UV/H2O2 oxidation of tri(2-chloroethyl) phosphate: Intermediate products, degradation pathway and toxicity evaluation

Tri(2-chloroethyl) phosphate(TCEP) with the initial concentration of 5 mg/L was degraded by UV/H₂O₂ oxidation process. The removal rate of TCEP in the UV/H₂O₂ system was 89.1% with the production of Cl-and PO₄^3- of 0.23 and 0.64 mg/L. The removal rate of total organic carbon of the reaction was 48.8% and the pH reached 3.3 after the reaction. The oxidative degradation process of TCEP in the UV/H₂O₂ system ...     

Degradation of micropolluants in flow-through VUV/UV/H2O2 reactors: Effects of H2O2 dosage and reactor internal diameter

The degradation of atrazine (ATZ), sulfamethoxazole (SMX) and metoprolol (MET) in flow-through VUV/UV/H₂O₂ reactors was investigated with a focus on the effects of H₂O₂ dosage and reactor internal diameter (ID). Results showed that the micropollutants were degraded efficiently in the flow-through VUV/UV/H₂O₂ reactors following the pseudo first-order kinetics (R² > 0.92). However, the steady-state assumption (SSA) kinetic model being vital in batch reactors was found invalid in flow-through reactors where fluid mixing was less sufficient. With the increase of H₂O₂ dosage, the ATZ removal efficiency remained almost constant while the SMX and MET removal was enhanced to different extents, which could be explained by the different reactivities of the pollutants towards HO^?. A larger reactor ID resulted in lower degradation rate constants for all the three pollutants on account of the lower average fluence rate, but the change in energy efficiency was much more complicated. In reality, the electrical energy per order (E_EO) of the investigated VUV/UV/H₂O₂ treatments ranged between 0.14–0.20, 0.07–0.14 and 0.09–0.26 kWh/m³/order for ATZ, SMX and MET, respectively, with the lowest E_EO for each pollutant obtained under varied H₂O₂ dosages and reactor IDs. This study has demonstrated the efficiency of VUV/UV/H₂O₂ process for micropollutant removal and the inadequacy of the SSA model in flow-through reactors, and elaborated the influential mechanisms of H₂O₂ dosage and reactor ID on the reactor performances.     

Formation of halonitromethanes from methylamine in the presence of bromide during UV/Cl2 disinfection

The UV/Cl₂ process is commonly used to achieve a multiple-barrier disinfection and maintain residuals. The study chose methylamine as a precursor to study the formation of high-toxic halonitromethanes (HNMs) in the presence of bromide ions (Br⁻) during UV/Cl₂ disinfection. The maximum yield of HNMs increased first and then decreased with increasing concentration of Br⁻. An excessively high concentration of Br⁻ induced the maximum yield of HNMs in advance. The maximum bromine incorporation factor (BIF) increased, while the maximum bromine utilization factor (BUF) decreased with the increase of Br⁻ concentration. The maximum yield of HNMs decreased as pH value increased from 6.0 to 8.0 due to the deprotonation process. The BUF value remained relatively higher under an acidic condition, while pH value had no evident influence on the BIF value. The maximum yield of HNMs and value of BUF maximized at a Cl₂:Br⁻ ratio of 12.5, whereas the BIF value remained relatively higher at low Cl₂:Br⁻ ratios (2.5 and 5). The amino group in methylamine was first halogenated, and then released into solution as inorganic nitrogen by the rupture of C-N bond or transformed to nitro group by oxidation and elimination pathways. The maximum yield of HNMs in real waters was higher than that in pure water due to the high content of dissolved organic carbon. Two real waters were sampled to verify the law of HNMs formation. This study helps to understand the HNMs formation (especially brominated species) when the UV/Cl₂ process is adopted as a disinfection technique.     

Photodegradation of nitroaromatic compounds in aqueous solutions in the UV/H2O2 process

Photodegradation of nitrobenzene and nitrophenols in aqueous solutions by means of UV/H2 O2 process was studied in the Rayox batch reactors. Three nitrophenol isomers were identified as main photoproducts in the irradiated NB aqueous solutions. The distribution of nitrophenol isomers follows the order p-〉 m-〉 o-nitrophenol. Other intermediates detected include nitrohydroquinone, nitrocatechol, catechol, benzoquinone, phenol, nitrate/nitrite ions, formic acid, glyoxylic acid, maleic acid, oxalic acid and some aliphatic ketones and aldehydes. The degradation of nitrobenzene and nitrophenols at initial stages follows the first-order kinetics and the decay rate constants for nitrobenzene（NB） are around l0^-3-10^-2 s^-1 and for nitrophenols are around 10^-2 s^-1. The decomposition of H2 O2 in the presence of NB and each nitrophenol isomers follows zero-order kinetics. The quantum yields at initial stages for NB decay were estimated around 0.30 to 0.36, and for NPs decay is around 0.31-0.54.     

UV/H2O2法处理焦化废水的试验研究

焦化废水是一种典型的成分复杂的难降解有机废水。实验利用UV／H2O2法对焦化废水的处理进行研究,探讨了不同反应时间、H2O2投加量、pH值等因素对COD去除率及色度降解效果的影响。结果表明．废水起始COD质量浓度为1334mg几时,H2O2投加浓度为45mmol/L,pH值=11,紫外灯照射60min,COD去除率可达70％以上;随着H2O2投加量的增加以及pH值的升高,污水的色度明显降低。     

Role of interfacial electron transfer reactions on sulfamethoxazole degradation by reduced nontronite activating H2O2

It has been documented that organic contaminants can be degraded by hydroxyl radicals ( • OH) produced by the activation of H₂ O₂ by Fe(II)-bearing clay. However, the interfacial electron transfer reactions between structural Fe(II) and H 2 O 2 for • OH generation and its effects on contaminant remediation are unclear. In this study, we first investigated the relation between • OH generation sites and sulfamethoxazole (SMX) degradation by activating H₂O₂ using nontronite with different reduction extents. SMX (5.2–16.9 μmol/L) degradation first increased and then decreased with an increase in the reduction extent of nontronite from 22% to 62%, while the • OH production increased continually. Passivization treatment of edge sites and structural variation results revealed that interfacial electron transfer reactions between Fe(II) and H 2 O 2 occur at both the edge and basal plane. The enhancement on basal plane interfacial electron transfer reactions in a high reduction extent rNAu-2 leads to the enhancement on utilization efficiencies of structural Fe(II) and H 2 O 2 for • OH generation.However, the • OH produced at the basal planes is less efficient in oxidizing SMX than that of at edge sites. Oxidation of SMX could be sustainable in the H 2 O 2 /rNAu-2 system through chemically reduction. The results of this study show the importance role of • OH generation sites on antibiotic degradation and provide guidance and potential strategies for antibiotic degradation by Fe(II)-bearing clay minerals in H 2 O 2 -based treatments.     

Inactivation and subsequent reactivation of Aspergillus species by the combination of UV and monochloramine: Comparisons with UV/chlorine

Ultraviolet (UV)/monochloramine (NH₂Cl) as an advanced oxidation process was firstly applied for Aspergillus spores inactivation. This study aims to: i) clarify the inactivation and photoreactivation characteristics of UV/NH₂Cl process, ii) compared with UV/Cl₂ in inactivation efficiency, photoreactivation and energy consumption. The results illustrated that UV/NH₂Cl showed better inactivation efficiency than that of UV alone and UV/Cl₂, and could effectively control the photoreactivation. For instance, the inactivation rates for Aspergillus flavus, Aspergillus niger and Aspergillus fumigatus in the processes of UV/NH₂Cl (2.0 mg/L) was 0.034, 0.030 and 0.061 cm²/mJ, respectively, which were higher than that of UV alone (0.027, 0.026 and 0.024 cm²/mJ) and UV/Cl₂ (0.023, 0.026 and 0.031 cm²/mJ). However, there was no synergistic effect for Aspergillus flavus and Aspergillus fumigatus. As for Aspergillus niger, the best synergistic effect can reach 1.86-log₁₀. This may be due to their different resistance to disinfectants, which were related to the size, an outer layer of rodlets (hydrophobins) and pigments. After UV/NH₂Cl inactivation, the degree of cell membrane damage and intracellular reactive oxygen species were higher than that of UV alone. UV/NH₂Cl had the advantages of high inactivation efficiency and inhibition of photoreactivation, which provides a new entry point for the disinfection of waterborne fungi.     

Enhanced cyanogen chloride formation after UV/PS and UV/H2O2 pre-oxidation and chlorination in natural river water

Ultraviolet/persulfate (UV/PS) and Ultraviolet/hydrogen peroxide (UV/H₂O₂) have attracted much attention in recent years as advanced oxidation processes for water treatment. However, it is not all clear how these two methods affect the formation of cyanogen chloride (CNCl) in the subsequent water chlorination process. In this study, it was found that both UV/H₂O₂ and UV/PS pre-oxidation promoted the formation of CNCl in six actual water samples collected from urban rivers. Glycine, uric acid, arginine and histidine were investigated as the model compounds to explore the effects of different methods on the production of CNCl. The results showed that compared with chlorination alone, pre-oxidation by UV/H₂O₂ and UV/PS can reduce the production of CNCl for glycine and uric acid by up to 95% during post-chlorination process. However, they can greatly promote the formation of CNCl for arginine and histidine by up to 120-fold. In a more detailed investigation, pre-oxidation of histidine formed highly reactive intermediates to chlorine, leading to increased CNCl formation and chlorine consumption. The results showed that the precursors of CNCl was altered after pre-oxidation, and need to be re-evaluated.     

UV/H2Ｏ2/微曝气联用工艺矿化内分泌干扰物BPA试验研究

采用UV/H₂Ｏ₂/微曝气工艺对水中内分泌干扰物双酚A(BPA)的降解与矿化进行了试验研究.该工艺是在UV/H₂Ｏ₂的基础上发展起来的一种新工艺,微曝气在UV光照射下产生了一定量的O₃,提高了·OH的发生率.本试验研究了UV光强、H₂Ｏ₂投加量以及pH值对BPA矿化速率的影响.结果表明,随着UV光强的增大,BPA的矿化速率呈线性增加;当H₂Ｏ₂投加量由5 mg/L增大到20 mg/L时,BPA矿化速率常数k由0.003 2上升到0.025 0;当pH为6.68时,在相同条件下BPA的矿化效果最好.在同一工况条件下,UV/H₂Ｏ₂/微曝气工艺降解BPA的速率远远大于其矿化速率,分析得出在开始反应阶段BPA首先被降解为小分子有机物,随着反应的进一步进行小分子有机物逐步被矿化为无机物.     

A/O生物法处理石化废水的研究

为了处理水质组成复杂,毒性大、有机物浓度较高的石化废水,采用先厌氧后好氧（即A/O生物法）的处理方法。研究结果表明,石化废水经厌氧处理后,其好氧可生化性提高20％～40％;当厌氧反应器进水有机负荷为5.2kgCOD/m³·d,水力停留时间为24h时,BOD5去除率为85％,COD去除率为83％,油去除率为91.1％;当曝气池污泥负荷为0.45kgCOD/kgMLSS·d,水力停留时间为4h时,BOD₅去除率为94.1％,COD去除率为92.7％,油去除率为96.3％。系统COD总去除率为85％～96％,BOD₅总去除率为95％～99％。A/O生物法为石化废水处理提供了理论依据。     

UV/H2O2光催化氧化法处理表面活性剂废水

采用UV/H2O2光催化氧化法处理含表面活性剂废水,考察了反应时间、体系pH值、表面活性剂初始浓度、H2O2投加量、表面活性剂的种类等因素对处理效果的影响,并初步探讨了表面活性剂降解的反应动力学.结果表明,当初始pH值为4、H2O2投加量为1mL/L,反应时间为20min时,表面活性剂DBS的去除率为96%,AOS的去除率为93%,且UV/H2O2体系中,表面活性剂DBS和AOS的降解反应均符合表观拟一级反应动力学特征.     

O/H/O生物工艺中焦化废水含氮化合物的识别与转化

富氮缺磷是焦化废水的特征之一,而含氮化合物存在多种组分与形态,其在废水处理过程中的利用与顺序会影响工艺条件与达标可行性,因此,通过识别含氮化合物的种类并了解其转化可以获得优化的运行工况.为考察含氮化合物的去除过程,在与实际生产330×104t·a-1焦炭工艺相配套的焦化废水处理工程O/H/O生物工艺中,检测了原水与生物出水中含氮化合物的种类与形态,以及各单元工艺中无机氮及部分有机氮化合物的浓度,分析特征化合物的转化.研究发现,焦化废水原水中含有的无机氮化合物主要为NH+4-N(33.6%)、氰化物(7.5%)、硫氰化物(40.4%),NO-2-N及NO-3-N的含量约为1%,折算总氮浓度约为240 mg·L-1,占82.5%左右;有机氮当中,可检测到胺类14种,有机腈类22种,含氮杂环化合物76种,以总氮形式表达其浓度低于50 mg·L-1,约占17.5%.处理过程中,O1反应器能够把氰化物、硫氰化物氧化为氨氮,有机氮发生形态改变;H反应器中,环状含氮化合物通过水解作用实现分子开环转变为氨氮,回流液中的硝态氮实现反硝化转变为氮气;O2反应器能够将低价状态的含氮化合物转变为硝态氮;生物出水中,硝态氮占总氮的70%以上;含氮化合物的转化受反应器的性质与运行条件控制,表现出复杂性.研究指出,焦化废水总氮的控制需要依据含氮化合物种类与形态判断、工艺组合及条件优化综合考虑.     

絮凝沉淀-H2O2/UV体系处理发制品废水的研究

研究了发制品废水经絮凝沉淀－H2O2／UV体系处理的可行性。结果表明，废水经处理后，COD去除率可达90％以上，色度去除率达100％，探讨了投药量、反应pH、反应时间等因素对COD去除率的影响，并比较了H2O2／F^2 、H2O2／UV、H2O2／Fe^2 ／UV三种体系的处理效果。     

Degradation of kanamycin from production wastewater with high-concentration organic matrices by hydrothermal treatment

It is known that many kinds of fermentative antibiotics can be removed by temperatureenhanced hydrolysis from production wastewater based on their easy-to-hydrolyze characteristics. However, a few aminoglycosides are hard to hydrolyze below 100 °C because of their stability expressed by high molecular energy gap( E). Herein, removal of hard-to-hydrolyze kanamycin residue from production wastewater by hydrothermal treatment at subcritical temperatures was investigated. The results showed the reac...     

溶液中阴离子对UV/H2O2降解4-硝基酚的影响

利用间歇式光反应器,研究了溶液中阴离子HCO3-、Cl-、及NO3-对UV/H2O2氧化4-硝基酚的影响.结果表明,UV/H2O2能有效地除去水溶液中4-硝基酚及TOC.随着HCO3-、Cl-及NO3-浓度的增加,4-硝基酚氧化速率减少.溶液中阴离子对UV/H2O2体系中主要氧化剂OH自由基的清除作用是4-硝基酚降解速率下降的原因.利用一级反应动力学对4-硝基酚的降解进行了拟合,得到了满意的结果.     

Removal of Ni(II) from strongly acidic wastewater by chelating precipitation and recovery of NiO from the precipitates

Strongly acidic wastewater produced in nonferrous metal smelting industries often contains high concentrations of Ni(II), which is a valuable metal. In this study, the precipitation of Ni(II) from strongly acidic wastewater using sodium dimethyldithiocarbamate (DDTC) as the precipitant was evaluated. The effects of various factors on precipitation were investigated, and the precipitation mechanism was also identified. Finally, the nickel in the precipitates was recovered following a pyrometallurgical method. The results show that, under optimised conditions (DDTC:Ni(II) molar ratio = 4:1; temperature = 25 °C), the Ni(II) removal efficiency reached 99.3% after 10 min. In strongly acidic wastewater, the dithiocarbamate group of DDTC can react with Ni(II) to form DDTCNi precipitates. Further recovery experiments revealed that high-purity NiO can be obtained by the calcination of DDTCNi precipitates, with the nickel recovery efficiency reaching 98.2%. The gas released during the calcination process was composed of NO₂, CS₂, H₂O, CO₂, and SO₂. These results provide a basis for an effective Ni(II) recovery method from strongly acidic wastewater.     

阴离子对UV/H2O2/微曝气工艺降解双酚A 的影响

试验研究了水中典型阴离子对UV/H₂O₂/微曝气工艺降解内分泌干扰物双酚A 的影响.结果表明,随着HCO₃^-和NO₃^-浓度的增大,BPA的降解速率下降,当HCO₃^-浓度增加到400mg/L 时,反应常数(k)从0.1613min-1 降低到0.0804min^-1;当NO₃^-的浓度增加到800mg/L 时, k 值降低到0.1107min^-1;而SO₄²-和Cl-浓度在一定范围内增加时,有利于BPA 的降解,当SO₄²-的浓度为800mg/L 左右时,对降解促进作用最大, k 值增加到0.1814min-1;当Cl-的浓度为400mg/L 左右时, k 值增加到0.1772min-1,但是当浓度继续增加时,BPA 的降解速度将降低.4 种离子对BPA 的降解影响大小顺序为HCO₃^-> NO₃^->SO₄²->Cl-.     

Construction of Ag2CO3/BiOBr/CdS ternary composite photocatalyst with improved visible-light photocatalytic activity on tetracycline molecule degradation

Photocatalytic degradation was considered as a best strategy for the removal of antibiotic drug pollutants from wastewater. The photocatalyst of ABC (Ag₂CO₃/BiOBr/CdS) composite synthesized by hydrothermal and precipitation method. The ABC composite used to investigate the degradation activity of tetracycline (TC) under visible light irradiation. The physicochemical characterization methods (e.g. scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution-transmission electron microscopy (HR-TEM), ultraviolet visible spectroscopy (UV), photoluminescence (PL) and time resolved photoluminescence (TRPL) clearly indicate that the composite has been construct successfully that enhances the widened visible light absorption, induces charge transfer and separation efficiency of electron – hole pairs. The photocatalytic activity of all samples was examined through photodegradation of tetracycline in aqueous medium. The photocatalytic degradation rate of ABC catalyst could eliminate 98.79% of TC in 70 min, which is about 1.5 times that of Ag₂CO_3, 1.28 times that of BiOBr and 1.1 times that of BC catalyst, respectively. The role of operation parameters like, TC concentration, catalyst dosage and initial pH on TC degradation activity were studied. Quenching experiment was demonstrated that ·OH and O₂^·− were played a key role during the photocatalysis process that was evidently proved in electron paramagnetic resonance (EPR) experiment. In addition, the catalyst showed good activity perceived in reusability and stability test due to the synergistic effect between its components. The mechanism of degradation of TC in ABC composite was proposed based on the detailed analysis. The current study will give an efficient and recyclable photocatalyst for antibiotic aqueous pollutant removal.     

Role of NO and SO2 in mercury oxidation over a La2O3/Fe2O3 catalyst with high thermal stability

In this study, the thermal stability of a ferric oxide catalyst for mercury oxidation was found to be considerably promoted by doping with La₂O₃. The catalysts doped with La₂O₃ maintained a higher surface area when subjected to high-temperature calcination, with lower average pore size and a narrower pore size distribution. X-ray diffraction (XRD) results revealed that La₂O₃ doping hinders the growth of catalyst particles and crystallization of the material at high temperatures. Both NO and SO₂ inhibited Hg⁰ oxidation over the La₂O₃/Fe₂O₃ catalyst. Fourier transform infrared (FTIR) spectra revealed that SO₂ reacts with O₂ over the catalysts to form several species that are inert for mercury oxidation, such as SO₄^2?, HSO₄^?, or other related species; these inert species cover the catalyst surface and consequently decrease Hg⁰ oxidation capacity. In addition, NO or SO₂ competed with Hg⁰ for active sites on the La₂O₃/Fe₂O₃ catalyst and hindered the adsorption of mercury, thereby inhibiting subsequent Hg⁰ oxidation. Hg⁰ oxidation on the La₂O₃/Fe₂O₃ catalyst mainly followed the Eley–Rideal mechanism. Moreover, the inhibition effects of NO and SO₂ were at least partially reversible, and the catalytic activity was temporarily restored after eliminating NO or SO₂.     

Significant influences of TiO2 crystal structures on NO2 and HONO emissions from the nitrates photolysis

The emissions of NO₂ and HONO from the KNO₃ photolysis in the presence of TiO₂ were measured using a round-shape reactor coupled to a NO_x analyzer. TiO₂ played important roles in the emission flux density of NO₂ (R_NO2) and HONO (R_HONO), depending on crystal structures and mass ratios of TiO₂. R_NO2 and R_HONO significantly decreased with increasing the rutile and anatase mass ratios from 0 to 8 and 0.5 wt.%, respectively. Nevertheless, with further increasing the anatase mass ratio to 8 wt.%, there was an increase in R_NO2 and R_HONO. R_NO2 on KNO₃/TiO₂/SiO₂ had positive correlation with the KNO₃ mass (1–20 wt.%), irradiation intensity (80–400 W/m²) and temperature (278–308 K), while it had the maximum value at the relative humidity (RH) of 55%. R_HONO on KNO₃/TiO₂/SiO₂ slightly varied with the KNO₃ mass and temperature, whereas it increased with the irradiation intensity and RH. In addition, the mechanism for NO₂ and HONO emissions from the nitrates photolysis and atmospheric implications were discussed.