Removal of carbamazepine from urban wastewater by sulfate radical oxidation

The occurrence of bioactive trace pollutants such as pharmaceuticals in natural waters is an emerging issue. Numerous pharmaceuticals are not completely removed in conventional wastewater treatment plants. Advanced oxidation processes may represent an interesting alternative to completely mineralize organic trace pollutants. In this article, we show that sulfate radicals generated from peroxymonosulfate/Co^II are more efficient than hydroxyl radicals generated from the Fenton’s reagent (H₂O₂/Fe^II) for the degradation of the pharmaceutical compound, carbamazepine. The second-order rate constant for the reaction of SO₄ ^·− with carbamazepine is 1.92·10⁹ M⁻¹ s⁻¹. In laboratory grade water and in real urban wastewater, SO₄ ^·− yielded a faster degradation of carbamazepine compared to HO^· . Under strongly oxidizing conditions, a nearly complete mineralization of carbamazepine was achieved, while under mildly oxidizing conditions, several intermediates were identified by LC–MS. These results show for the first time in real urban wastewater that sulfate radicals are more selective than hydroxyl radicals for the oxidation of an organic pollutant and may represent an interesting alternative in advanced oxidation processes.     

改性天然沸石的除氟性能研究

高效除氟材料的应用能降低饮用水中的氟质量浓度.采用静态吸附实验,比较了天然沸石和实验室制得的氢氧化铝、硫酸铝、聚合硫酸铁(PFS)改性天然沸石的除氟性能.结果表明,PFS改性的天然沸石具有良好的除氟效果,静态除氟容量可达25 mg·g~(-1).通过动态吸附试验,进一步探讨了饮用水的氟质量浓度、流速、停留时间、床层高度等因素对PFS改性天然沸石除氟性能的影响.研究发现,原水氟质量浓度越低,最佳除氟停留时间越短,PFS改性天然沸石滤柱床层高度越小.当停留时间为68 s,滤柱床层高度为47 mm时,含氟为5.8 mg·L~(-1)的模拟水样经吸附滤柱后,其氟质量浓度降到0.95 mg·L~(-1),低于国家生活饮用水标准的上限值1 mg·L~(-1).当含氟为4.14 mg·L~(-1)时,停留时间缩短为58 s,最小床层高度为40 mm;含氟为2.5 mg·L~(-1)时.停留时间为47 s,最小床层高度为32 mm,出水即可符合国家生活饮用水标准.因此,可根据不同高氟水地区的氟质量浓度来确定停留时间和床层高度,从而确定材料的适宜用量和流量.     

Bacteria inactivation by sulfate radical: progress and non-negligible disinfection by-products

● Status of inactivation of pathogenic microorganisms by SO₄^•− is reviewed. ● Mechanism of SO₄^•− disinfection is outlined. ● Possible generation of DBPs during disinfection using SO₄^•− is discussed. ● Possible problems and challenges of using SO₄^•− for disinfection are presented. Sulfate radicals have been increasingly used for the pathogen inactivation due to their strong redox ability and high selectivity for electron-rich species in the last decade. The application of sulfate radicals in water disinfection has become a very promising technology. However, there is currently a lack of reviews of sulfate radicals inactivated pathogenic microorganisms. At the same time, less attention has been paid to disinfection by-products produced by the use of sulfate radicals to inactivate microorganisms. This paper begins with a brief overview of sulfate radicals’ properties. Then, the progress in water disinfection by sulfate radicals is summarized. The mechanism and inactivation kinetics of inactivating microorganisms are briefly described. After that, the disinfection by-products produced by reactions of sulfate radicals with chlorine, bromine, iodide ions and organic halogens in water are also discussed. In response to these possible challenges, this article concludes with some specific solutions and future research directions.     

Broadening of appropriate demulsifier dosage range for latex-containing wastewater by sulfate addition

Investigation of demulsification of polybutadiene latex (PBL) wastewater by polyaluminum chloride (PAC) indicated that there was an appropriate dosage range for latex removal. The demulsification mechanism of PAC was adsorption-charge neutralization and its appropriate dosage range was controlled by zeta potential. When the zeta potential of the mixture was between -15 and 15 mV after adding PAC, the demulsification effect was good. Decreasing the latex concentration in chemical oxygen demand (COD) from 8.0 g/L to 0.2 g/L made the appropriate PAC dosage range narrower and caused the maximum latex removal efficiency to decrease from 95% to 37%. Therefore, more accurate PAC dosage control is required. Moreover, adding 50 mg/L sulfate broadened the appropriate PAC dosage range, resulting in an increase in maximum latex removal efficiency from 37% to 91% for wastewater of 0.2 g COD/L. The addition of sulfate will favor more flexible PAC dosage control in demulsification of PBL wastewater.

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Fenton——聚硅铝铁处理生活垃圾压滤液研究

为了降低生活垃圾压滤液污染负荷,为后续生化处理的正常运行创造良好条件,针对垃圾压滤液污染特性,以CODCr去除率为指标,通过正交实验和单因素实验研究了Fenton—聚硅铝铁混凝法处理城市生活垃圾压滤液的最优反应条件和处理效果。结果表明:采用该工艺处理垃圾压滤液时,pH值对CODCr去除率影响最大,其次是PSAF,再次是H2O2和FeSO4,在最优反应条件下,浊度去除率达到95.3%,CODCr去除率达到86.7%,BOD5去除率达到81.6%,浊度、CODCr、BOD5分别下降到86NTU、4201 mg.L-1、855 mg.L-1。     

Modeling and optimization of Nile blue sulfate mineralization by heterogeneous fenton oxidation

Artificial neural network and response surface methodology have been used to develop a model for simulation and optimization of the removal of Nile blue sulfate by heterogeneous Fenton oxidation. Experimental data were used to train an artificial neural network model with linear transfer function at the output layer and a tangent sigmoid transfer function at the hidden layer. A Box–Behnken design was employed to assess the effects of input process parameters on the total organic carbon removal. First order kinetics and lumped kinetics models were used to describe the reaction; a high regression coefficient indicated that the latter fitted best. The formation of non-oxidizable compounds was shown by liquid chromatography–mass spectrometry.     

Rapid dephosphorylation of glyphosate by Cu-catalyzed sulfite oxidation involving sulfate and hydroxyl radicals

Environmental Chemistry Letters - Glyphosate is a broad-spectrum toxic herbicide that has entered the environment. Advanced oxidation processes efficiently remove various persistent organic...     

Fenton试剂-硫酸镁深度处理酵母废水实验研究

采用Fenton试剂-硫酸镁对广东某酵母厂经厌氧、好氧、缺氧处理后的酵母废水进行深度处理。实验结果表明:采用Fenton试剂,在初始pH值为9、H2O2用量为5.55g/L、Fe2 加入量为1.41g/L、反应时间为20min的条件下,废水COD去除率达90%;继续采用硫酸镁对上清液进行处理,在调节pH为11～11.5、加入硫酸镁0.25～1.0g/L时,出水COD可降至138.0mg/L,颜色清澈。出水水质可达到《污水综合排放标准》(GB8978—1996)的二级标准。     

Metallic wastewater treatment by sulfate reduction using anaerobic rotating biological contactor reactor under high metal loading conditions

An-RBC reactor is highly suited to treat metallic wastewater. Metal removal is due to sulfide precipitation via sulfate reduction by SRB. Cu(II) removal was the best among the different heavy metals. Maximum metal removal is achieved at low metal loading condition. Metal removal matched well with the solubility product values of respective metal sulfide salts. This study was aimed at investigating the performance of anaerobic rotating biological contactor reactor treating synthetic wastewater containing a mixture of heavy metals under sulfate reducing condition. Statistically valid factorial design of experiments was carried out to understand the dynamics of metal removal using this bioreactor system. Copper removal was maximum (>98%), followed by other heavy metals at their respective low inlet concentrations. Metal loading rates less than 3.7 mg/L?h in case of Cu(II); less than 1.69 mg/L?h for Ni(II), Pb(II), Zn(II), Fe(III) and Cd(II) are favorable to the performance of the An-RBC reactor. Removal efficiency of the heavy metals from mixture depended on the metal species and their inlet loading concentrations. Analysis of metal precipitates formed in the sulfidogenic bioreactor by field emission scanning electron microscopy along with energy dispersive X-ray spectroscopy (FESEM-EDX) confirmed metal sulfide precipitation by SRB. All these results clearly revealed that the attached growth biofilm bioreactor is well suited for heavy metal removal from complex mixture.     

Overlooked involvement of phosphate radicals in the degradation of the atrazine herbicide by sulfate radical-based advanced oxidation

Environmental Chemistry Letters - The persistence of recalcitrant pollutants in water is a major health issue calling for advanced and green techniques to clean polluted waters. For instance,...     

Sedimentation and sulfate reduction under a mussel culture

The sedimentation and dissimilatory sulfate reduction under a blue-mussel culture were quantified in order to gain information on the environmental impact of intense mussel farming. The sedimentation rate (3 g C·m^-2·d^-1) under a culture is nearly three times higher than at a nearby reference station. A build-up of sediment rich in organic material and sulfide takes place under the mussels. At 15°C the sulfate reduction rate was 30.5 mmol SO ₌ ⁴ ·m^-2·^-1 in the upper 10 cm of the mussel sediment. The increase in sedimentation under a mussel culture and the consequent effects should be considered when establishing mussel farms.     

Reactivity of sulfate radicals with natural organic matters

Advanced oxidation processes based on sulfate radicals (SO ₄ ^·? ) are capable of efficiently degrade organic pollutants from ground, surface and wastewaters. However, this degradation may be limited by aqueous natural organic matter (NOM). Here we measured the absolute rate constants of reaction of SO ₄ ^·? with four types of organic matter: two fulvic acids and two lake organic matter. We used laser flash photolysis technique to monitor the SO ₄ ^·? decay and the formation of the transients from organic matters. Reaction rate constants comprised between 1530 and 3500 s^?1 mgC^?1 L were obtained by numerical analysis of differential equations and the weighted average of the extinction coefficient of the generated organic matters radicals between 400 and 800 M^?1 cm^?1.     

A sustainable sulfate process to produce TiO2 pigments

Titanium dioxide (TiO₂) is a widely used white pigment. TiO₂ production in 2006 was about 1,400,000 metric tons in the USA. The two major processes to manufacture TiO₂ are the chloride process and the sulfate process. Currently, the TiO₂ industry finds the waste generated in the chloride process less than the waste generated in the sulfate process in its present design, despite generating large quantities of process-related carbon dioxide and carbon monoxide. As a consequence, the sulfate process appears less economical, notably due to the production of green vitriol, FeSO₄·7H₂O, as a major waste. Here, we describe a more sustainable sulfate process based on an earlier study on thermal decomposition of iron(II) sulfates. In the sustainable sulfate process, FeSO₄·7H₂O waste is used for greener production of sulfuric acid, H₂SO₄, used in turn for the digestion of ilmenite. Theoretical and actual yields of waste byproducts per metric ton of TiO₂ produced are used to show the environmental and economic advantages of the sustainable sulfate process.     

High removal of phosphate from wastewater using silica sulfate

This report shows that silica sulfate is removing phosphate from wastewater very efficiently. Phosphorus removal and recovery from wastewater is a worldwide issue due to pollution of natural waters by phosphate and depletion of phosphate ores. Adsorption is a process that can remove phosphate at low concentrations. Adsorption also allows the recovery of phosphate for possible re-use. Here, we studied the adsorption of phosphate from wastewater using commercial Zr ferrite, Zr-MCM 41 and silica sulfate. We calculated equilibrium isotherms, kinetic models and thermodynamic effects under conditions similar to real wastewaters. We found that the equilibrium data for the adsorption of phosphate were best fitted to the Freundlich model. The results show that the maximum uptake of phosphate was 3.36 mg g⁻¹ for Zr-MCM, 27.73 mg g⁻¹ for Zr ferrite and 46.32 mg g⁻¹ for silica sulfate. The kinetic results of the three adsorbents were satisfactorily predicted using a pseudo-second-order model. We found that silica sulfate provided excellent characteristics in terms of the maximum adsorption and rate constant for the adsorption of phosphate. The thermodynamic data showed that increasing the temperature enhanced the adsorption of phosphate onto silica sulfate. Our findings will help to define efficient methods to remove phosphate from wastewater.     

酸性硫酸盐土的酸度类型及其测定方法

酸性硫酸盐土是一种广泛分布于沿海低地和矿区的污染源土壤，对生态环境和人类健康具有潜在或实际的负面影响。酸性硫酸盐土中各类酸度是评估酸性硫酸盐土环境风险最重要的指标。酸性硫酸盐土的酸度可分为水溶性酸度、吸持性酸度和金属硫化物起源潜在酸度等3种类型。文章根据最新的研究结果，简要地介绍酸性硫酸盐土的酸度类型及其测定方法。     

Enhanced methane hydrate storage using sodium dodecyl sulfate and coal

A potential solution to reduce global warming is to store greenhouse gases. Greenhouse gas storage has been recently improved using several materials and techniques. However, the actual storage capacity is slow, limited, and costly. Here, we tested the use of an accelerating agent, sodium dodecyl sulfate, and coal to produce methane hydrate for methane storage. Experiments of storing methane gas in coal samples have been carried out under high pressures, 4 or 6 MPa, and low temperature of 273.15 K. Results reveal that sodium dodecyl sulfate improved the rate up to 58.26 cm³/min and the capacity up to 179.97 volume at standard temperature and pressure per unit volume of coal. This finding shows that sodium dodecyl sulfate is efficient to accelerate the formation of methane hydrate. We also found that storage capacity increased with pressure. We conclude that our method allows a gas storage capacity higher than any other medium materials reported previously.     

Anaerobic biodegradation of trimethoprim with sulfate as an electron acceptor

Anaerobic biodegradation of trimethoprim (TMP) coupled with sulfate reduction. Demethylation of TMP is the first step in the acclimated microbial consortia. The potential degraders and fermenters were enriched in the acclimated consortia. Activated sludge and river sediment had similar core microbiomes. Trimethoprim (TMP) is an antibiotic frequently detected in various environments. Microorganisms are the main drivers of emerging antibiotic contaminant degradation in the environment. However, the feasibility and stability of the anaerobic biodegradation of TMP with sulfate as an electron acceptor remain poorly understood. Here, TMP-degrading microbial consortia were successfully enriched from municipal activated sludge (AS) and river sediment (RS) as the initial inoculums. The acclimated consortia were capable of transforming TMP through demethylation, and the hydroxyl-substituted demethylated product (4-desmethyl-TMP) was further degraded. The biodegradation of TMP followed a 3-parameter sigmoid kinetic model. The potential degraders (Acetobacterium, Desulfovibrio, Desulfobulbus, and unidentified Peptococcaceae) and fermenters (Lentimicrobium and Petrimonas) were significantly enriched in the acclimated consortia. The AS- and RS-acclimated TMP-degrading consortia had similar core microbiomes. The anaerobic biodegradation of TMP could be coupled with sulfate respiration, which gives new insights into the antibiotic fate in real environments and provides a new route for the bioremediation of antibiotic-contaminated environments.     

Bacterial sulfate reduction within reduced microniches of oxidized marine sediments

Bacterial sulfate reduction was demonstrated in the oxidized surface layers of a coastal marine sediment using a radiotracer technique. The obligate anaerobic process takes place within reduced sediment pellets of 50 to 200 m diameter. The H₂S produced diffuses out into the interstitial solution and is oxidized before any detectable accumulation takes place. This microniche structure explains the presence of sulfate-reducing (Desulfovibrio spp.) and sulfide oxidizing (Beggiatoa spp.) bacteria and of ferrous sulfide and pyrite in the oxidized sediment. Sulfate reduction was also demonstrated within detrital particles experimentally decomposed in oxic seawater or sediment. The limiting conditions for the maintenance of a reduced microniche within an oxic environment is discussed in terms of a theoretical model.