不同源胡敏酸对磺胺嘧啶紫外光降解的影响及作用机制

研究了紫外光照条件下不同来源的胡敏酸（HA）,包括标准品胡敏酸（SPHA）、水稻土胡敏酸（SDHA）、泥炭土胡敏酸（NTHA）和落叶覆盖地胡敏酸（LYHA）对抗生素磺胺嘧啶（SDZ）光降解的影响以及主要活性物种对其光降解效能的贡献.结果表明：SDZ在纯水中及与HA共存条件下,其光降解过程均符合一级动力学模型,且HA对SDZ的光降解具有促进作用,其促进效果从大到小为SPHA > SDHA > NTHA > LYHA.通过羟基自由基（·OH）和单线态氧（¹O₂）淬灭实验发现,不同来源HA产生·OH和¹O₂的能力具有一定差异性.同等背景条件下,SPHA产生的·OH量相对较多,其对SDZ光降解的贡献率（26.97%）最大,而LYHA贡献相对较小（9.33%）.同时,¹O₂对SDZ光降解起主导作用,其降解贡献率为41.33%~51.95%.     

紫外老化微塑料衍生DOM理化特性及其与磺胺嘧啶、铜的络合机制

微塑料在老化过程中所释放的溶解性有机质(MPDOM)可与有机污染物、重金属等污染物发生络合反应,影响污染物的迁移转化.选取聚对苯二甲酸乙二醇酯(PET)和聚苯乙烯(PS)两种微塑料,利用荧光猝灭法及多种光谱分析技术和方法,同时结合Ryan-Weber模型,探究了MPDOM的光谱特性以及MPDOM与磺胺嘧啶(SDZ)、铜离子(Cu²⁺)的络合机制.紫外-可见吸收光谱分析结果表明,老化后两种MPDOM的相对分子量减小、芳香性及腐殖化程度增加,芳环上的羧基、羰基、羟基及酯类取代基增多.MPDOM与SDZ、 Cu²⁺的荧光猝灭均属于静态猝灭,猝灭后两种MPDOM的芳香性和腐殖化程度相近,相对分子质量相当.三维荧光光谱结合平行因子分析法共鉴定出两种类腐殖质组分和一种类蛋白质组分.同步荧光光谱分析结果表明,两种MPDOM均以类蛋白组分优先与SDZ发生反应,与Cu²⁺反应时更为敏感.结合Ryan-Weber模型可知,两种猝灭体系均以类腐殖质组分与PET-DOM的结合能力更高,但总体来说SDZ猝灭体系中MPDOM的结合能力要强于Cu     

典型可溶有机质与磺胺二甲嘧啶的络合作用研究

以藻源有机质(AOM)和腐殖酸(HA)作为典型生物大分子可溶有机质(DOM)和腐殖化DOM,采用荧光猝灭滴定和光谱分析考察磺胺二甲嘧啶(SMZ)与DOM的络合作用.三维荧光光谱结合平行因子分析显示AOM荧光组分主要由类酪氨酸和类色氨酸物质组成,而类富里酸和类腐殖酸物质是HA荧光组分的主要构成.4种荧光组分可与SMZ发生不同程度的静态猝灭,且猝灭过程中DOM分子构象改变.同步荧光光谱结合二维相关图谱进一步发现类酪氨酸优先于类色氨酸组分与SMZ发生络合作用.Ryan-Weber非线性模拟拟合表明AOM中各荧光组分与SMZ的络合稳定常数(logK)大小为:类富里酸(3.33)类酪氨酸(3.12)类色氨酸(2.15)类腐殖酸(1.57);而HA中大小为:类富里酸(3.06)类腐殖酸(2.02).总体上生物大分子DOM对SMZ的亲和力高于腐殖化DOM.DOM与SMZ的相互作用可改变水环境中抗生素的形态和归趋,影响其生物有效性和生态毒性.     

渗滤液中DOM的表征及特性研究

提取和分离了填埋场和焚烧厂渗滤液中的溶解性有机质,采用官能团滴定、紫外-可见吸收光谱、红外光谱和元素分析对其进行了表征.官能团滴定实验表明,渗滤液中总酸度和羧基官能团含量分别为：HyI＞FA＞HA和FA＞HA＞HyI,填埋场中各组分含量均小于焚烧厂中的相应组分;紫外-可见吸收光谱研究表明,填埋场渗滤液中各组分的芳香化程度均远大于焚烧厂中的相应组分,腐殖质的腐殖化程度依次为：C-HA>L-HA>I-HA和 L-FA>I-FA;红外光谱分析表明,相同来源垃圾渗滤液的腐殖质在官能团和分子结构组成方面较为相似,L-HA比L-FA含有更多芳环结构,L-FA中含有更多酸性基团;元素分析表明,渗滤液腐殖质中N元素含量远高于其它环境腐殖质,并发现填埋场渗滤液中腐殖质的芳香化程度大于焚烧厂.     

环境因子对胡敏酸介导下SDZ光解行为的影响

研究了在纯水条件及两种不同来源胡敏酸（HA）介导下,磺胺嘧啶（SDZ）和水稻土胡敏酸（SDHA）、泥炭土胡敏酸（NTHA）的不同浓度、pH值、光敏离子（NO₃^-和Fe³⁺）、离子强度（NaCl）以及金属离子（Ca²⁺、Mg²⁺和K⁺）等环境因子对SDZ紫外光降解的影响.结果表明：光照下,pH=7.1对两种体系的SDZ光降解有促进作用且效果最好.低SDZ浓度（2mg/L）以及低HA浓度（15mg/L）条件下使SDZ光解速率较快.光敏离子中NO₃^-通过光生·OH,促进了纯水中SDZ的光解,但在HA体系中,HA具有猝灭·OH的效应造成SDZ的光解速率低于纯水;Fe³⁺在HA体系下均表现为抑制作用,且抑制强度为NTHA>SDHA.在纯水中SDZ的光解速率随NaCl浓度增加而增加,HA介导下,较低浓度NaCl（C_NaCl=50mmol/L）抑制作用较强.金属离子（K⁺、Ca²⁺和Mg²⁺）在纯水中对SDZ的光解影响程度较弱,但在HA体系中均表现为抑制作用,抑制强度为K⁺ > Ca²⁺ > Mg²⁺,单价阳离子对SDZ光降解影响较为明显.     

光和生物改性溶解性有机质介导17α-乙炔基雌二醇厌氧降解

自然水体溶解性有机质(DOM)在光照和微生物存在的条件下理化性质会发生改变,从而影响其对类固醇类雌激素降解的介导作用.本研究通过对从洱海沉积物中提取的两种典型DOM物质—胡敏酸(HA)和富里酸(FA)分别经过72 h的微生物改性和48 h的光改性,分别比较厌氧条件下光改性前后DOM介导微生物降解17α-乙炔基雌二醇(EE2)的能力变化,以及微生物改性前后DOM介导光降解EE2的能力变化.同时,通过紫外可见吸收光谱、三维荧光光谱和电子供给能力对改性前后的DOM进行分析.结果表明:经过微生物改性后,HA和FA的荧光强度和腐殖化程度都有所提高,但紫外吸光强度和芳香性降低,并且与污染物的结合能力提高,使得光照条件下其介导的EE2更容易发生降解反应.微生物改性后HA介导下的EE2光降解效果要明显好于FA的介导效果.经过光改性后,HA和FA紫外吸光强度和芳香性升高,荧光强度和电子供给能力降低.光改性后HA介导下的EE2微生物降解效果要明显好于FA的介导效果.可见自然水体中微生物改性DOM介导的EE2降解效果相比光改性DOM的介导更加明显.     

次氯酸钠对水中腐殖酸结构及光学特性的影响

以腐殖酸（HA）作为溶解性有机质模型化合物,采用高压排阻色谱、有机元素分析、傅里叶红外光谱、紫外-可见光谱、荧光光谱及光降解动力学等手段研究了NaOCl对HA元素组成、结构特征、抗氧化性及光学特性等的影响.结果显示,当NaOCl与HA的浓度比由0增至20.0μmol/mg时,HA的分子量逐渐减小,并趋于集中分布;HA中的芳香酸、脂肪酸、酚和醇等含氧组分先增多后减少,使得HA的极性呈现出先增大后减小的变化趋势.值得注意的是,尽管实验浓度范围内的NaOCl不改变HA的腐殖特性,但其能显著减小HA的吸光能力、抗氧化能力和芳香度,并增大HA的荧光发光强度和表观光敏化活性.研究结果能促进对深度氧化处理改变溶解性有机质结构的认识,并为污水处理厂出水中溶解性有机质的环境效应评估提供基础信息.     

泥炭腐殖化度的测定方法研究

泥炭腐殖化度能反映沉积物中泥炭的分解程度,常被用作恢复古气候与环境的代用指标。本文对当前泥炭腐殖化度的5种测定方法:化学计算法、碱提取溶液吸光度法、经验公式法、标准曲线计算法和灰度度量法进行了系统分析和比较,重点介绍了碱提取溶液吸光度法,并依据哈尼地区的泥炭数据,对碱提取溶液吸光度法测定泥炭腐殖化度的可行性和可靠性进行了检验。     

DOM结构特征及其对17β-雌二醇光降解的影响

参照国际腐殖酸协会(IHSS)推荐的方法从滇池底泥提取出胡敏酸(HA)和富里酸(FA),以Sigma Aldrich胡敏酸(SAHA)为参照,利用元素分析、13C核磁共振和紫外-可见光谱对HA和FA的来源和结构进行了表征,并探讨了3种溶解性有机质(DOM)对17β-雌二醇(E2)光降解的影响.结果表明:HA、FA和SAHA具有相似的元素组成,3种腐殖酸的(N+O)/C值分别为0.50、0.82和0.55,与核磁共振13C谱分析的极性指数(0.32、0.42和0.33)一致.HA和FA来自于内源,具有较高的N含量和较多的缔合芳香结构,而SAHA是外源性有机质,具有更高的芳香度.低浓度的3种腐殖酸均能促进E2发生服从准一级动力学规律的光化学降解过程.E2在纯水中光降解速率为0.0071h-1,而在5mgC/L的HA、FA和SAHA作用下,E2光降解速率分别为0.0597、0.1178和0.2048h-1.3种腐殖酸促进E2光降解能力的差异主要是由含氧能团和芳香结构含量差异所致.活性氧分子探针鉴定显示HO?是腐殖酸体系受光照后产生的一种重要活性氧,其氧化降解E2的量占到了E2降解总量的70%左右.与低浓度腐殖酸相比,高浓度的3种腐殖酸均会对E2光降解产生抑制作用.     

湖泊草源DOM与磺胺二甲基嘧啶的荧光猝灭研究

磺胺二甲基嘧啶(SMT)作为一种常见的磺胺类抗生素,在富营养化湖泊中的迁移和归趋与溶解性有机质(DOM)密切相关。该研究采用荧光猝灭光谱法研究马来眼子菜释放的DOM与SMT的相互作用。同步荧光光谱和紫外可见吸收光谱表明SMT可引起DOM的构象变化,静态猝灭是主要机制。通过三维荧光光谱结合平行因子分析将DOM分为4个独立荧光组分,并结合Ryan-Weber非线性模型分析各组分与SMT的结合能力。模型拟合度较高,结合稳定常数(logK_b)大小顺序为类酪氨酸(7.22)>类色氨酸(5.54)>小分子类腐殖(5.04)>大分子类腐殖组分(无猝灭),说明DOM对SMT的络合作用较强。二维相关图谱显示类酪氨酸荧光团优先于类色氨酸荧光团与SMT发生反应。草源DOM与SMT之间的相互作用可影响SMT在富营养化湖泊中的生物有效性和毒性等环境行为。     

Comparative characterization of two natural humic acids in the Pearl River Basin, China and their environmental implications

Two humic acids (HAs) were isolated from contaminated river sediments present under comparative conditions in the Pearl River Basin, China. YFHA (the HA extracted at an open pyrite mining area in Yunfu) exhibited a lower absorption intensity for certain bands in the Fourier transform infrared spectra, a lower E4/E6 value (the UV absorbances at 465 nm (E4) and 665 nm (E6)), a lower apparent molecular weight, a lower polarity and a lower oxygen functionality in comparison with GZHA (the HA isolated at an urban living area in Guangzhou). All these differences indicated a higher degree of humification of YFHA than GZHA. Overall, the enrichment patterns of permanent heavy metals in the studied HAs were similar to those in corresponding sediments. In particular, YFHA exhibited high enrichment of trace element Tl, a characteristic concomitant from the mining of the pyrite minerals. The adsorption isotherms of two HAs for goethite and pyrolusite, two representative geological materials, conformed to the Langmuir equation. Based on the qualitative relationships between the Langmuir constants of the adsorption isotherms and the chemical characteristics of HAs, the main mechanism of HA adsorption on these materials was suggested to be hydrophobic interaction. This study highlighted the promising use of HA as a peculiar bio-indicator of uncommon trace metal contaminations. The HA adsorption mechanism on representative geological materials further provided a theoretical basis for the study on the unusual metal behavior in complex environmental settings.     

盐酸羟胺/铁基MOFs/过硫酸盐体系降解磺胺嘧啶

使用盐酸羟胺（HA）促进Fe （Ⅲ）/Fe （Ⅱ）循环,强化铁基金属有机骨架（Fe-MOFs）/过硫酸盐（PS）体系降解水中磺胺嘧啶（SDZ）.通过X射线衍射（XRD）、扫描电子显微镜（SEM）、傅立叶变换红外光谱（FTIR）和X射线光电子能谱仪（XPS）对Fe-MOFs进行结构和形貌的表征.探究了溶液初始pH值、PS浓度、Fe-MOFs投加量、HA浓度、SDZ浓度、共存离子、腐殖酸等对SDZ去除效果的影响,并考察了该体系的实际应用前景.结果表明,Fe-MOFs/PS/HA体系在较宽的初始pH值范围（3~6）内,对于SDZ的180min去除率可达到90.1%以上.适量的HA可以促进Fe-MOFs/PS体系降解SDZ的性能.自由基清扫实验和电子顺磁共振实验表明,Fe-MOFs/PS/HA体系降解SDZ的过程中产生了SO₄^-·、·OH、O₂^-·以及¹O₂.在本文考察范围内,Fe-MOFs/PS/HA体系对SDZ的降解性能随pH值（pH=3~6）升高逐渐下降;随着PS、HA、Fe-MOFs浓度的升高,SDZ去除率呈现率先上升后下降的趋势.氯离子、腐殖酸等因素对该体系应用于实际地表水存在负面作用,但HA可以强化该体系在自然环境下降解SDZ的效果.循环实验结果表明,Fe-MOFs具有良好的重复使用性,表现出了良好的应用潜力.     

A comparison of the compositional differences between humic fractions isolated by the IHSS and exhaustive extraction procedures

Humic substances (HSs), consisting, on the basis of solubilities in aqueous acid and basic media, of humic acids (HAs), fulvic acids (FAs), and humin (Hu), are the major components of soil organic matter (SOM). Most studies of soil/natural organic matter (SOM/NOM) have been carried out on extracts of soils in dilute sodium hydroxide solutions, the solvent used to extract the Standards of the International Humic Substances Society (IHSS). However, Hu, the major component in the classical definition of HSs, is insoluble in aqueous base and is not isolated by the traditional IHSS method. Recently, a sequential exhaustive extraction (SEE) process has been shown to be capable of isolating and separating the major components of the classically defined HSs from the soils of the temperate and tropical regions. The SEE system was used in the present study to isolate the HA/FA and Hu fractions from a subtropical volcanic Taiwanese soil. Chemical and compositional properties of these extracts were then compared with similarly obtained isolates from soils from the different climatic regions. Increases in the aliphatic relative to aromatic carbon contents were observed for both the HA and FA fractions when the pH values of the extraction media were increased. HAs and FAs isolated using the SEE method have spectroscopic profiles similar to those from the IHSS isolate; however, the cumulative extraction efficiency (%) of the SEE method (65 %) for the volcanic soil was much higher than for the traditional IHSS method (33 %). When the residual volcanic soil, following extractions once, three, and eight times with 0.1 M NaOH were then extracted with dimethyl sulphoxide (DMSO) plus concentrated sulphuric acid (the final solvent in the SEE sequence) it was seen that the content of crystalline polymethylene hydrocarbon (33 ppm ¹³C-NMR resonance in the Hu (or DMSO/acid)) extract increased relative to the amorphous methylene (30 ppm). That highlights the difficulty in dissolving the more highly ordered hydrocarbon structures that would be expected to have closer associations with the mineral colloids. Although the SEE procedure isolated all of the HAs and FAs from the Yangmingshan soil, extractability of the Hu from the volcanic soil in the DMSO/acid solvent was low (21 %), and contrasted with the much higher yields from temperate and tropical regions. The decreased Hu extraction may arise from its associations with the extensive iron and aluminium hydroxide mineral colloids in the soil. The Hu from this sub-tropical soil was different from the Hus isolated from other soil types, indicating the need to isolate and characterise these recalcitrant organic material in order to understand the organic carbon components in soils in greater detail. Such results would indicate that more attention should be given to mineral colloids in soils, and to the organo/mineral associations that will have an important role in the stabilities of OM in the soil environment.     

Comparative sorption and desorption behaviors of PFHxS and PFOS on sequentially extracted humic substances

The sorption and desorption behaviors of two perfluoroalkane sulfonates（PFSAs）, including perfluorohexane sulfonate（PFHx S） and perfluorooctane sulfonate（PFOS） on two humic acids（HAs） and humin（HM）, which were extracted from a peat soil, were investigated. The sorption kinetics and isotherms showed that the sorption of PFOS on the humic substances（HSs） was much higher than PFHx S. For the same PFSA compound, the sorption on HSs followed the order of HM 〉 HA2 〉 HA1. These suggest that hydrophobic interaction plays a key role in the sorption of PFSAs on HSs. The sorption capacities of PFSAs on HSs were significantly related to their aliphaticity, but negatively correlated to aromatic carbons,indicating the importance of aliphatic groups in the sorption of PFSAs. Compared to PFOS,PFHx S displayed distinct desorption hysteresis, probably due to irreversible pore deformation after sorption of PFHx S. The sorption of the two PFSAs on HSs decreased with an increase in p H in the solution. This is ascribed to the electrostatic interaction and hydrogen bonding at lower p H. Hydrophobic interaction might also be stronger at lower p H due to the aggregation of HSs.     

水质对UV/H2O2降解17α-乙炔基雌二醇（EE2）的影响

采用UV/H₂O₂间歇式光氧化反应器,研究了溶液pH值、腐殖酸及水中常见阴离子HCO₃^-、NO₃^-、CO₃^2-、Cl^-和SO₄^2-对UV/H₂O₂工艺降解17α-乙炔基雌二醇(EE2)的影响.结果表明,UV/H₂O₂工艺可以有效地去除水中的EE2,光降解过程符合一级反应动力学模型.双氧水投加量为5 mg/L时,在14W低压汞灯照射下,EE2在自来水和蒸馏水中的光降解一级反应速率常数为0.063 0min^-1和0.132 4min^-1.溶液中的腐殖酸和阴离子HCO₃^-、NO₃^-、Cl^-、SO₄^2-对EE2的光降解反应有抑制作用,4种阴离子浓度为5 mmol/L时,抑制作用依次为HCO₃^->SO₄^2->Cl^->NO₃^-,HCO₃^-可使光降解速率常数降低到50%.自来水中的光降解速率常数低于蒸馏水中的光降解速率常数是水中多种离子影响的结果.     

电场促进畜禽粪便好氧堆肥中DOM演化的光谱学研究

好氧堆肥是畜禽粪便处置和资源化利用的主要途径.传统好氧堆肥（CAC）技术存在堆体温度低、发酵周期长、腐熟效果差等缺陷.最近研究发现,电场辅助好氧堆肥（EAAC）可快速促进堆肥腐熟,缩短堆肥周期,减少温室气体排放,具有潜在的应用前景.然而,电场促进堆肥过程中水溶性有机物（DOM）演化及腐殖化过程尚未清晰.基于此,本文采用紫外-可见光谱（UV-Vis）、傅里叶变换红外光谱（FTIR）和三维荧光光谱（3D-EEM）等多种光谱技术分析了EAAC过程中DOM的演变规律.UV-Vis与3D-EEM分析表明,EAAC过程中,蛋白类物质在3 d内几乎被完全分解,富里酸和腐殖酸类物质在高温期（6~18 d）大量形成.EAAC的腐殖化指数（HI=HA/FA）高于CAC,E₄/E₆低于CAC,说明堆肥过程中DOM芳香化和腐殖化的速度与程度均优于CAC. FTIR分析显示,EAAC过程中DOM的碳水化合物、脂肪类物质逐渐减少,芳香族化合物不断增加,其腐殖化趋势明显比CAC更快.相关性分析显示,P_Ⅴ,n/P_Ⅲ,n与A_240~400、SUVA₂₅₄、E₂₅₃/E₂₂₀等UV-Vis光谱指标呈显著正相关（r>0.8, p<0.05）,可以作为评价EAAC腐熟度的重要指标.上述结果表明,电场辅助好氧堆肥可加速DOM中蛋白类物质分解,加快富里酸和腐殖酸类物质形成,促进DOM结构的芳香化.