Interaction between Humic Acid and p-Arsanilic Acid Using Fluorescence Quenching Approach

P-arsanilic acid(p-ASA),as a kind of organoarsenic feed additive,has been widely used in poultry and swine breeding.However,it has caused the arsenic pollution around the farm.Currently data shows humic acid(HA)is closely to the migration and transformation of p-ASA.Therefore,the interaction between p-ASA and HA was investigated by using the method of fluorescence quenching titration.The association constant changed from2.74 to 4.88 L·mol-1at a p H varying from 5 to 9 and reached the maximum at p H 7.In addition,log K varied from4.15 to 5.02 L·mol-1when the temperature increased from 15℃to 35℃.The log K increased with an increase in the concentration of HA.The dominant mechanism between p-ASA and HA is static quenching.The primary interaction force was likely the hydrogen bond,and the binding behavior occurred on the As-O stretch of p-ASA and the carboxylic acid C=O stretch of HA.The results showed that dissolved organic matters could affect the fate and biogeochemical cycling of organoarsenic pharmaceuticals in aquatic ecosystems.     

Formation of Soluble Complexes of Metals with Humic Acid and Its Environmental Significance

In order to investigate the role of functional groups present in humic acid(s) (HA) during complex formation, water soluble complexes between HA isolated from soil and metals (Pb, Ca, As, Ni, Cr, Co, Cu, Cd, Fe, Mn, Mg and Zn) were prepared and subjected to infrared (IR) spectroscopy. the IR data revealed the involvement of the - OH group of humic acid in complex formation with all metals except copper and arsenic, whereas the - COOH group of HA was found to be the preferred site of binding for all the metals. the significance of findings in relation to detoxification of environmental pollutants is discussed in this paper.     

Studies of Thermal Transformations of Humic and Fulvic Acids in Soils I. Infrared Spectroscopy and Temperature-Programmed Pyrolysis Mass Spectrometry

Temperature-programmed pyrolysis mass spectrometry and Fourier-transform infrared spectroscopy have been used to monitor structural changes of humic and fulvic acids isolated from soils in China, in the temperature range of 25-550°C. in this work, we found that decarboxylation is obvious as the main reaction with dehydration reaction from 150°C to 400°C, the anhydride can be identified from FT-IR spectra at temperature range from 200°C to 400°C; there are evident changes of the aromatic nucleus of humic and fulvic acids above 400°C, even remaining up to 550°C. Besides, some changes of adsorption water can be distinguished before 200°C, and the mass signal of sulphur dioxide was detected.     

Studies of Thermal Transformations of Humic and Fulvic Acids in Soils I. Infrared Spectroscopy and Temperature-Programmed Pyrolysis Mass Spectrometry

Temperature-programmed pyrolysis mass spectrometry and Fourier-transform infrared spectroscopy have been used to monitor structural changes of humic and fulvic acids isolated from soils in China, in the temperature range of 25-550°C. in this work, we found that decarboxylation is obvious as the main reaction with dehydration reaction from 150°C to 400°C, the anhydride can be identified from FT-IR spectra at temperature range from 200°C to 400°C; there are evident changes of the aromatic nucleus of humic and fulvic acids above 400°C, even remaining up to 550°C. Besides, some changes of adsorption water can be distinguished before 200°C, and the mass signal of sulphur dioxide was detected.     

胡敏酸、富里酸对土壤-地下水系统中BDE-47迁移的影响

多溴联苯醚(polybrominated diphenyl ethers,PBDEs)是土壤-地下水系统中广泛存在的有机污染物,研究土壤组分对其迁移行为的影响是解决土壤-地下水系统中多溴联苯醚归趋问题的关键。以典型多溴联苯醚同系物2,2',4,4'-四溴联苯醚(2,2',4,4'-tetrabromodiphenyl ether,BDE-47)为研究对象,选取胡敏酸(humic acid,HA)、富里酸(fulvic acid,FA)2种代表性土壤有机组分,配制不同浓度的FA、HA溶液(150 mg·L~(-1)、50 mg·L~(-1)),分别对不同浓度的BDE-47(100μg·g~(-1)、10μg·g~(-1))污染土壤进行土柱淋滤实验,探讨FA、HA对土壤-地下水系统中BDE-47迁移的影响。结果表明,HA作用下,实验组下层土壤中BDE-47的残留比例分别为0.62%和0.40%,分别低于对照组的0.72%和3.36%;FA作用下,实验组下层土壤中BDE-47的残留比例分别为6.40%和6.71%,分别高于对照组的0.72%和3.36%。结合HA和FA的元素组成和结构特征分析可知,疏水性强的HA能够促进BDE-47随水流迁移进入地下水系统;亲水性强的FA促进BDE-47在土壤系统中的分布,阻滞了土壤系统中BDE-47进入地下水系统。本文为评估HA、FA对土壤-地下水系统中BDE-47迁移的影响提供依据。     

Studies of Thermal Transformation of Humic and Fulvic Acids in Soils Ii. Thermogravimetry

The thermogravimetry and differential curves of the humic and fulvic acids in the soils from five areas of China were determined and the peaks of these curves were classified according to the results of infra-red (IR) spectra at high temperature and pyrolysis-mass spectra (Py/Ms). the kinetic parameters for heat-degradation of these humic and fulvic acids were calculated by the Coast-Redfern method. the initial temperatures, the final temperatures, and the peaks of DTG curves, the activation energies, the reaction orders and the percentages of weight loss at different reaction stages for these samples were analysed. Thus, the similarity of thermal transformation of humic and fulvic acids in the soils from different areas of China was demonstrated. in addition, the DTA curves of red earth HA and FA were determined.     

不同分子量的腐殖酸存在下2种无机砷的生物毒性效应研究

水环境中天然有机质会与砷形成络合物,进而影响砷的迁移、转化和生物毒性。研究利用超滤方法将腐殖酸(humic acid, HA)分为5个不同分子量的组分,以大型溞为受试生物,探究了不同分子量HA存在下砷对大型溞的毒性效应。结果表明,不同分子量的HA均缓解了As(Ⅲ)和As(Ⅴ)对大型溞的氧化应激损伤和细胞膜损伤,并降低了砷对MT的诱导量。其中1～30 k Da的HA对砷的缓解效果最好,1 k Da的HA毒性缓解效果最差,可能的原因是HA与砷的络合增加溶液中络合态砷的含量,而络合态砷难以进入细胞并被生物利用。不同分子量的HA对砷毒性的缓解差异与其跟砷的络合比例不同有关。     

Adsorption of humic acid from aqueous solution on bilayer hexadecyltrimethyl ammonium bromide-modified zeolite

Surfactant-modified natural zeolites (SMNZ) with different coverage types were prepared by loading hexadecyltrimethyl ammonium bromide (HTAB) onto the surface of a natural zeolite. The adsorption behavior of humic acid (HA) on SMNZ was investigated. Results indicate that the adsorbent SMNZ exhibited a higher affinity toward HA than the natural zeolite. HA removal efficiency by SMNZ increased with HTAB loading. Coexisting Ca²⁺ in solution favored HA adsorption onto SMNZ. Adsorption capacity decreased with an increasing solution pH. For typical SMNZ with bilayer HTAB coverage, HA adsorption process is well described by a pseudo-second-order kinetic model. The experimental isotherm data fitted well with the Langmuir model. Calculated maximum HA adsorption capacities for SMNZ with bilayer HTAB coverage at pH 5.5 and 7.5 were 63 and 41 mg·g^-1, respectively. E2/E3 (absorbance at 250 nm to that at 365 nm) and E4/E6 (absorbance at 465 nm to that at 665 nm) ratios of the residual HA in solution were lower than that of the original HA solution. This indicates that the HA fractions with high polar functional groups, low molecular weight (MW), and aromaticity had a stronger tendency for adsorption onto SMNZ with bilayer HTAB coverage. Results show that HTAB-modified natural zeolite is a promising adsorbent for removal of HA from aqueous solution.     

腐殖酸(HA)作用下纳米氧化锌对鲫鱼的毒性效应

通过静态模拟实验,研究不同浓度(0、1、1.5、2.5 mg L-1)腐殖酸(Humic acid,HA)对纳米ZnO(5 mg L–1)毒性效应的影响.将鲫鱼暴露于HA与纳米ZnO混合体系中7 d后,分析Zn在鲫鱼体内的富集分布,及对鲫鱼脑部和肝脏自由基含量、抗氧化系统等的影响.结果显示:随HA浓度的增加,鲫鱼鳃部和肌肉中Zn的含量增高,眼、脑和肝部Zn含量则随之下降.纳米ZnO诱导鲫鱼肝脏和脑产生羟基自由基,HA浓度增大诱导鲫鱼肝脏和脑中SOD活性升高,MDA、GSH含量增加.纳米ZnO胁迫导致鲫鱼肝脏和脑氧化损伤,HA的浓度增加会促进纳米ZnO对鲫鱼肝脏和脑部的氧化损伤.研究表明HA改变了纳米ZnO在环境中的生物效应,因此在关注纳米材料的水生态安全时,不能忽视环境因子的影响.     

Humic Acids from Endemic Arsenicosis Areas in Inner Mongolia and from the Blackfoot-Disease Areas in Taiwan: A Comparative Study

The physical and chemical properties of humic acids (HA) extracted from drinking waters from the endemic arsenicosis areas in Inner Mongolia and from the Blackfoot disease (BD) areas in Taiwan are studied by using AAS (atomic absorption spectrophotometry), ICP-MS (inductively coupled plasma emission-mass spectrometry), IR (Infrared spectroscopy), FR (fluorescence spectrometry) and TLS (total luminescence spectroscopy) in order to shed light on the pathogenesis of BD with the concern as to whether the disease may eventually occur in arsenicosis-affected areas in the Mainland of China. Ames test and lipid peroxidation experiments were also conducted on these HA samples. It is found that water samples from the two regions are high in arsenic (As) with strong fluorescence and apparent positive correlations between As content, fluorescence, pH and total dissolved solids (TDS). The water samples are similar in fluorescence spectra but differ somewhat in IR and TLS between the two regions. The difference may be a reflection of the difference in radicals and structure of the HA owing to different hydrogeological conditions, and may also be related to the difference in their biological effects, i.e., HA from Inner Mongolia have a stronger ability to cause lipid peroxidation while HA from Taiwan exhibits a more prominent effect of mutation with respect to TA98(±S9).     

运用关联度分析硒镧复合作用下巴西蘑菇氨基酸含量与砷含量的关系

通过采用混合培养料试验、日立8810型氨基酸自动分析仪和原子吸收法测定氨基酸含量和砷含量以及灰色系统理论分析关联度,研究了硒镧复合作用下巴西蘑菇子实体氨基酸含量和砷含量的变化和关系,为栽培砷含量低的巴西蘑菇提供科学依据.各硒镧复合处理的关联度排序为:B4>B1>B2>B0>B3.其中B4处理关联度最大,为0.835 1,B2最小,为0.726 9,说明硒镧浓度对巴西蘑菇子实体各氨基酸含量与砷含量有一定影响.各氨基酸含量与重金属砷含量关联度顺序为:丙氨酸>酪氨酸>胱氨酸>苯丙氨酸>赖氨酸>组氨酸>天门冬氨酸>异亮氨酸>苏氨酸>缬草氨酸>亮氨酸>甘氨酸>脯氨酸>精氨酸>丝氨酸>谷氨酸>甲硫氨酸.其中丙氨酸含量与砷含量关联度最大,为0.856 6,说明硒镧复合作用下巴西蘑菇子实体中丙氨酸含量与重金属砷含量的关系最为密切;关联度最小的是甲硫氨酸.     

Electrochemical oxidation of humic acid at the antimony- and nickel-doped tin oxide electrode

This work investigated the degradation of humic acid （HA） in aqueous solution by electrochemical oxidation with Antimony- and Nickel-doped Tin oxide electrode （Ni-Sb-SnO2/Ti electrode） as the anode. Initial concentrations of HA ranged from 3 to 9 mg-L 1. Under such a concentration scope, the degradation of HA was a mass transfer controlled process. Degradation rate increased with the increase of HA initial concentration. Test on the effect of tert-butanol revealed that · OH played an important role in the oxidation of HA. The absence of cation Ca2＋ was beneficial to HA degradation, which suggested that both indirect and direct electrolyze happened during the whole electrochemical oxidation process. Alkaly （pH = 12） and neutral （pH = 7） conditions were benefical to HA degradation.     

受体报告基因实验及其在维甲酸和维甲酸X受体干扰物监测中的应用

受体报告基因实验具有快速、经济、灵敏、方便等诸多优势,在高通量筛选类或抗雌雄激素等通过核受体起作用的环境内分泌干扰物方面得到了广泛的应用。环境中的维甲酸和维甲酸X受体干扰物如有机锡等有着类似的作用机制,研究者也开始采用受体报告基因实验的方法对该类污染物进行筛选与监测。本文综述了受体报告基因实验的技术方法,包括报告基因和宿主细胞的选择,并介绍了该方法在人工合成的维甲酸和维甲酸X受体干扰物筛选以及环境样品中该类污染监测中的应用。综述总结了应用受体报告基因实验检测环境内分泌干扰物研究中的不足并对该方法的未来发展进行了展望,希望为该方法在环境监测和评估中的应用提供新的思路。     

水体中胺鲜酯残留量的测定及其光解特性

建立了利用固相萃取-气相色谱(SPE-GC)测定水体中胺鲜酯残留量的方法.考查了3种不同固相萃取柱(C18、florisil、OasisR HLB)对水溶性农药胺鲜酯的吸附效果,发现它们对水中胺鲜酯的萃取效率依次为8%、13% 和96%;进一步研究了利用OasisR HLB萃取水中胺鲜酯的最佳条件(洗脱剂二氯甲烷用量4～8 mL),OasisR HLB(60 mg)小柱对胺鲜酯的保留容量高达200 μg·柱-1.运用该方法测定胺鲜酯光解试验样品,结果表明胺鲜酯质量浓度的对数与光照时间呈良好的线性关系.胺鲜酯在氙灯下的光化学降解符合一级动力学反应,光解半衰期为82 min,较易光解.     

珠江流域湖库型水源集水区酞酸酯(PAEs)类污染物环境健康风险评估

以饮用水源集水区为中心,沿支流采集水样,采用美国环境保护署(USEPA)暴露风险评价方法,结合该地区的参数计算环境健康风险。结果表明:(1)所有采样点均检出PAEs类污染物邻苯二甲酸正丁酯(DBP)、邻苯二甲酸二(2-乙基己基)酯(DOP)和邻苯二甲酸二乙酯(DEP),其中DOP高于DBP和DEP。(2)该饮用水源集水区3种PAEs污染物质量浓度均高于流域内其他乡镇饮用水源,在国内外同类地区也属于中上水平。DOP是集水区内需首要控制的PAEs类污染物。(3)在人类活动干扰少的地区河流污染物的环境健康风险水平较低,而在人口密集区和工业集中区风险水平较高。河流上游风险值低,中游高,下游和库区又逐渐回落。该水源集水区的PAEs类污染物环境健康风险值未超过USEPA规定,但与国内外其它地区相比属于中上水平,存在一定的潜在健康风险,需要根据PAEs的可能来源在水源地环境风险管理中加以防范。     

环境化学物对雄(男)性生殖损伤的评价指标及检测技术

随着工业的迅速发展,迄今为止,已有大约10万种化学物进入人们的日常生活.人们在生产和生活中接触的许多种环境化学物都会影响人类的生殖功能,使人类的生育能力特别是精子的质量和数量发生显著改变.环境化学物所造成的生殖损伤日益受到人们的重视,检测方法和检测技术日益成熟和完善.但大多数环境化学物对生殖的损害目前尚未得到全面地研究和认识,某些毒物的生殖毒性也需要重新认识与评价,生殖毒理学的研究任务迫切而艰巨.动物实验是生殖毒性评价中最主要的方法.在总结近年来国内外相关研究基础上综述了环境化学物动物实验中雄(男)性生殖损伤评价指标及检测技术,以期对环境化学物生殖毒性评价提供借鉴和参考.     

利用化学分析和生物毒性监测方法综合评价污水污泥环境影响的研究

利用化学分析和发光细菌生物毒性联合检测方法评价了上海地区7处污水处理厂污水污泥(分别用S1～S7表示)中主要污染物水平和毒性大小.结果表明,污水污泥样品S5和S7的重金属超过CJ/T 309-2009《城镇污水处理厂污泥处置农用泥质》标准和全国平均水平,主要超标重金属为Cd、Hg和Cu;污水污泥中多氯联苯、有机氯农药和二(噁)英类含量与组成则处于安全水平;样点S1～S6的多环芳烃(PAHs)平均含量低于CJ/T 309-2009中A级标准与欧盟和美国关于污水污泥的土地倾倒标准,但样点S7的w(ΣPAHs)达到34.61 mg·kg-1,超过CJ/T 309-2009最高允许限值的6倍.污水污泥浸出液化学分析结果表明,PAHs和重金属含量低于GB 5085.3-2007《危险废物鉴别标准浸出毒性鉴别》和欧盟EN 12457.2-2002 《废弃物表征浸出颗粒废弃物和污泥浸出一致性试验》标准,但所有样点的溶解性总有机碳均超过欧盟EN 12457.2-2002标准.发光细菌综合生物毒性结果表明:样点S3的综合毒性最高,S1、S6和S7次之,S2、S4和S5较低,以生活污水为主要来源的污水污泥的综合生物毒性较高.该结果可为污水污泥的后续处理和处置提供基础数据.     

植物体内水杨酸分析方法的探讨及其应用(Investigation and Application of Analysis Methods of Salicylic Acid in Plant Tissue)

准确测定植物中水杨酸的含量是深入研究其重要作用和抗病机理的必要前提.采用高效液相色谱(HPLC)对植物中内源水杨酸进行了分析,比较了紫外检测器和荧光检测器不同的检测结果,发现荧光监测器灵敏度更高,是紫外检测器的15倍.论文同时比较了使水杨酸与其他组分很好分离的液相色谱条件,结果表明,pH5.5的乙酸钠:甲醇(9:1,V/V)的流动相效果最好.用该方法测得的精密度的相对标准偏差为1.73%,重现性和稳定性均较好(稳定性的相对标准偏差为4.6%).论文以模式植物拟南芥(Arabidopsis thaliana)的野生型和水杨酸突变体两种类型为供试材料,对其体内水杨酸进行了提取测定,检测结果发现野生型体内的水杨酸的含量大约是水杨酸突变体的9倍,与文献报道吻合.     

牛磺熊脱氧胆酸在棕榈酸诱导的INS-1细胞凋亡中的作用（Effects of Tauroursodeoxycholic Acid on the Apoptosis of INS-1 Cells Cultured by Palmitate）

为观察牛磺熊脱氧胆酸(Tauroursodeoxycholic acid,TUDCA)对棕榈酸(Palmitate)诱导的INS-1细胞凋亡的影响,分别用不同浓度棕榈酸(0.25mmol·L-1、0.5mmol·L-1、1.0mmol·L-1),棕榈酸(0.5mmol·L-1)+不同浓度TUDCA(25μmol·L-1、50μmol·L-1、100μmol·L-1)培养INS-1细胞12h,用MTT法检测细胞毒性作用,流式细胞术检测细胞凋亡,RT-PCR技术检测凋亡相关基因Bax/Bcl-2的表达.结果表明,与空白对照组比较,棕榈酸组(浓度≥0.5mmol·L-1)INS-1细胞凋亡率显著上升(p<0.05);加TUDCA培养组,当浓度≥50μmol·L-1时,与棕榈酸组相比,INS-1细胞凋亡率显著下降(p<0.05),呈剂量-效应关系.此外,棕榈酸组(浓度≥0.5mmol·L-1)INS-1细胞凋亡相关基因Bax表达显著上升(p<0.05),Bcl-2则明显下降;加TUDCA后,Bax基因表达显著下降(p<0.05),而Bcl-2则明显上升(p<0.05),并呈剂量-效应关系.以上结果表明,TUDCA能够减少游离脂肪酸引起的INS-1细胞凋亡,对INS-1细胞发挥保护作用.而凋亡促进基因Bax的表达下调,凋亡抑制基因Bcl-2的表达上调可能是其作用机制之一.     

含铬污液在土壤中迁移规律的研究

通过静态吸附和动态土柱淋溶实验,研究了含铬污液中Ｃｒ（Ⅲ）、Ｃｒ（Ⅵ）在土壤中的迁移规律。结果表明,土壤对Ｃｒ（Ⅲ）、Ｃｒ（Ⅵ）的等温吸附过程均符合Ｌａｎｇｍｕｉｒ方程,土壤对Ｃｒ（Ⅲ）、Ｃｒ（Ⅵ）的饱和吸附量分别为２．１７＊１０＾４ｍｇ／ｋｇ、１７５ｍｇ／ｋｇ;动态截留量分别为７．００＊１０＾３ｍｇ／ｋｇ、５６．７ｍｇ／ｋｇ。