头孢中间体合成废水组成分析及主要污染物识别

为了识别头孢抗生素生产废水中的主要污染物,掌握其水质特点,对头孢抗生素中间体合成废水进行了物质组成分析。水样取自天津某头孢生产企业废水处理系统的进水和出水。采用气相色谱-质谱联用(GC-MS)技术对污染物进行检测,经色谱柱分离后将各组分的质谱图与NIST08数据库对比、定性,确定了样品预处理方法和GC-MS分析的条件。研究结果表明,头孢中间体合成废水中存在7大类30余种化合物,通过对比废水处理系统进出水组成,确定了含N多环和杂环类化合物为最难降解的污染物,为此类废水的物理强化预处理和深度处理提供了依据。     

抗生素制药废水有机污染物分布特性研究

采用气相色谱/质谱法对β-内酰胺类抗生素制药废水中有机污染物进行了定性与定量分析,得到了废水中有机污染物的种类、相对含量及分子量分布特性.通过理论COD计算公式,计算分析了废水中有机污染物对COD指标的贡献程度.结果表明,该类废水中含有84种有机物,其中以胺类、烷烃类和烯烃类有机物的相对含量最高.有机污染物的分子量集中在100～400,分子量小于100或大于500的有机物含量相对较低,其中分子量在100～200的有机物含量最大.通过对比有机污染物的理论COD贡献度可知,胺类、烷烃类和烯烃类有机物含量对废水污染负荷影响最大.根据有机物污染源分析,提出了此类抗生素制药废水合理化处理的生产工艺建议和处理工艺方案.     

肝素提取废水的GC-MS分析和处理研究

肝素钠废水含有高浓度无机盐和大量有机污染物,对环境具有潜在的毒性且难以处理,已经受到环境工作者的关注。为了了解废水的主要成分和处理此类废水,本实验用GC-MS对废水进行了分析,并且利用芬顿试剂对其进行了处理,结果发现废水中有机物有26种,其中脂肪酸和芳香衍生物占有较大比例,处理后,有机成分只有3种;讨论了影响处理效果的因素和最佳的工艺条件,发现当pH 值为6.66,硫酸亚铁和过氧化氢的量分别为2.5 g/L和2.8‰ (v/v),搅拌速度为2 000 r/min, 搅拌时间为15 min时,COD的去除率可达到94.50%。     

芦苇湿地对造纸废水中有机污染物的去除效果及机理

为了对芦苇湿地对造纸废水中有机污染物的去除效果及降解机理进行研究,本文采用GC-MS联用仪对经芦苇湿地处理前后造纸废水中有机污染物的组成和含量进行测定,并通过叠放色谱图的方法对造纸废水中有机污染物的降解效果进行分析。结果表明:(1)经芦苇湿地处理前造纸废水中共测出30种有机污染物,其中8种被列入美国EPA环境优先控制污染物黑名单。(2)纸浆造纸废水生物塘-芦苇湿地复合处理系统对有毒有机污染物基本上达到了较好的去除效果:有机污染物总量减少80%以上,且降解后的产物多为毒性较小的烷烃类。(3)利用质谱手段对有机污染物的降解规律进行了初步研究。该研究为造纸废水处理和资源化利用提供了科学依据,为"造纸废水-芦苇-造纸"生态纸业循环经济模式的进一步推广应用奠定了基础。     

印染工业园区集中废水处理达标难点及DOM特征解析

以太湖流域某印染工业园区中集中废水处理厂为研究对象,分析有机物、氮、磷等污染物的水质变化特征,发现其出水TP、TN、NH3-N、COD的平均浓度分别为0.20、5.39、0.60和55 mg·L-1,COD应对新标准DB32-2018要求存在达标风险。为解决COD能够稳定达标的问题,通过3D-EEM、FT-IR和GC-MS等方法分析了该印染废水在处理过程中溶解性有机物的去除及迁移转化规律。结果表明:经生化处理后的废水荧光强度显著降低,深度处理后的色氨酸类物质被显著去除,出水中荧光特征峰明显减弱,大部分蛋白质与腐殖酸类物质被去除;各单元出水中存在不饱和双键类和芳香类化合物,典型官能团以—OH、C=O和C≡N等不饱和键为主;出水中主要成分为2,4'-二氟二苯甲酮和4-羟基-4-甲基-2-戊酮,判断其为该印染园区废水中的特征有机污染物。该方法明确了印染园区集中废水处理难点及溶解性有机物特征,为类似废水处理提供数据和技术支撑。     

焦化废水臭氧催化氧化过程的污染物降解特征

为了考察焦化废水臭氧催化氧化深度处理过程中污染物的降解特征,对处理过程中的废水进行了COD、TOC、BOD、紫外可见光谱、高效液相色谱、气相色谱-质谱联用(GC-MS)和凝胶色谱等多种分析。结果表明:经臭氧催化氧化处理后,废水的COD、TOC和UV_(254)均降低,降低速度大小为UV_(254)CODTOC;臭氧催化氧化可提高废水的可生化性,但氧化时间进一步延长,可生化性反而降低;液相色谱表明非极性物质优先得到去除;凝胶色谱表明分子量较小的物质优先去除;GC-MS结果表明焦化废水混凝出水中主要成分为苯酚类、杂环化合物、多环芳烃及其衍生物,臭氧催化氧化处理后这些化合物都得到有效降解。     

HUSB反应器提高以印染废水为主的城镇废水可生化性的研究

以印染废水为主的城镇废水中含有大量难降解有机物,可生化性较差。为提高该类废水的可生化性,采用HUSB反应器对环太湖城镇的实际混合工业废水进行预处理,通过紫外-可见光光谱、GC-MS等手段对废水中的有机组分在处理前后的变化进行表征,评价了废水可生化性的差异。结果显示,废水B/C值从0.251提升至0.423,废水中部分大分子有机物分解为小分子有机物,含有不饱和键的芳香类及环烃化合物含量有所下降,说明该类废水经过HUSB反应器处理后可生化性得到了显著提高。     

Fenton-水解酸化-接触氧化处理模拟磷霉素钠制药废水

对模拟磷霉素钠制药废水进行Fenton-水解酸化-接触氧化小试处理实验,考察了COD、有机磷的去除效果,并对处理前后的废水进行了GC-MS分析。结果显示,增加了Fenton预处理后磷霉素钠制药废水的COD和有机磷分别降低到100和2 mg/L,去除率均可达87%以上,出水COD满足化学制药行业污染物排放标准(GB 21904-2008);Fenton过程对制药厂废水中的复杂有机物去除效果明显,GC-MS结果表明,出水中基本检测不到复杂有机物。与制药厂采用的水解酸化-接触氧化处理效果相比,增加Fenton预处理可以提高废水的可生化性和系统的处理效率。     

超声波辅助萃取GC／MS法测定垃圾渗滤液中的有机污染物

垃圾渗滤液中有机污染物众多,成分复杂.以二氯甲烷为萃取剂,超声波辅助萃取后用GC/MS法测定垃圾渗滤液中的有机污染物.与传统振荡萃取相比,超声波辅助萃取明显提高了萃取效率.在GC/MS分析部分,研究了不同极性色谱柱对有机污染物分析结果的影响.实验结果表明,极性柱比较适于测定垃圾渗滤液中极性大的有机酸、醇类等物质.非极性柱能大大提高难生化降解的烷烃类、酯类等物质的检出率.     

压裂废水粘度对二氧化锰臭氧催化氧化处理特性的影响

通过FT-IR和GC-MS检测分析,表明了压裂废水中有机物主要以苯环结构为主的芳香类化合物和其他杂环化合物,苯环及杂环上的主要官能团包括酮、酯、羧酸、醛、酚、氨基等。同时,压裂废水中的粘度为常规水粘度的2~3倍。针对压裂废水高粘度和高COD污染水质特征,实验研究了压裂废水二氧化锰臭氧催化氧化处理特性以及粘度对处理效果的影响,研究结果表明,在粘度较高(2.2×10^-3Pa·s)压裂废水中,投加的化学药剂很难扩散,羟基自由基·OH的利用效率较低,处理效果较差。通过投加过硫酸钾(5 g/L)降粘后,可在很大程度上提高二氧化锰臭氧催化氧化的处理效果。通过对压裂废水中有机物分子量分布、FT-IR分析以及GC-MS分析可知,二氧化锰臭氧催化氧化处理压裂废水是通过激发羟基自由基,破坏水中有机物极性和有机物化学构造,将复杂长链有机物转变为简单有机物,其出水COD可达到国家污水综合排放标准中的二级排放标准。     

Comprehensive two-dimensional gas chromatography time of flight mass spectrometry (GC×GC-TOFMS) for environmental forensic investigations in developing countries

The disposal and dumping of toxic waste is a matter of growing concern in developing countries, including South Africa. Frequently these countries do not possess access to gas chromatography-high resolution mass spectrometry (GC-HRMS) for the determination of persistent organic pollutants (POPs). This publication describes an alternative approach to the investigation of toxic waste using comprehensive gas chromatography coupled to time of flight mass spectrometry (GC × GC-TOFMS). The technology permits both comprehensive screening of toxic samples for numerous classes of organic pollutants and also quantitative analysis for the individual compounds. This paper describes the use of this technique by analysing samples obtained from a hazardous waste treatment facility in South Africa. After sampling and extraction the samples were analysed for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and four dioxin-like non-ortho substituted polychlorinated biphenyls (PCBs). The quantitative values, as well as detection limits, obtained using the GC × GC-TOFMS methodology compares well with those obtained using GC-HRMS; the accepted benchmark technology for this analysis. Although GC × GC-TOFMS is not a target compound analytical technique (as is GC-HRMS), it is possible to obtain information on numerous other classes of organic pollutants present in the samples in one analytical run. This is not possible with GC-HRMS. Several different column combinations have been investigated for handling very complex waste samples and suggestions are presented for the most suitable combination.     

Monitoring the photochemical degradation of triclosan in wastewater by UV light and sunlight using solid-phase microextraction

Photo solid-phase microextraction (photo-SPME) is applied for the first time to study the photochemical behavior of an emerging pollutant, triclosan, in real contaminated wastewater samples using a solar simulator. In this study, water samples are extracted by SPME and then, the fiber coating is irradiated for a selected time. This on-fiber procedure, so-called photo-SPME, followed by gas chromatography-mass spectrometry makes it possible to study photodegradation kinetics and the generation of byproducts. Several photoproducts were identified in the real samples including the 2,8-dichlorodibenzo-p-dioxin, dichlorophenols and a compound tentatively identified as other DCDD congener or a dichlorohydroxydibenzofuran. Accordingly, it was possible to postulate main photodegradation mechanisms. Photo-SPME demonstrated slower kinetics in wastewater than in spiked ultrapure water probably due to the presence of dissolved organic matter. This technique was extensively compared with conventional aqueous photodegradation showing high similarity. The influence of pH on the triclosan photolysis and on the triclosan-dioxin conversion was also investigated in wastewater. Photodegradation of triclosan and formation of 2,8-DCDD occurred independently of sample pH. This study represents an advance in the use of photo-SPME to understand the photochemical fate of environmental organic pollutants and demonstrates its clear advantages with real samples.     

Elucidation of the behavior of tannery wastewater under advanced oxidation conditions

Diverse advanced oxidation process (AOP) techniques applying UV, TiO2/UV, O3 and O3/UV were used to degrade pollutants contained in tannery wastewater. The total mineralization of these pollutants is desirable, but it is quite energy consuming and sometimes impossible. Therefore the objective was to achieve an enhancement of biodegradability, preferentially with a decrease in toxicity in parallel. This work demonstrates that the dominant pollutants were chemically degraded by oxidation, while changes in carbon content were only marginal. These results were obtained monitoring the total organic carbon content (TOC), chemical and biochemical oxygen demand (COD and BOD), and substance-specific pollutant content by application of gas chromatography/mass spectrometry (GC-MS) and liquid chromatography/mass spectrometry (LC-MS). Daphnia magna toxicity testing performed in parallel proved a decrease in toxicity after AOP treatment of the tannery wastewater.     

Analysis of target and nontarget pollutants in aqueous leachates from the hazardous waste site Stringfellow, California, via ion chromatography - particle beam and inductively coupled plasma mass spectrometry

Liquid chromatography particle beam mass spectrometry (PB/MS is a powerful tool for the analysis of target pollutants but complementary methods are required for nontarget compounds. Preliminary data are presented on an anion exchange chromatography PB/MS based method for the detection of the target compound 4-chlorobenzene sulfonic acid (a contamlnant found in hazardous waste leachates) and also for nontarget pollutants in aqueous leachate samples from the Stringfellow hazardous waste site in California. Anion exchange chromatography coupled to inductively coupled plasma mass spectrometry yields qualitative and quantltative elemental analysis showing the presence or absence of key heteroatoms in organic pollutants including chlorine, other halogens, phosphorus and sulfur.     

焦化厂A/O出水中的有机污染物分析

采用色谱－质谱（GC／MS）联用仪分析和鉴定了上海宝钢焦化厂A／O生化阶段出水的有机污染物组成,共检出各类有机污染物70多种。结合焦化废水专用混凝剂的混凝处理实验结果,指出了各类有机污染物的去除情况。     

Simple digestion procedure followed by the azomethine-H method for accurate boron analysis and discrimination between its fractions in wastewater and soils

Excess boron is a growing environmental problem. It often affects agricultural yields, where reuse of wastewater for irrigation is practiced. This problem raises the need for reliable, simple and economical methods to monitor boron concentrations in wastewater and soil extracts. One such method, the commonly used azomethine-H spectrophotometric method, suffers from color interference, originating from high concentrations of dissolved organic matter, when applied to many wastewater and agricultural soil extracts. Moreover, this method only quantifies free dissolved boron and lacks the ability to quantify boron that is adsorbed to either the dissolved organic matter or suspended solids that are present in the sample. This work suggests a modification of the standard azomethine-H method, in which the solution is digested with potassium persulfate prior to the standard procedure. We show that this pretreatment can overcome the color interference and lead to highly accurate and precise boron analyses in wastewater. In soil extracts, the boron concentrations obtained using the suggested procedure were better correlated to inductively coupled plasma (ICP) spectrometry results than those measured by the standard method, because whereas the standard method quantifies the free dissolved boron only, the modified method, like the ICP method, quantifies the total dissolved boron in the sample. Thus, the suggested modification can be used to quantify the respective distributions of free dissolved boron, boron adsorbed to dissolved organic matter and boron adsorbed to suspended solids in soil extracts and water samples.     

Using phytoremediation technologies to upgrade waste water treatment in Europe

Goal, Scope and Background One of the burning problems of our industrial society is the high consumption of water and the high demand for clean drinking water. Numerous approaches have been taken to reduce water consumption, but in the long run it seems only possible to recycle waste water into high quality water. It seems timely to discuss alternative water remediation technologies that are fit for industrial as well as less developed countries to ensure a high quality of drinking water throughout Europe. Main Features The present paper discusses a range of phytoremediation technologies to be applied in a modular approach to integrate and improve the performance of existing wastewater treatment, especially towards the emerging micro pollutants, i.e. organic chemicals and pharmaceuticals. This topic is of global relevance for the EU. Results Existing technologies for waste water treatment do not sufficiently address increasing pollution situation, especially with the growing use of organic pollutants in the private household and health sector. Although some crude chemical approaches exist, such as advanced oxidation steps, most waste water treatment plants will not be able to adopt them. The same is true for membrane technologies. Discussion Incredible progress has been made during recent years, thus providing us with membranes of longevity and stability and, at the same time, high filtration capacity. However, these systems are expensive and delicate in operation, so that the majority of communities will not be able to afford them. Combinations of different phytoremediation technologies seem to be most promising to solve this burning problem. Conclusions To quantify the occurrence and the distribution of micropollutants, to evaluate their effects, and to prevent them from passing through wastewater collection and treatment systems into rivers, lakes and ground water bodies represents an urgent task for applied environmental sciences in the coming years. Recommendations Public acceptance of green technologies is generally higher than that of industrial processes. The EU should stimulate research to upgrade existing waste water treatment by implementing phytoremediation modules and demonstrating their reliability to the public.     

臭氧高级氧化技术在废水处理中的应用

综述了近年来迅速发展的臭氧高级氧化技术，包括臭氧氧化技术、臭氧／过氧化氢、臭氧／紫外辐射、臭氧与活性炭协同作用等技术，介绍了各种高级氧化技术的基本原理及在废水处理中的应用，并对其特点进行了评述。     

Spectroscopic changes on fulvic acids from a kraft pulp mill effluent caused by sun irradiation

Large volumes of wastewater with a high organic load are generated by the pulp and paper industry that negatively affect the quality of receiving waters. The main waste products in the pulp mill effluents are lignin derived macromolecular compounds, which are similar to natural humic substances and very resistant to wastewater treatments. Fulvic acids (FA) represent the higher percentage of these humic substances and it was observed that solar irradiation modify their properties. Several analytic tools, namely, UV–Visible, molecular fluorescence and FTIR spectroscopies, were used to assess the effect of solar exposition on fulvic acids from a kraft pulp mill effluent. It may be concluded that sun irradiation may alter to a high extent the physicochemical properties of macromolecular organic matter, namely fulvic acids, released by kraft pulp mill effluents. After solar exposition, the aromaticity decreases, the aliphatic structures become more oxygenated, and the fulvic acids from the pulp mill effluent remaining in solution are more similar to aquatic fulvic acids from non polluted sites.     

Spectroscopic changes on fulvic acids from a kraft pulp mill effluent caused by sun irradiation

Large volumes of wastewater with a high organic load are generated by the pulp and paper industry that negatively affect the quality of receiving waters. The main waste products in the pulp mill effluents are lignin derived macromolecular compounds, which are similar to natural humic substances and very resistant to wastewater treatments. Fulvic acids (FA) represent the higher percentage of these humic substances and it was observed that solar irradiation modify their properties. Several analytic tools, namely, UV–Visible, molecular fluorescence and FTIR spectroscopies, were used to assess the effect of solar exposition on fulvic acids from a kraft pulp mill effluent. It may be concluded that sun irradiation may alter to a high extent the physicochemical properties of macromolecular organic matter, namely fulvic acids, released by kraft pulp mill effluents. After solar exposition, the aromaticity decreases, the aliphatic structures become more oxygenated, and the fulvic acids from the pulp mill effluent remaining in solution are more similar to aquatic fulvic acids from non polluted sites.