Facile fabrication of dolomite-doped biochar/bentonite for effective removal of phosphate from complex wastewaters

● Dolomite-doped biochar/bentonite was synthesized for phosphate removal. ● DO/BB exhibited a high phosphate adsorption capacity in complex water environments. ● PVC membrane incorporated with DO/BB can capture low concentration phosphate. ● Electrostatic interaction, complexation and precipitation are main mechanisms. The removal of phosphate from wastewater using traditional biological or precipitation methods is a huge challenge. The use of high-performance adsorbents has been shown to address this problem. In this study, a novel composite adsorbent, composed of dolomite-doped biochar and bentonite (DO/BB), was first synthesized via co-pyrolysis. The combination of initial phosphate concentration of 100 mg/L and 1.6 g/L of DO/BB exhibited a high phosphate-adsorption capacity of 62 mg/g with a removal efficiency of 99.8%. It was also stable in complex water environments with various levels of solution pH, coexisting anions, high salinity, and humic acid. With this new composite, the phosphate concentration of the actual domestic sewage decreased from 9 mg/L to less than 1 mg/L, and the total nitrogen and chemical oxygen demand also decreased effectively. Further, the cross-flow treatment using a PVC membrane loaded with DO/BB (PVC-DO/BB), decreased the phosphate concentration from 1 to 0.08 mg/L, suggesting outstanding separation of phosphate pollutants via a combination of adsorption and separation. In addition, the removal of phosphate by the PVC-DO/BB membrane using NaOH solution as an eluent was almost 90% after 5 cycles. The kinetic, isotherm and XPS analysis before and after adsorption suggested that adsorption via a combination of electrostatic interaction, complexation and precipitation contributed to the excellent separation by the as-obtained membranes.     

Adsorption of phosphate ions from water using a novel cellulose-based adsorbent

A novel cellulose-based adsorbent, iron(III)-coordinated amino-functionalised poly(glycidylmethacrylate)-grafted cellulose [Fe(III)–AM-PGMACell] was developed for the removal of phosphate from water and wastewater. The scanning electron micrograph showed that AM-PGMACell has a rougher surface than cellulose and the adsorption of Fe(III) on AM-PGMACell made the surface even rougher. Infrared spectroscopy revealed that amino groups on the surface of AM-PGMACell complexed with Fe(III) played an important role in the removal of phosphate from solutions. X-Ray diffraction patterns showed a decrease in crystallinity after graft copolymerisation onto cellulose. The effects of contact time, initial sorbate concentration, pH, agitation speed, dose of adsorbent and temperature on the removal process were investigated. Maximum removal of 99.1% was observed for an initial concentration of 25 mg·L ^?1 at pH 6.0 and an adsorbent dose of 2.0 g·L ^?1. A two-step pseudo-first-order kinetic model and Sips isotherm model represented the measured data very well. Complete removal of 11.6 mg·L ^?1 phosphate from fertiliser industry wastewater was achieved by 1.6 g·L ^?1 Fe(III)–AM-PGMACell. The adsorbent exhibited very high reusability for several cycles. Overall, the study demonstrated that Fe(III)–AM-PGMACell can be used as an efficient adsorbent for the removal and recovery of phosphate from water and wastewater.     

一株新的反硝化短程除硫菌的鉴定及主要培养因素筛选

依据反硝化除硫原理,以味精废水污泥为种泥,利用全混流反应器富集并分离出同步反硝化短程除硫菌(SNBI),采用传统与现代分子生物学相结合的手段对其鉴定,以确定其分类地位;同时对SNB1的主要培养因素(营养和环境)进行筛选.结果表明:SNB1的形态特征及生理生化指标与Thauera selenatis最相似,同源性达99.0%,属短杆菌属,尚无中文命名;生理生化指标、富集条件及富集过程物料平衡显示SNB1是一株兼性厌氧反硝化除硫菌;培养SNB1的最佳碳源为蔗糖,最佳氮源为蛋白胨,最佳培养温度为35℃,最适宜pH范围为7～9;最佳条件培养时,OD_(650)和对数细菌数量(CFU)呈直线相关,相关系数R~2=0.981.     

Fabrication of magnetic multi-template molecularly imprinted polymer composite for the selective and efficient removal of tetracyclines from water

• Magnetic multi-template molecularly imprinted polymer composite was synthesized. • MIP composite was used as the adsorbent for removal of tetracyclines from water. • MIP composite showed excellent adsorption selectivity toward tetracyclines. • MIP composite possessed good reusability. Antibiotic contamination of the water environment has attracted much attention from researchers because of their potential hazards to humans and ecosystems. In this study, a multi-template molecularly imprinted polymer (MIP) modified mesoporous silica coated magnetic graphene oxide (MGO@MS@MIP) was prepared by the surface imprinting method via a sol-gel process and was used for the selective, efficient and simultaneous removal of tetracyclines (TCs), including doxycycline (DC), tetracycline (TC), chlorotetracycline (CTC) and oxytetracycline (OTC) from water. The synthesized MIP composite was characterized by Fourier transform infrared spectroscopy, transmission electron microscope and thermogravimetric analysis. The adsorption properties of MGO@MS@MIP for these TCs were characterized through adsorption kinetics, isotherms and selectivity tests. The MIP composite revealed larger adsorption quantities, excellent selectivity and rapid kinetics for these four tetracyclines. The adsorption process was spontaneous and endothermic and followed the Freundlich isotherm model and the pseudo-second-order kinetic model. The MGO@MS@MIP could specifically recognize DC, TC, CTC and OTC in the presence of some chemical analogs. In addition, the sorption capacity of the MIP composite did not decrease significantly after repeated application for at least five cycles. Thus, the prepared magnetic MIP composite has great potential to contribute to the effective separation and removal of tetracyclines from water.     

Simultaneous removal of hydrogen sulfide and volatile organic sulfur compounds in off-gas mixture from a wastewater treatment plant using a two-stage bio-trickling filter system

A two-stage BTF system was established treating odorous off-gas mixture from a WWTP. The two-stage BTF system showed resistance for the lifting load of H₂S and VOSC. Miseq Illumina sequencing showed separated functional microbial community in BTFs. Avoiding H₂S inhibition and enhancement of VOSC degradation was achieved. Key control point was discussed to help industrial application of the system. Simultaneous removal of hydrogen sulfide (H₂S) and volatile organic sulfur compounds (VOSCs) in off-gas mixture from a wastewater treatment plant (WWTP) is difficult due to the occasional inhibitory effects of H₂S on VOSC degradation. In this study, a two-stage bio-trickling filter (BTF) system was developed to treat off-gas mixture from a real WWTP facility. At an empty bed retention time of 40 s, removal efficiencies of H₂S, methanethiol, dimethyl sulfide, and dimethyl disulfide were 90.1, 88.4, 85.8, and 61.8%, respectively. Furthermore, the effect of lifting load shock on system performance was investigated and results indicated that removal of both H₂S and VOSCs was slightly affected. Illumina Miseq sequencing revealed that the microbial community of first-stage BTF contained high abundance of H₂S-affinity genera including Acidithiobacillus (51.43%), Metallibacterium (25.35%), and Thionomas (8.08%). Analysis of mechanism demonstrated that first stage of BTF removed 86.1% of H₂S, mitigating the suppression on VOSC degradation in second stage of BTF. Overall, the two-stage BTF system, an innovative bioprocess, can simultaneously remove H₂S and VOSC.     

Release of phosphorous from igneous phosphate rock through bioturbation: a low-cost approach for phosphorous fertilization in fish farms

The influence of bioturbation caused by common carp fry was treated in 24 transparent polythene jars (5?L each) in the laboratory and in outdoor vats (150?L), increasing the fertilizer value of phosphate rock in eight treatment combinations in triplicate. Input of water soluble reactive phosphate (SRP) was determined to quantify the effects of bioturbation, fish excrements and soil. The level of SRP in water was always lowest in the control series. Introduction of common carp fry resulted in a net increase of 0.009–0.010?mg phosphate g^?1day^?1 of SRP attributable to the effect of fish excrement. Bioturbation caused by common carp resulted in as high as a 64.8 to 90% influx of phosphate from bottom soil in the presence of phosphate rock but only about 6.3 to 7.2% in the absence of phosphate rock. The bioturbation that occurred in this treatment resulted in a significant release of phosphorous into the overlying water from an apatite source. The results confirm the environment friendly application of phosphate rock in fish-farming ponds at low cost.     

Fabrication of highly efficient Bi2WO6/CuS composite for visible-light photocatalytic removal of organic pollutants and Cr(VI) from wastewater

• A novel Bi₂WO₆/CuS composite was fabricated by a facile solvothermal method. • This composite efficiently removed organic pollutants and Cr(VI) by photocatalysis. • The DOM could promoted synchronous removal of organic pollutants and Cr(VI). • This composite could be applied at a wide pH range in photocatalytic reactions. • Possible photocatalytic mechanisms of organic pollutants and Cr(VI) were proposed. A visible-light-driven Bi₂WO₆/CuS p-n heterojunction was fabricated using an easy solvothermal method. The Bi₂WO₆/CuS exhibited high photocatalytic activity in a mixed system containing rhodamine B (RhB), tetracycline hydrochloride (TCH), and Cr (VI) under natural conditions. Approximately 98.8% of the RhB (10 mg/L), 87.6% of the TCH (10 mg/L) and 95.1% of the Cr(VI) (15 mg/L) were simultaneously removed from a mixed solution within 105 min. The removal efficiencies of TCH and Cr(VI) increased by 12.9% and 20.4%, respectively, in the mixed solution, compared with the single solutions. This is mainly ascribed to the simultaneous consumption electrons and holes, which increases the amount of excited electrons/holes and enhances the separation efficiency of photogenerated electrons and holes. Bi₂WO₆/CuS can be applied over a wide pH range (2–6) with strong photocatalytic activity for RhB, TCH and Cr(VI). Coexisiting dissolved organic matter in the solution significantly promoted the removal of TCH (from 74.7% to 87.2%) and Cr(VI) (from 75.7% to 99.9%) because it accelerated the separation of electrons and holes by consuming holes as an electron acceptor. Removal mechanisms of RhB, TCH, and Cr(VI) were proposed, Bi₂WO₆/CuS was formed into a p-n heterojunction to efficiently separate and transfer photoelectrons and holes so as to drive photocatalytic reactions. Specifically, when reducing pollutants (e.g., TCH) and oxidizing pollutants (e.g., Cr(VI)) coexist in wastewater, the p-n heterojunction in Bi₂WO₆/CuS acts as a “bridge” to shorten the electron transport and thus simultaneously increase the removal efficiencies of both types of pollutants.     

Combined Fenton process and sulfide precipitation for removal of heavy metals from industrial wastewater: Bench and pilot scale studies focusing on in-depth thallium removal

Addition of alkali to pH 10 is effective for precipitation of precipitable metals. Fenton treatment is effective for substantial removal of Tl, Cd, Cu, Pb, and Zn. Sulfide precipitation is a final step for removal of trace Tl, Cd, Cu, Pb, and Zn. Bench and pilot studies demonstrated the effectiveness of this combined technique. Thallium (Tl) in industrial wastewater is a public health concern due to its extremely high toxicity. However, there has been limited research regarding Tl removal techniques and engineering practices to date. In this investigation, bench and pilot studies on advanced treatment of industrial wastewater to remove Tl to a trace level were conducted. The treatment process involved a combination of hydroxide precipitation, Fenton oxidation, and sulfide precipitation. While hydroxide precipitation was ineffective for Tl+ removal, it enabled the recovery of approximately 70%–80% of Zn as Zn hydroxide in alkaline conditions. The Fenton process provided good Tl removal (>95%) through oxidation and precipitation. Tl was then removed to trace levels (<1.0 µg/L) via sulfide precipitation. Effective removal of other heavy metals was also achieved, with Cd<13.4 µg/L, Cu<39.6 µg/L, Pb<5.32 µg/L, and Zn<357 µg/L detected in the effluent. X-ray photoelectron spectroscopy indicated that Tl2S precipitate formed due to sulfide precipitation. Other heavy metals were removed via the formation of metal hydroxides during hydroxide precipitation and Fenton treatment, as well as via the formation of metal sulfides during sulfide precipitation. This combined process provides a scalable approach for the in-depth removal of Tl and other heavy metals from industrial wastewater.     

Achieving biodegradability enhancement and acute biotoxicity removal through the treatment of pharmaceutical wastewater using a combined internal electrolysis and ultrasonic irradiation technology

Actual pharmaceutical wastewater was treated using a combined ultrasonic irradiation (US) and iron/coke internal electrolysis (Fe/C) technology. A significant synergetic effect was observed, showing that ultrasonic irradiation dramatically enhanced the chemical oxygen demand (COD) removal efficiencies by internal electrolysis. The effects of primary operating factors on COD removal were evaluated systematically. Higher ultrasonic frequency and lower pH values as well as longer reaction time were favorable to COD removal. The ratio of biochemical oxygen demand (BOD) and COD (B/C) of the wastewater increased from 0.21 to 0.32 after US-Fe/C treatment. An acute biotoxicity assay measuring the inhibition of bioluminescence indicated that the wastewater with overall toxicity of 4.3 mg-Zn²⁺·L^-1 was reduced to 0.5 mg-Zn²⁺·L^-1 after treatment. Both the raw and the treated wastewater samples were separated and identified. The types of compounds suggested that the increased biodegradability and reduced biotoxicity resulted mainly from the destruction of N,N-2 dimethyl formamide and aromatic compounds in the pharmaceutical wastewater.     

Low-cost and efficient adsorbent derived from pyrolysis of Jatropha curcas seeds for the removal of Cu2+ from aqueous solutions

Biochar, is a low-cost material that can be used as an alternative adsorbent for the removal of heavy metals. In this study, a low-cost and efficient adsorbent synthesised from Jatropha curcas seeds was used for the uptake of Cu²⁺ from aqueous solutions. The as-prepared adsorbent was characterised by scanning electron microscopy and Brunauer–Emmett–Teller analysis post calcination at 500 °C, its BET surface area and total pore volume were 39.62?m²?g^?1 and 0.049?m³?g^?1, respectively. Subsequently, the effects of initial pH of the solution, contact time, and adsorbent material dosage on the adsorption of Cu²⁺ by the prepared adsorbent were investigated. The as-prepared adsorbent exhibited a high performance, with a maximum adsorption amount of 32.895?mg?g^?1 for Cu²⁺ at pH 5.0 and 25 °C, owing to the presence of ?OH, C=O, C–O, Si-O-Si, and O-Si-O on its surface. The predominant Cu²⁺ adsorption mechanism was assumed to be ion exchange. Notably, the Cu²⁺ adsorption could attain equilibrium within 90?min. In addition, the fact that the Langmuir model was a better fit than the Freundlich model for the isotherm data of Cu²⁺ adsorption by the as-prepared adsorbent suggested that the adsorption of Cu²⁺ was a monolayer adsorption process.     

Adsorptive removal of rhodamine B from textile wastewater using water chestnut (Trapa natans L.) peel: adsorption dynamics and kinetic studies

Water chestnut peel, an agricultural bio-waste, was used as a biosorbent for removal of rhodamine B (RhB), basic textile dye, from an aqueous solution. The effects of various experimental parameters were studied. The equilibrium data correlated well with a Freundlich isotherm (R² = 0.98–0.99) followed by a Halsey isotherm model (R² = 0.98–0.99) which indicated heterogeneity of the adsorbent surface and multilayer adsorption of RhB dye onto the water chestnut peel waste (WCPW). High correlation coefficients (R² = 0.99) together with close agreement between experimental q_e (0.4–1.7 mg g^?1) and calculated q_e (0.4–2.5 mg g^?1) suggested that the adsorption process followed pseudo-second-order kinetics, with k₂ values in the range of 52–3.4 × 10^?1 g mg^?1 min^?1 at different concentrations. The overall mechanism of adsorption was controlled by both liquid-film and intra-particle diffusions. The negative values of change in Gibb's free energy (?ΔG⁰ = 19.2–29.2 kJ mol^?1) and positive values of change in enthalpy (ΔH⁰ = 30.9–117.6 kJ mol^?1) revealed the process to be spontaneous and endothermic. WCPW was found to be an effective adsorbent for removal of RhB, a cationic dye, from an aqueous solution.     

Effective removal of Cobalt(II) ions from aqueous solutions and nuclear industry wastewater using sulfhydryl and carboxyl functionalised magnetite nanocellulose composite: batch adsorption studies

A new adsorbent sulfhydryl and carboxyl functionalized magnetite nanocellulose composite [(MB-IA)-g-MNCC] was synthesized by graft co-polymerization of itaconic acid onto magnetite nanocellulose (MNCC) using EGDMA as cross linking agent and K₂S₂O₈ as free radical initiator. The adsorption occurs maximum in the pH 6.5. The best fitted kinetic model was found to be pseudo-second-order kinetics. Therefore the mechanism of Co(II) adsorption onto (MB-IA)-g-MNCC follows ion exchange followed by complexation. The Langmuir model was the best fitted isotherm model for the adsorption of Co(II) onto the (MB-IA)-g-MNCC. Simulated nuclear power plant coolant water samples were also treated with (MB-IA)-g-MNCC to demonstrate its efficiency for the removal of Co(II) from aqueous solutions in the presence of other metal ions. To recover the adsorbed Co(II) ions and also to regenerate the adsorbent to its original state 0.1?M HCl was used as suitable desorbing agent. Six cycles of adsorption-desorption experiments were conducted and was found that adsorption capacity of (MB-IA)-g-MNCC has been decreased from 97.5% in the first cycle to 84.7% in the sixth cycle. Recovery of Co(II) using 0.1?M HCl decreased from 93.2% in the first cycle to 79.3% in the sixth cycle.

Abbreviations: T: absolute temperature; q_e: amount adsorbed at equilibrium; q_t: amount adsorbed at time t; CELL: cellulose; Co: cobalt; C_e: concentration at equilibrium; C_HCl: concentration of HCl; C_NaOH: concentration of NaOH; C_A: concentrations of acid; C_B: concentrations of base; W_g: dry weight of composite; W_i: dry weight of MNCC; DS: energy dispersive spectra; EGDMA: ethylene glycol dimethacrylate; Ce: equilibrium concentration; K_L: equilibrium constant; F: Faradays constant; FTIR: Fourier transform infrared spectra; ΔG^o: free energy change; K_F: Freundlich adsorption capacity; 1/n: Freundlich constant; R: gas constant; D: grafting density; EC_o: initial concentration; IA: itaconic acid; IA-g-MNCC: itaconic acid-grafted-magnetite nanocellulose composite; b: Langmuir constant; MNCC: magnetite nanocellulose composite; Q⁰: Maximum adsorption capacity; (MB-IA)-g-MNCC: 2-mercaptobenzamide modified itaconic acid-grafted-magnetite nanocellulose composite; NC: nanocellulose; pH_pzc: Point of zero charge; K₂S₂O₈: potassium peroxy sulphate; k₁: pseudo-first-order rate constant; k₂: pseudo-second-order rate constant; SEM: scanning Electron Microscope; b_s: Sips adsorption capacity; Q_s: Sips maximum adsorption capacity; ΔH°: standard enthalpy change; ΔS°: standard entropy change; A: surface area; σ₀: surface charge density; 1/n_s: surface heterogeneity factor; VSM: vibrating sample magnetometer; V: volume of solution; W: weight of (MB-IA)-g-MNCC; M_composite: weight of the composite; XRD: X-ray diffraction     

Principal components derived from soil physicochemical data explained a land degradation gradient,and suggested the applicability of new indexes for estimation of soil productivity in the Sakaerat Environmental Research Station,Thailand

To find a principal component (PC) that quantifies the degree of soil degradation, we analyzed various physicochemical characteristics of soils over a land degradation gradient related to aboveground vegetation in the Sakacrat Environmental Research Station (SERS), Thailand. The aboveground vegetative types representing the degradation gradient were bare ground (BG, highly degraded), dry dipterocarp forest (DDF, moderately disturbed) and dry evergreen forest (DEF, the original vegetation). Soils under these vegetative types were sampled in February (dry season). March just after temporal precipitation) and June (rainy season) 2001. Through the period of this research, the degradation was consistently explained by sandy texture, high bulk density, lower pH, high exchangeable acidity, poor mineral and organic nutrients and dryness. Principal component analysis (PCA) was applied to determine significant principal components (PCs) that clarify the differences in soil properties between the vegetative types and between the timing of soil sampling. The PC loadings suggested that the first PC was the component that indicates total fertility of soil in the site, while the fifth PC indicates the dry to wet seasonal transition. The first PC was named the total fertility component (TFC). The linear regression between the TFC score and recently proposed indexes, the soil fertility index (SFI) or the soil evaluation factor (SEF), was highly significant (p < 0.001), indicating that the SFI and the SEF are applicable to measuring total fertility of soils in the SERS.