Evolution rates and PCB content of surface films that develop on impervious urban surfaces

Surface films on impervious surfaces mediate the fate of organic contaminants in urban areas. Using sheltered 3-mm diameter glass beads as a surrogate impervious urban surface, studies in downtown Toronto showed that surface films developed at a consistent rate of 1.6–2.6 nm day⁻¹. Linear film growth was observed up to and including the last day of three studies of 89-, 273-, and 84-day duration. Total PCB content (sum of 15 PCB congeners) also increased linearly, at a similar rate as the surface film. A complementary study using unsheltered beads showed that up to 80% of film mass and PCB content were removed by film wash-off during rain events. The film growth rate on beads exposed at a rural site, 200 km northeast of Toronto, was 12–20 times lower with PCB burdens that were 7–22 times lower compared to Toronto. Based on these findings, it is estimated that approximately 56–226 g of PCBs are captured by a 70 nm thick film covering just the horizontal surface area of Toronto. This is a substantial quantity of PCB that is available for rapid surface–air exchange and wash-off.     

几种阴阳离子对磷钨酸光催化降解甲基橙的影响

以磷钨酸为光催化剂,在紫外灯照射下,对甲基橙溶液进行光催化降解,考察了几种阴阳离子对磷钨酸光催化降解甲基橙溶液的影响。结果表明：Mg²⁺、Ca²⁺、NO^-₃、SO^2-₄和CO^2-₃均对催化活性有促进作用,其中Mg²⁺和Ca²⁺仅有微弱的促进作用;NO^-₃和SO^2-₄随着浓度的增加促进作用也有所增加;CO^2-₃则随着浓度的增加促进作用呈下降趋势;Mn²⁺、Al³⁺和Cl^-对光解反应存在较强的抑制作用,且Al³⁺和Cl^-随着其浓度的增加,抑制作用增强。     

TiO2与Cu2O光催化降解对硝基苯酚比较研究

分别采用自制的纳米TiO2和Cu2O研究对硝基苯酚的光催化降解.结果表明,模拟阳光条件下,100mg·l-1对硝基苯酚水溶液的氧化亚铜催化反应半衰期为20.0min,而二氧化钛不具备可见光催化能力;在SGY-1多功能光化学反应器中,TiO2催化降解对硝基苯酚的半衰期是48.1min.产物分析表明,n-型半导体二氧化钛的光催化反应存在两种降解历程,生成二羟基硝基苯或脱除硝基.而p-型半导体氧化亚铜催化的光降解反应未检出脱硝基产物,仅检出1,2-二羟基-4-硝基苯.     

TiO2薄膜光催化降解双酚A的研究

采用sol-gel法制备TiO2薄膜.以该薄膜为催化剂,研究了在H2O2存在的条件下,对内分泌干扰物质双酚A的光催化降解反应.分别讨论了pH值、H2O2的加入量、双酚A的初始浓度以及光照时间对降解反应的影响.结果表明,在pH=4,30 mg/L的H2O2中对初始浓度为50 mg/L的双酚A溶液光照180 min有较好的降解效果.     

克百威光催化降解动力学的研究

采用TiO2光催化技术对克百威的降解进行了研究,并系统地考察了催化剂用量,溶液初始pH值,底物浓度,活性氧物种和各种阴阳离子对其降解动力学的影响.用Langmuir-Hinshelwood动力学模型对克百威的光催化降解进行了研究,结果表明,克百威在弱碱性条件下降解速率最快,×OH对克百威降解贡献比约为93.4%,h+和其他ROSs的贡献则相对较小.而水溶液中的阴离子BrO3-和S2O82-对克百威的光催化降解有促进作用,I-则有明显的抑制作用,并且水溶液中的K+,Ca2+,Na+,Mg2+和Cu2+等金属阳离子对克百威的降解也均体现了一定程度的抑制作用.     

单偶氮染料AY17的光催化降解动力学及机制

为了研究水体环境中单偶氮染料酸性黄17(AY17)有效地去除方式及其可能的降解途径、转化和归趋等,实验首先探索了AY17在不同深度氧化体系中降解的可行性,研究发现其去除效率的大小按照UV/H_2O_2UV/Na_2S_2O_8≈UV/FeSO_4·7H_2OUV/KHSO_5UV/TiO_2排列.然后选取UV/TiO_2体系,研究了催化剂用量,反应温度,底物浓度以及溶液初始p H值等因素对其光催化降解动力学的影响,结果表明AY17的光催化降解遵循假一级动力学,其降解速率常数为0.011 2 min~(-1);当催化剂TiO_2用量为3 g·L~(-1)时其降解效果最好;高温有利于AY17的光催化降解,而随着底物浓度和溶液初始p H值的升高,其降解速率常数显著下降.最后利用GC/MS对AY17光催化降解中间产物进行了初步鉴定,研究发现在·OH等活性氧物种的作用下偶氮键的断裂、羟基自由基对芳香环上基团的取代以及吡唑环的裂解是其主要降解途径.     

聚丙烯酸钠为结合相的梯度扩散薄膜技术预测甘蔗田土壤中镉的生物有效性

DGT技术一直以固态结合相原位采集和测量水体、土壤或沉积物中有效态重金属,液态结合相的DGT主要应用于现场水体中金属离子的检测.本研究分别采用固态结合相梯度扩散薄膜(chelex100-DGT)装置和改进的液态结合相梯度薄膜扩散(CDM-PAAS-DGT)装置,对广西甘蔗田土壤中有效态Cd进行了测定.结果表明,2种装置提取的土壤有效态Cd含量与甘蔗(根、茎、叶)体内Cd含量都呈极显著正相关,改进的CDM-PAAS-DGT装置对土壤中有效态Cd的提取能力更强;融合土壤pH、阳离子交换量(CEC)、有机质(OM%)和土壤颗粒组成等理化指标影响,运用多元统计分析,提取出2种主成分因子,建立了多元回归模型.液态结合相DGT技术能较好地预测甘蔗田土壤中Cd的生物有效性,拓展了其应用范围.     

Phosphorus removal from sediments by Potamogeton crispus: New high-resolution in-situ evidence for rhizosphere assimilation and oxidization-induced retention

Macrophytes are usually chosen for phytoremediation tools to remove P in eutrophic aquatic ecosystems, but the lack of test methods hinders the understanding of removal mechanism and application. In this study, we used the novel technologies combined of Diffusive gradients in thin films (DGT), Planar optode (PO), and Non-invasive micro-test technology (NMT) to explore P dynamics in water-sediment continuum and rhizosphere of Potamogeton crispus over time. Results of the high-resolution in situ measurement showed that labile P(LP_DGT) fluxes at the surficial sediment significantly decreased from approximate 120, 140, and 200 pg/ (cm²?sec) via 30 days incubation period to 17, 40, and 56 pg/(cm²?sec) via that of 15 days. Obvious synchronous increase of LP_DGT was not detected in overlying water, suggesting the intense assimilation of dissolve reactive P via root over time. PO measurement indicated that O₂ concentration around the rhizosphere remarkably increased and radially diffused into deeper sediment until 100% saturation along with the root stretch downwards. NMT detection of roots showed the obvious O₂ inflow into root tissue with the uppermost flux of 30 pmol/(cm²?sec) from surroundings via aerenchyma on different treatment conditions. Different from previous reports, gradually saturating O₂ concentrations around the rhizosphere was principally driven by O₂ penetration through interspace attributing to root stretch downward rather than root O₂ leakage. Increased O₂ concentrations in deep sediment over time finally induced the oxidization of labile Fe(II) into Fe(III) bound P and local P immobilization.     

Bi5O7I/g-C3N4Z型异质结的常温沉淀制备及其光催化性能研究

以Bi（NO₃）₃·5H₂O、KI和g-C₃N₄为前驱体,采用常温沉淀法制备Bi₅O₇I/g-C₃N₄Z型异质结复合光催化剂,表征其光吸收性能、微观形貌、光生电子-空穴的分离效率等特性,研究新型光催化剂对RhB的可见光催化降解性能,探讨其可见光催化过程活性基团种类以及作用机理.结果表明：利用沉淀法合成Bi₅O₇I/g-C₃N₄的条件为：Bi（NO₃）₃·5H₂O、KI和g-C₃N₄的投加量分别为4.85g、1.66g和1.61g,乙二醇的用量为50mL,反应液的pH值为12,反应搅拌速度为200r/min,反应温度为25℃.Bi₅O₇I/g-C₃N₄异质结无杂相生成且纯度高,异质结复合发生在g-C₃N₄的（002）晶面和Bi₅O₇I的（203）晶面,但g-C₃N₄和Bi₅O₇I的化学结构未受影响.Bi₅O₇I/g-C₃N₄呈三维纳米花瓣形貌结构,为光生电子-空穴的迁移提供了大量的接触位点.Bi₅O₇I的g-C₃N₄掺杂改性使其光催化活性显著增强,其光吸收边缘由425nm红移至462nm,Bi₅O₇I/g-C₃N₄的能带排列结构与Z型异质结匹配,促进了光生电子-空穴的分离.其光电流密度（11.5mA/cm）约为g-C₃N₄和Bi₅O₇I对应值的2.66倍和1.47倍.Bi₅O₇I/g-C₃N₄对罗丹明B的可见光催化降解率为93.9%,显著高于g-C₃N₄（58%）和Bi₅O₇I（49.7%）的降解效果,其光催化氧化活性主要来自羟基基团、超氧基团和光生空穴等中间态自由基.     

抗坏血酸改性Br掺杂g-C3N4光催化降解污染物

以尿素和溴化铵分别作为前驱体和溴源,同时利用抗坏血酸对g-C₃N₄进行改性,通过二次焙烧法成功制备了抗坏血酸改性的Br掺杂g-C₃N₄-AA-Br纳米片光催化剂.利用XRD、TEM、XPS、UV-Vis DRS、PL、N₂吸附-脱附等测试手段对催化剂的结构、形貌、光学性能进行了表征.结果表明g-C₃N₄-AA-Br具有较大的比表面积、拓宽的可见光吸收范围以及较低的电子-空穴复合率.在可见光下考察了不同催化剂对RhB、甲基橙、活性蓝染料降解的光催化性能,结果表明g-C₃N₄-AA-Br-2在可见光下在180min内对RhB降解率为72%,其速率常数k=0.00847min^-1,是纯g-C₃N₄的5.6倍.通过活性物种捕获剂实验发现降解RhB的主要活性物种为羟基自由基（·OH）和超氧自由基（·O₂^-）,并推测了可能的反应机理.