Sulfur cycle as an electron mediator between carbon and nitrate in a constructed wetland microcosm

• Fe(III) accepted the most electrons from organics, followed by NO₃^‒, SO₄^2‒, and O₂. • The electrons accepted by SO₄^2‒ could be stored in the solid AVS, FeS₂-S, and S⁰. • The autotrophic denitrification driven by solid S had two-phase characteristics. • A conceptual model involving electron acceptance, storage, and donation was built. • S cycle transferred electrons between organics and NO₃^‒ with an efficiency of 15%. A constructed wetland microcosm was employed to investigate the sulfur cycle-mediated electron transfer between carbon and nitrate. Sulfate accepted electrons from organics at the average rate of 0.84 mol/(m³·d) through sulfate reduction, which accounted for 20.0% of the electron input rate. The remainder of the electrons derived from organics were accepted by dissolved oxygen (2.6%), nitrate (26.8%), and iron(III) (39.9%). The sulfide produced from sulfate reduction was transformed into acid-volatile sulfide, pyrite, and elemental sulfur, which were deposited in the substratum, storing electrons in the microcosm at the average rate of 0.52 mol/(m³·d). In the presence of nitrate, the acid-volatile and elemental sulfur were oxidized to sulfate, donating electrons at the average rate of 0.14 mol/(m³·d) and driving autotrophic denitrification at the average rate of 0.30 g N/(m³·d). The overall electron transfer efficiency of the sulfur cycle for autotrophic denitrification was 15.3%. A mass balance assessment indicated that approximately 50% of the input sulfur was discharged from the microcosm, and the remainder was removed through deposition (49%) and plant uptake (1%). Dominant sulfate-reducing (i.e., Desulfovirga, Desulforhopalus, Desulfatitalea, and Desulfatirhabdium) and sulfur-oxidizing bacteria (i.e., Thiohalobacter, Thiobacillus, Sulfuritalea, and Sulfurisoma), which jointly fulfilled a sustainable sulfur cycle, were identified. These results improved understanding of electron transfers among carbon, nitrogen, and sulfur cycles in constructed wetlands, and are of engineering significance.     

Catalytic oxidation of CO over Pt/Fe3O4 catalysts: Tuning O2 activation and CO adsorption

• Strong metal-support interaction exists on Pt/Fe₃O₄ catalysts. • Pt metal particles facilitate the formation of oxygen vacancies on Fe₃O₄. • Fe₃O₄ supports enhance the strength of CO adsorption on Pt metal particles. The self-inhibition behavior due to CO poisoning on Pt metal particles strongly impairs the performance of CO oxidation. It is an effective method to use reducible metal oxides for supporting Pt metal particles to avoid self-inhibition and to improve catalytic performance. In this work, we used in situ reductions of chloroplatinic acid on commercial Fe₃O₄ powder to prepare heterogeneous-structured Pt/Fe₃O₄ catalysts in the solution of ethylene glycol. The heterogeneous Pt/Fe₃O₄ catalysts achieved a better catalytic performance of CO oxidation compared with the Fe₃O₄ powder. The temperatures of 50% and 90% CO conversion were achieved above 260°C and 290°C at Pt/Fe₃O₄, respectively. However, they are accomplished on Fe₃O₄ at temperatures higher than 310°C. XRD, XPS, and H₂-TPR results confirmed that the metallic Pt atoms have a strong synergistic interaction with the Fe₃O₄ supports. TGA results and transient DRIFTS results proved that the Pt metal particles facilitate the release of lattice oxygen and the formation of oxygen vacancies on Fe₃O₄. The combined results of O₂-TPD and DRIFTS indicated that the activation step of oxygen molecules at surface oxygen vacancies could potentially be the rate-determining step of the catalytic CO oxidation at Pt/Fe₃O₄ catalysts. The reaction pathway involves a Pt-assisted Mars-van Krevelen (MvK) mechanism.     

A review of measurement methods for peracetic acid (PAA)

• Physical and chemical properties and application of peracetic acid solution. • Determination method of high concentration peracetic acid. • Determination method of residual peracetic acid (low concentration). Peroxyacetic acid has been widely used in food, medical, and synthetic chemical fields for the past several decades. Recently, peroxyacetic acid has gradually become an effective alternative disinfectant in wastewater disinfection and has strong redox capacity for removing micro-pollutants from drinking water. However, commercial peroxyacetic acid solutions are primarily multi-component mixtures of peroxyacetic acid, acetic acid, hydrogen peroxide, and water. During the process of water treatment, peroxyacetic acid and hydrogen peroxide (H₂O₂) often coexist, which limits further investigation on the properties of peroxyacetic acid. Therefore, analytical methods need to achieve a certain level of selectivity, particularly when peroxyacetic acid and hydrogen peroxide coexist. This review summarizes the measurement and detection methods of peroxyacetic acid, comparing the principle, adaptability, and relative merits of these methods.     

Diffusive gradients in thin films using molecularly imprinted polymer binding gels for in situ measurements of antibiotics in urban wastewaters

• Selective molecularly imprinted polymer (MIP) binding gel was prepared. • MIP-DGT showed excellent uptake performance for antibiotics. • In situ measurement of antibiotics in wastewaters via MIP-DGT was developed. • The MIP-DGT method was robust, reliable, and highly sensitive. Urban wastewater is one of main sources for the introduction of antibiotics into the environment. Monitoring the concentrations of antibiotics in wastewater is necessary for estimating the amount of antibiotics discharged into the environment through urban wastewater treatment systems. In this study, we report a novel diffusive gradient in thin films (DGT) method based on molecularly imprinted polymers (MIPs) for in situ measurement of two typical antibiotics, fluoroquinolones (FQs) and sulfonamides (SAs) in urban wastewater. MIPs show specific adsorption toward their templates and their structural analogs, resulting in the selective uptake of the two target antibiotics during MIP-DGT deployment. The uptake performance of the MIP-DGTs was evaluated in the laboratory and was relatively independent of solution pH (4.0–9.0), ionic strength (1–750 mmol/L), and dissolved organic matter (DOM, 0–20 mg/L). MIP-DGT samplers were tested in the effluent of an urban wastewater treatment plant for field trials, where three SA (sulfamethoxazole, sulfapyridine, and trimethoprim) and one FQ (ofloxacin) antibiotics were detected, with concentrations ranging from 25.50 to 117.58 ng/L, which are consistent with the results measured by grab sampling. The total removal efficiency of the antibiotics was 80.1% by the treatment plant. This study demonstrates that MIP-DGT is an effective tool for in situ monitoring of trace antibiotics in complex urban wastewaters.     

A fractal derivative model to quantify bed-load transport along a heterogeneous sand bed

Environmental Fluid Mechanics - Bed-load transport is a complex process exhibiting anomalous dynamics, which cannot be efficiently described using the traditional advection–diffusion...     

In situ electron-induced reduction of NOx via CNTs activated by DBD at low temperature

• An in situ electron-induced deNO_x process with CNT activated by DBD was achieved. • Carbon atoms on CNT surface were verified to be excited by plasma in DBD-CNT system. • Reactions between NO_x and excited C result in synergistic effect of DBD-CNT system. In this study, a new in situ electron-induced process is presented with carbon nanotubes (CNTs) as a reduction agent activated by dielectric barrier discharge (DBD) for nitrogen oxide (NO_x) abatement at low temperature (<407 K). Compared with a single DBD system and a DBD system with activated carbon (DBD-AC), a DBD system with carbon nanotubes (DBD-CNT) showed a significant promotion of NO_x removal efficiency and N₂ selectivity. Although the O₂ content was 10%, the NO_x conversion and N₂ selectivity in the DBD-CNT system still reached 64.9% and 81.9% at a specific input energy (SIE) of 1424 J/L, and these values decreased to 16.8%, 31.9% and 43.2%, 62.3% in the single DBD system and the DBD-AC system, respectively. X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were utilized to investigate surface changes in the CNTs after activation by DBD to explore the NO_x reduction abatement mechanism of this new process. Furthermore, the outlet gas components were also observed via Fourier transform infrared spectroscopy (FTIR) to help reveal the NO_x reduction mechanism. Experimental results verified that carbon atoms excited by DBD and the structure of CNTs contributed to the synergistic activity of the DBD-CNT system. The new deNO_x process was accomplished through in situ heterogenetic reduction reactions between the NO_x and carbon atoms activated by the plasma on the CNTs. In addition, further results indicated that the new deNO_x process exhibited acceptable SO₂ tolerance and water resistance.     

二氧化锰基纳米材料对重金属离子的去除及机理研究进展

重金属离子对人类健康和环境安全产生了严重威胁,因此重金属废水高效处理成为了环境领域最具挑战性的热点问题之一.二氧化锰(MnO_2)是一种环境友好型金属氧化物,具有来源广泛、成本低廉、形貌多样、晶型丰富、结构稳定、粒径可控等优异的性质,在重金属离子的去除应用上展现出巨大的潜力.近年来,人们利用MnO_2基纳米材料在重金属离子的有效治理方面开展了大量的研究.本文综述了MnO_2基纳米材料在重金属离子环境修复方面取得的研究进展,包括MnO_2的制备和改性方法,MnO_2基纳米材料在水溶液重金属离子去除中的应用及吸附作用机制,并对研究方向进行了总结和展望,旨在为进一步设计合成对重金属离子的吸附去除具有实际应用价值的MnO_2基纳米材料提供参考.     

全氟辛烷磺酸盐(PFOS)对半滑舌鳎(Cynoglossus semilaevis)免疫相关基因表达的影响

为了解全氟辛烷磺酸盐(perfluorooctane sulfonate, PFOS)暴露对半滑舌鳎(Cynoglossus semilaevis)免疫功能的影响,在实验室条件下,运用RT-PCR方法分析了PFOS暴露对半滑舌鳎热休克蛋白hsp70、hsp90、C型凝集素(c-type lectin)和细胞色素c氧化酶(cytochrome c oxidase, cox)等4种免疫相关基因表达水平的影响。实验测定了上述4种基因在半滑舌鳎肝、鳃、肠及肌肉4种不同组织中随时间(0、24 h、48 h、96 h和7 d)的表达变化情况。结果表明,在4种组织中,hsp70基因的表达与对照相比为上调,其中,肝组织hsp70基因的表达量显著高于其他各组织,且表达高峰值的出现也早于其他各组织;hsp90基因在肝和鳃组织中表达量随时间不同而波动,在肠组织中表达上调,在肌肉中表达显著下调;c-type lectin基因表达量与对照组相比表达显著下调或无明显差异;cox基因在肝组织和肠组织中表达下调,在鳃和肌肉中表达上调。上述研究结果表明,PFOS能引起免疫相关基因的表达变化,对半滑舌鳎具有潜在的免疫毒性。肝组织中各免疫基因对PFOS胁迫的响应高于其他组织。本研究可为阐明全氟辛烷磺酸盐对半滑舌鳎的免疫毒性提供基础数据。     

Increasing polybrominated diphenyl ether (PBDE) contamination in sediment cores from the inner Clyde Estuary,UK

The concentrations of 16 polybrominated diphenyl ether (PBDE) congeners in six short sediment cores from the Clyde Estuary were determined by gas-chromatography mass-spectrometry. Total PBDE concentrations ranged from 1 to 2,645 μg/kg and the average concentration was 287 μg/kg. BDE-209 was the main congener and varied from 1 to 2,337 μg/kg. Elevated total PBDE concentrations were observed close to the sediment surface in the uppermost 10 cm of four of the six sediment cores. Comparison of the down core PBDE profiles revealed that the increase was driven by the accumulation of deca-BDE. Although the deca-BDE mix was dominant, the presence of lower molecular weight congeners BDE-47, BDE-99, BDE-183 and BDE-153 at most sediment intervals suggested additional sources of penta-BDE and octa-BDE pollution. Changing PBDE source input was the major factor in influencing the proportion of nona-brominated congeners, although other explanations such as post burial photo-debromination of BDE-209 cannot be entirely discounted. A clear cascading to lower hepta-, hexa-, and penta-homologues was not found. The increase in total PBDE concentrations and particularly the deca-BDE may possibly be ascribed to the use and subsequent disposal of electrical appliances such as televisions and computers. In the Clyde sediments, the proportion of nona-brominated congeners was higher than that reported for commercial mixtures. This might be due to changing sources of PBDEs or post burial photo-debromination of BDE-209.     

Photo-polymerization of triclosan in aqueous solution induced by ultraviolet radiation

The formation of 2,8-dichlorodibenzo-p-dioxin and other harmful degradation products in the photo-degradation process of triclosan is of increasing concern. Here we worked on the identification of polymerized products at high triclosan concentration and on the mechanism of photoreaction. Five dimmers and two trimers of triclosan were detected by liquid chromatography-mass spectrum analysis. 2,8-dichlorodibenzo-p-dioxin was also identified by comparing with an authentic standard. Relatively low pH and high concentration favored the polymerization of triclosan. Three main routes of photoreaction were postulated, namely dechlorination, ring closure and polymerization.