, and a specific enzyme activity of the mutant strain of 4.325 U?mg–1 dry mass. All parameters decreased as CO2 concentration increased from 5% to 10% and further to 15% CO2, except enzyme activity, which increased from 5% to 10% CO2. However, the mutant culture still grew at 15% CO2 concentration, as reflected by the biomass productivity (0.26 g?L–1?d–1), biomass concentration (2.416 g?L–1), and specific enzyme activity (3.247 U?mg–1 dry mass).
Biological synthesis of quantum dots (QDs) as an environmental-friendly and facile preparation method has attracted increasing interests. However, it is difficult to distinguish the roles of bio-thiols in QDs synthesis process because of the complex nature in organisms. In this work, the CdSe QDs synthesis conditions in organisms were reconstructed by using a simplified in vitro approach to uncover the roles of two small bio-thiols in the QDs formation. CdSe QDs were synthesized with glutathione (GSH) and L-cysteine (Cys) respectively. Compared with Cys at the same molar concentration, the CdSe QDs synthesized by GSH had a larger and broader particle size distribution with improved optical properties and crystal structure. Furthermore, quantum chemical calculations indicate that the stronger Cd2+ binding capacity of GSH contributed a lot to the CdSe QDs formation despite of the greater capability Cys for selenite reduction. This work clearly demonstrates the different roles of small thiols in the Cd2+ stabilization in the environment and biomimetic QDs synthesis process.
Conventional biological removal of nitrogen and phosphorus is usually limited due to the lack of biodegradable carbon source, therefore, new methods are needed. In this study, a new alternative consisting of enhanced biological phosphorus removal (EBPR) followed by partial nitritationanammox (PN/A), is proposed to enhance nutrients removal from municipal wastewater. Research was carried out in a laboratory-scale system of combined two sequencing batch reactors (SBRs). In SBR1, phosphorus removal was achieved under an alternating anaerobic-aerobic condition and ammonium concentration stayed the same since nitrifiers were washed out from the reactor under short sludge retention time of 2–3 d. The remaining ammonium was further treated in SBR2 where PN/A was established by inoculation. A maximum of nitrogen removal rate of 0.12 kg N?m–3?d–1 was finally achieved. During the stable period, effluent concentrations of total phosphorus and total nitrogen were 0.25 and 10.8 mg?L–1, respectively. This study suggests EBPR-PN/A process is feasible to enhance nutrients removal from municipal wastewater of low influent carbon source.
Sulfamethoxzole (SMX) and trimethoprim (TMP), two combined-using sulfonamide antibiotics, have gained increasing attention in the surface water, groundwater and the drinking water because of the ecological risk. The removal of TMP and SMX by artificial composite soil treatment system (ACST) with different infiltration rates was systematically investigated using K+, Na+, Ca2+, Mg2+ hydrogeochemical indexes. Batch experiments showed that the sorption onto the low-cost and commercially available clay ceramsites was effective for the removal of SMX and TMP from water. The column with more silty clay at high infiltration rate (1.394 m·d–1) had removal rates of 80% to 90% for TMP and 60% to 70% for SMX. High SMX and TMP removal rates had a higher effluent concentration of K+, Ca2+ and Mg2+ and had a lower effluent Na+ concentration. Removal was strongly related to sorption. The results showed that the removal of SMX and TMP was related to hydrogeochemical processes. In this study, ACST is determined to be applicable to the drinking water plants.
A biofilm membrane bioreactor (BF-MBR) and a conventional membrane bioreactor (MBR) were parallelly operated for treating digested piggery wastewater. The removal performance of COD, TN, NH4+-N, TP as well as antibiotics were simultaneously studied when the hydraulic retention time (HRT) was gradually shortened from 9 d to 1 d and when the ratio of influent COD to TN was changed. The results showed that the effluent quality in both reactors was poor and unstable at an influent COD/TN ratio of 1.0±0.2. The effluent quality was significantly improved as the influent COD/TN ratio was increased to 2.3±0.5. The averaged removal rates of COD, NH4+-N, TN and TP were 92.1%, 97.1%, 35.6% and 54.2%, respectively, in the BF-MBR, significantly higher than the corresponding values of 91.7%, 90.9%, 17.4% and 31.9% in the MBR. Analysis of 11 typical veterinary antibiotics (from the tetracycline, sulfonamide, quinolone, and macrolide families) revealed that the BF-MBR removed more antibiotics than the MBR. Although the antibiotics removal decreased with a shortened HRT, high antibiotics removals of 86.8%, 80.2% and 45.3% were observed in the BF-MBR at HRTof 5–4 d, 3–2 d and 1 d, respectively, while the corresponding values were only 83.8%, 57.0% and 25.5% in the MBR. Moreover, the BF-MBR showed a 15% higher retention rate of antibiotics and consumed 40% less alkalinity than the MBR. Results above suggest that the BF-MBR was more suitable for digested piggery wastewater treatment.
The effect of microwave pretreatment on the anaerobic degradation of hyacinth was investigated using response surface methodology (RSM). The components of lignin and the other constituents of hyacinth were altered by microwave pretreatment. Comparison of the near-infrared spectra of hyacinth pretreated by microwave irradiation and water-heating pretreatment revealed that no new compounds were generated during hyacinth pretreatment by microwave irradiation. Atomic force microscopy observations indicated that the physical structures of hyacinth were disrupted by microwave pretreatment. The yield of methane per gram of the microwave-irradiated substrate increased by 38.3% as compared to that of the substrate pretreated via water-heating. A maximum methane yield of 221 mL?g-sub–1 was obtained under the optimum pretreatment conditions (substrate concentration (PSC) = 20.1 g?L–1 and pretreatment time (PT) = 14.6 min) using RSM analysis. A maximum methane production rate of 0.76 mL?h–1?g-sub–1 was obtained by applying PSC = 9.5 g?L–1 and PT = 11 min. Interactive item coefficient analysis showed that methane production was dependent on the PSC and PT, separately, whereas the interactive effect of the PSC and PT on methane production was not significant. The same trend was also observed for the methane production rate.
Mercury enrichment in response to elevated atmospheric mercury concentrations in the organs of rape (Brassica napus) was investigated using an open top chamber fumigation experiment and a soil mercury enriched cultivation experiment. Results indicate that the mercury concentration in leaves and stems showed a significant variation under different concentrations of mercury in atmospheric and soil experiments while the concentration of mercury in roots, seeds and seed coats showed no significant variation under different atmospheric mercury concentrations. Using the function relation established by the experiment, results for atmospheric mercury sources in rape field biomass showed that atmospheric sources accounted for at least 81.81%of mercury in rape leaves and 32.29% of mercury in the stems. Therefore, mercury in the aboveground biomass predominantly derives from the absorption of atmospheric mercury.
Leaching behavior and gastrointestinal bioaccessibility of rare earth elements (REEs) from hospital waste incineration (HWI) fly and bottom ash samples collected from Beijing and Nanjing Cities were assessed. In the same ash sample, the leaching concentrations of individual REEs determined by the Toxicity Characteristic Leaching Procedure (TCLP) were higher than those detected by the European standard protocol (EN-type test), thereby suggesting that the low pH value of leaching solution was an important factor influencing the leachability of REE. The REE bioaccessibility results, which were evaluated using the physiologically based extraction test (PBET), indicated that REEs were highly absorbed during gastric phase by dissolution; and subsequently precipitated and/or re-adsorbed in small intestinal phase. The relative amounts of the total REEs extracted by the TCLP method, EN-type test and PBET test were compared. In addition to the pH value of extraction solutions, the chelating role of REEs with organic ligands used in the PBET method was also an important parameter affecting REE adsorption in human body. Additionally, this study showed that REEs were extracted by these methods as concomitants of heavy metals and anions (NO3–, F–, SO42–, and Cl–) from HWI ash, which probably caused the remarkably complex toxicity on human body by the exposure pathway.
Cadmium (Cd) and lead (Pb) in water and soil could be adsorbed by biochar produced from corn straw. Biochar pyrolyzed under 400°C for 2 h could reach the ideal removal efficiencies (99.24%and 98.62% for Cd and Pb, respectively) from water with the biochar dosage of 20 g·L–1 and initial concentration of 20 mg·L–1. The pH value of 4–7 was the optimal range for adsorption reaction. The adsorption mechanism was discussed on the basis of a range of characterizations, including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and Raman analysis; it was concluded as surface complexation with active sorption sites (-OH, -COO-), coordination with π electrons (C = C, C = O) and precipitation with inorganic anions (OH-, CO32–, SO42–) for both Cd and Pb. The sorption isotherms fit Langmuir model better than Freundlich model, and the saturated sorption capacities for Cd and Pb were 38.91 mg·g-1 and 28.99 mg·g–1, respectively. When mixed with soil, biochar could effectively increase alkalinity and reduce bioavailability of heavy metals. Thus, biochar derived from corn straw would be a green material for both removal of heavy metals and amelioration of soil.
Chromium oxide and manganese oxide promoted ZrO2-CeO2 catalysts were prepared by a homogeneous precipitation method for the selective catalytic reduction of NOx with NH3. A series of characterization including X-ray diffraction (XRD), high-resolution transmission electron microscope (HR-TEM), Brunauer–Emmett–Teller (BET) surface area analysis, H2 temperatureprogrammed reduction (H2-TPR), and X-ray photoelectron spectroscopy (XPS) were used to evaluate the influence of the physicochemical properties on NH3-SCR activity. Cr-Zr-Ce and Mn-Zr-Ce catalysts are much more active than ZrO2-CeO2 binary oxide for the low temperature NH3-SCR, mainly because of the high specific surface area, more surface oxygen species, improved reducibility derived from synergistic effect among different elements. Mn-Zr-Ce catalyst exhibited high tolerance to SO2 and H2O. Cr-Zr-Ce mixed oxide exhibited>80% NOx conversion at a wide temperature window of 100°C–300°C. In situ DRIFT studies showed that the addition of Cr is beneficial to the formation of Bronsted acid sites and prevents the formation of stable nitrate species because of the presence of Cr6 +. The present mixed oxide can be a candidate for the low temperature abatement of NOx.
Eutrophication with a large number of Microcystis aeruginosa commonly occurs worldwide, thereby threatening the aquatic ecosystem and human health. In this study, four kinds of algicides were tested to explore their influence on cell density and chlorophyll-a of M. aeruginosa. Results showed that aluminum silicate agent, which inhibited more than 90% cell growth compared with the control group, demonstrated the strongest inhibition effect immediately on M. aeruginosa growth. Furthermore, the production and release of microcystin (MC)-LR were investigated. Aluminum silicate, CuSO4, and Emma-11 were more effective than pyrogallic acid in disrupting the cells of M. aeruginosa, thereby increasing the extracellular MC-LR concentration. Aluminum silicate caused the highest extracellular MC-LR concentration of more than 45 mg·L–1. Biotoxicity was also detected to evaluate the environmental risks of MC-LR release, which were related to the usages of different algicides. Extracellular MC-LR concentration mostly increased when the biotoxicity of algae solution increased. The experiments were also designed to reveal the effects of physical conditions in riverways, such as natural sunlight, aeration and benthal sludge, on MC-LR degradation. These findings indicated that UV rays in sunlight, which can achieve a MC-LR removal efficiency of more than 15%, played an important role in MC-LR degradation. Among all the physical pathways of MC-LR removal, benthal sludge adsorption presented the optimal efficiency at 20%.
With extensive use of lithium ion batteries (LIBs), amounts of LIBs were discarded, giving rise to growth of resources demand and environmental risk. In view of wide usage of natural graphite and the high content (12%–21%) of anode graphite in spent LIBs, recycling anode graphite from spent LIBs cannot only alleviate the shortage of natural graphite, but also promote the sustainable development of related industries. After calcined at 600°C for 1 h to remove organic substances, anode graphite was used to prepare graphene by oxidation-reduction method. Effect of pH and N2H4·H2O amount on reduction of graphite oxide were probed. Structure of graphite, graphite oxide and graphene were characterized by XRD, Raman and FTIR. Graphite oxide could be completely reduced to graphene at pH 11 and 0.25 mL N2H4·H2O. Due to the presence of some oxygen-containing groups and structure defects in anode graphite, concentrated H2SO4 and KMnO4 consumptions were 40% and around 28.6% less than graphene preparation from natural graphite, respectively.
