硼掺杂介孔炭吸附四环素的效能与机制

以椰壳和硼酸为原料,通过简单的一步热解法制备出新型硼掺杂椰壳介孔炭材料（B-CSC）用于水中四环素类污染物的高效吸附去除.系统研究了关键制备条件热解温度和硼碳质量比对其吸附性能的影响,使用比表面积及孔径分析仪（BET）、场发射扫描电镜（SEM）、X射线光子能谱仪（XPS）、拉曼光谱仪（Raman）以及Zeta电位仪（Zeta）对其微观结构及物化性质进行了表征分析.系统考察了初始pH值、不同金属阳离子以及不同背景水质条件对其吸附效果的影响.结合材料表征与相关分析等对其强化吸附机制进行了深入讨论与分析.结果表明,一步热解能够将硼掺入椰壳炭的表面及晶格,导致其拥有更大的比表面积和孔体积,引入硼的形态主要是H₃BO₃、B₂O₃、B和B₄C.B-CSC对四环素的吸附量达到297.65 mg·g^-1,是原始椰壳介孔炭（CSC）的8.9倍.同时,B-CSC对于水环境中常见污染物罗丹明B（RhB）、双酚A（BPA）和亚甲基蓝（MB）的吸附量分别高达372.65、255.24和147.82 mg·g^-1.B-CSC对四环素的吸附过程是物理化学作用共同主导的,主要涉及液膜扩散、表面吸附、介孔与微孔内扩散和活性位点吸附,H₃BO₃是其主要吸附位点.吸附强化机制主要是硼掺杂降低了其碳网络的化学惰性,增强了其与四环素分子的π—π相互作用和氢键作用.     

Sorption and desorption of glyphosate,MCPA and tetracycline and their mixtures in soil as influenced by phosphate

Phosphate fertilizers and herbicides such as glyphosate and MCPA are commonly applied to agricultural land, and antibiotics such as tetracycline have been detected in soils following the application of livestock manures and biosolids to agricultural land. Utilizing a range of batch equilibrium experiments, this research examined the competitive sorption interactions of these chemicals in soil. Soil samples (0-15 cm) collected from long-term experimental plots contained Olsen P concentrations in the typical (13 to 20 mg kg^?1) and elevated (81 to 99 mg kg^?1) range of build-up phosphate in agricultural soils. The elevated Olsen P concentrations in field soils significantly reduced glyphosate sorption up to 50%, but had no significant impact on MCPA and tetracycline sorption. Fresh phosphate additions in the laboratory, introduced to soil prior to, or at the same time with the other chemical applications, had a greater impact on reducing glyphosate sorption (up to 45%) than on reducing tetracycline (up to 13%) and MCPA (up to 8%) sorption. The impact of fresh phosphate additions on the desorption of these three chemicals was also statistically significant, but numerically very small namely < 1% for glyphosate and tetracycline and 3% for MCPA. The presence of MCPA significantly reduced sorption and increased desorption of glyphosate, but only when MCPA was present at concentrations much greater than environmentally relevant and there was no phosphate added to the MCPA solution. Tetracycline addition had no significant effect on glyphosate sorption and desorption in soil. For the four chemicals studied, we conclude that when mixtures of phosphate, herbicides and antibiotics are present in soil, the greatest influence of their competitive interactions is phosphate decreasing glyphosate sorption and the presence of phosphate in solution lessens the potential impact of MCPA on glyphosate sorption. The presence of chemical mixtures in soil solution has an overall greater impact on the sorption than desorption of individual organic chemicals in soil.     

四环素对污泥蚯蚓粪中微生物种群和抗性基因的影响

城市污泥中高含量的四环素可能会致使污泥蚯蚓堆肥产物中携带高丰度的抗性基因,降低其利用价值.本实验采用赤子爱胜蚓处理添加不同含量四环素(100、500和1 000 mg·kg-1)的新鲜污泥,以不添加为对照组,分析微生物种群和四环素抗性基因(tet C、tet G、tet M、tet W和tet X)及整合子基因(int I1)在不同四环素选择性压力下的变化,揭示四环素含量对污泥蚯蚓堆肥中微生物种群和抗性基因的影响.结果表明,添加四环素降低了污泥蚯蚓堆肥产物中变形菌门的丰度但增加了拟杆菌门的丰度,且四环素的含量与细菌的Shannon和Pielou指数有明显的负相关关系.同时,添加四环素致使int I1增加了4. 25倍;四环素类抗性基因增加了4. 7～186. 9倍,其中tet M基因丰度与四环素含量呈现出显著的正相关关系.因此初始污泥中较高含量的四环素会改变污泥蚯蚓粪的微生物种群结构,增加抗生素抗性基因的丰度和传播风险.     

城市污水处理厂四环素抗性菌的筛选及其抗性基因分析

城市污水处理厂中抗生素抗性菌的富集和扩散对受纳水体及公共卫生安全造成严重的威胁.本研究从上海某城市污水处理厂活性污泥中筛选得到一株四环素抗性菌株TC-1,基于形态特征、生理生化特性和16S r DNA结果鉴定,菌株TC-1属于节杆菌属(Arthrobacter sp.).对节杆菌属菌株的全基因组分析表明,菌株TC-1含有多种抗生素抗性基因,包括四环素、氯霉素、大环内酯类和青霉素抗性基因.对比节杆菌属抗生素抗性基因的基因簇分析表明,这些抗性基因在节杆菌属中具有普遍存在性,表明其来源于相关菌株的遗传而非单个菌株的偶然获得.鉴于节杆菌属是潜在的病原性微生物,该结论可为废水生物处理系统中含抗生素抗性基因的致病微生物环境行为和风险评估提供参考.     

两性修饰蒙脱石对水中镉和四环素的吸附性能研究

以两性表面活性剂十二烷基二甲基甜菜碱(BS-12)为改性剂制备两性修饰蒙脱石(BS-Mt),在单一体系和Cd~(2+)+TC复合体系中研究其对Cd~(2+)和四环素的吸附行为,同时利用XRD、FTIR、TG-DSC和Zeta电位对两性修饰蒙脱石进行表征分析.表征结果显示,BS-12已成功负载到蒙脱石上,改性后材料表面的负电荷增加;吸附实验结果显示,BS-Mt对Cd~(2+)和四环素的吸附量较Mt有较大的提高;其中BS-Mt对Cd~(2+)的吸附行为符合Langmuir等温吸附模型和准一级动力学模型,吸附机理主要为电荷吸附和螯合作用;BS-Mt对四环素的吸附随p H的升高而降低,吸附行为符合Freundlich等温吸附模型和准二级动力学模型,吸附机理主要为电荷吸附和物理吸附.在Cd~(2+)+TC复合体系中Cd~(2+)和TC会形成复合物,Mt和BS-Mt对四环素和Cd~(2+)的吸附量比单一体系增加.     

Removal of tetracycline from water by Fe-Mn binary oxide

Significant concerns have been raised over the presence of antibiotics including tetracyclines in aquatic environments. A series of Fe-Mn binary oxide with different Fe:Mn molar ratios was synthesized by a simultaneous oxidation and coprecipitation process for TC removal. Results showed that Fe-Mn binary oxide had higher removal efficiency than that of hydrous iron oxide and hydrous manganese oxide, and that the oxide with a Fe:Mn molar ratio of 5:1 was the best in removal than other molar ratios. The tetracycline removal was highly pH dependent. The removal of tetracycline decreased with the increase of initial concentration, but the absolute removal quantity was more at high concentration. The presence of cations and anions such as Ca²⁺, Mg²⁺, CO₃^2- and SO₄^2- had no significant effect on the tetracycline removal in our experimental conditions, while SiO₃^2- and PO₄^3- had hindered the adsorption of tetracycline. The mechanism investigation found that tetracycline removal was mainly achieved by the replacement of surface hydroxyl groups by the tetracycline species and formation of surface complexes at the water/oxide interface. This primary study suggests that Fe-Mn binary oxide with a proper Fe:Mn molar ratio will be a very promising material for the removal of tetracycline from aqueous solutions.     

一种纳米级不定形碳对水中四环素的吸附研究

研究了一种新型纳米级不定形碳对水中四环素的吸附作用.结果表明,在Li-Na-K碳酸盐的共熔体系中生成的碳粉对四环素表现出了良好的吸附性能.在298K下,碳粉对四环素的吸附行为更符合拟二级动力学模型和Freundlich吸附等温线,最大吸附容量达到127.76 mg·g-1.热力学计算结果表明,吸附过程是吸热的、自发的,以化学吸附为主.吸附行为表现出明显的p H依赖性,当溶液的起始p H在2~11,p H为4时碳粉对四环素的吸附量最大.溶液中的阳离子对吸附有一定的影响,但影响不大,随着阳离子浓度的增加,吸附量在一定程度上逐渐减小.离子交换作用可能是吸附的原理之一,还可能同时存在静电引力、氢键等作用.分别使用0.25 mol·L-1的Ca Cl2和Na Cl溶液进行解吸实验,解吸效率在7.42%~25%,解吸效率较低,说明吸附的化学作用较强.     

紫外光协助高锰酸钾降解四环素的研究

高锰酸钾氧化法在实际水处理中得到了一定的应用,但对有机污染物的去除和降解能力相对有限,为此提出了以外加紫外光照射协助高锰酸钾氧化的方法。以四环素作为模型污染物,考察了四环素浓度、高锰酸钾浓度、反应时间、初始pH条件和不同紫外光照射等的影响。结果表明,高锰酸钾能够氧化并去除四环素,紫外光照射明显提高了高锰酸钾对四环素的降解效果,并且254 nm紫外光照射对降解的促进作用远大于365 nm紫外光。在所考察的pH范围内,无论紫外光照射与否,高锰酸钾在酸性条件下的降解效率最高,中性条件较高,碱性条件次之。     

Environmental fate of tetracycline resistance genes originating from swine feedlots in river water

Tetracyclines are antibiotics commonly used in swine farms to treat disease and promote growth. However, there are growing concerns regarding the discharge of animal feces into the environment owing to the potential for development and dissemination of tetracycline resistance genes (TRGs). In this study, farming wastewater from one Chinese swine farm as well as river water from seven locations downstream of the farm was sampled. Polymerase chain reaction (PCR) showed that 12 TRGs, including six efflux pump genes (tet(B), tet(C), tet(D), tet(E), tet(G) and tet(L)), five ribosomal protection proteins (RPPs) genes (tet(O), tet(M), tet(Q), tet(W) and tet(S)), and one enzymatic modification gene (tet(X)), were present in all wastewater and river water samples. Quantitative real-time PCR (qPCR) showed that the abundance of tet(C), tet(X), tet(O), tet(M), tet(Q) and tet(W) decreased with downstream flow. Among the detected TRGs, tet(C) had the highest abundance, ranging from 459.5 copies/16S rRNA gene copies in wastewater to 33.8 copies/16S rRNA gene copies in river water samples collected from the last location. Furthermore, pig-specific Bacteroidales 16S rRNA genetic marker was quantified by qPCR to determine the level of fecal pollution in the river water. Bivariate correlation analysis confirmed that the total relative abundance of the six TRGs was significantly correlated with the level of swine feces in the aquatic environment (R² = 0.63, P < 0.05), suggesting that swine feces mainly contributed to the spread of TRGs in the river water.

Supplemental materials are available for this article. Go to the publisher's online edition of Journal of Environmental Science and Health, Part A to view the free supplemental file.     

四环素在石墨上的吸附行为研究

考察了石墨和四环素的相关性质,并通过静态吸附实验探讨了四环素在石墨表面的吸附行为及其机理。结果表明,四环素在石墨表面的吸附量、四环素的K_(ow)值以及四环素(+,-,0)的形态分布在pH尺度上的变化趋势表现出较高的相似性。据此推断四环素主要通过疏水力作用吸附于石墨表面,该作用力最大值出现在pH=5～6之间,而其他pH条件下,该作用力会随吸附剂、吸附质间静电斥力的增强和四环素自身溶解度的增加而被削弱。