重金属离子存在下腐植酸和芘之间的相互作用

建立并验证了腐植酸(HA)和芘结合常数(Koc)测定的荧光猝灭法,进而研究了重金属离子对HA和芘相互作用的影响,测定了重金属离子存在下HA和芘之间的Koc.结果表明:纯化后的HA是分子质量较小的部分,水溶性较高,具有羟基、羧基和碳氧键等极性基团;HA利用其分子中的羟基、羧基、碳氧键等基团和重金属离子产生络合作用,这种络合作用影响了HA的结构;随着重金属离子浓度的增大,Koc遵循先增大,再减小,最后趋于不变的趋势.     

腐殖酸作用下沉积物中纳米氧化铜对铜锈环棱螺生态毒性的影响

为了探讨不同水平腐殖酸作用下沉积物中纳米氧化铜(CuO-NPs)对底栖生物生态毒理学效应的影响,以铜锈环棱螺(Bellamya aeruginosa)为受试生物,通过腐殖酸和CuO-NPs加标沉积物的慢性(28 d)生物测试,研究了肝胰脏中Cu的生物积累、Na+K+-ATP酶(ATPase)、超氧化物歧化酶(SOD)以及过氧化氢酶(CAT)活性的变化规律.结果表明,在低浓度CuO-NPs处理组(60 μg·g1),沉积物中腐殖酸水平对Cu的生物积累以及ATPase、SOD和CAT活性均没有显著影响.在中、高浓度CuO-NPs处理组(≥180 μg·g-1),Cu的生物积累均随腐殖酸水平的增加而显著升高;肝胰脏ATPase活性随腐殖酸水平的增加而显著下降;当腐殖酸水平为0.05 g·g-1时,SOD活性显著高于未添加腐殖酸组,表现为显著诱导,当腐殖酸水平≥0.1g·g-1时,SOD活性开始下降,并具有浓度依赖性;随腐殖酸水平的增加,肝胰脏CAT活性总体上表现为浓度依赖性显著下降.由于沉积物中腐殖酸的存在,显著增加CuO-NPs在沉积物中的分散稳定性,更容易被铜锈环棱螺摄取,从而通过增加CuO-NPs的生物积累而增强对铜锈环棱螺的生态毒性.     

Abiotic association of phthalic acid esters with humic acid of a sludge landfill

The abiotic association between phthalic acid esters (PAEs) and humic substances (HS) in sludge landfill plays an important role in the fate and stability of PAEs. An equilibrium dialysis combined with ¹⁴C-labeling was used to study the abiotic association of two abundant PAEs (diethyl phthalate and di-n-butyl phthalate) with humic acid (HA) isolated from a sludge landfill with different stabilization times and different molecular weights. Elemental analysis and Fourier Transform Infrared Spectrophotometer (FTIR) suggested that high K _A value of HA was related to the high aromatic content and large molecular weight of HA. The results indicated that the association strength of PAEs with HA depended on both the properties of the PAEs and the characteristics of HA. The K _A values of the association were strongly dependent on solution pH, and decreased dramatically as the pH was increased from 3.0 to 9.0. The results suggested that nonspecific hydrophobic interaction between PAEs and HA was the main contributor to the association of the PAEs with HA. The interactive hydrogen-bonds between the HA and the PAEs molecules may also be involved in the association.     

五氯苯酚与腐殖酸作用的荧光猝灭效应研究

通过对五氯苯酚与腐殖酸作用的荧光猝灭效应研究,探讨了五氯苯酚与腐殖酸之间的相互作用机理.结果表明,五氯苯酚可以有规律地猝灭腐殖酸的内源荧光,其猝灭机理可认为是五氯苯酚和腐殖酸形成复合物的静态猝灭,五氯苯酚与腐殖酸的结合常数较大,说明腐殖酸能够有效吸附五氯苯酚分子,形成复合物;并获得了不同温度下,五氯苯酚与腐殖酸作用的结合常数和热力学参数.根据所得结果可推断五氯苯酚与腐殖酸的主要作用力为氢键和范德华力.     

环丙氨嗪在Aldrich胡敏酸中吸附-解吸特征的研究

采用批平衡法,研究了不同温度下环丙氨嗪在Aldrich胡敏酸中的吸附与解吸特征。结果表明：环丙氨嗪吸附和解吸过程都包含极快速、快速和缓慢阶段。伪二级动力学方程能较好地描述不同温度下环丙氨嗪的吸附动力学特性,表明吸附速率决定于胡敏酸表面吸附位点的可用度,而不是溶液中环丙氨嗪的浓度。环丙氨嗪在极快速吸附阶段的吸附速率随温度的升高而增大,但平衡时的吸附量却随温度的增加而降低。吸附等温线和解吸曲线符合Langmuir方程和Freundlich方程。环丙氨嗪在胡敏酸上的解吸速率小于吸附速率,表明存在滞后效应。吸附焓变、熵变和自由能都为负值,表明环丙氨嗪在胡敏酸上的吸附是一个自发、熵减小的放热过程。-Go〈40 kJ.mol^-1表明环丙氨嗪在胡敏酸表面以物理吸附为主。     

氯酚在胡敏酸上的吸附

用静态平衡法了白洋研究泥中胡敏酸对氯酚的吸附情况,当温度升高或ＰＨ值降低时,ＨＡ对４－氯酚的吸附量增大,对４－氯酚和３,５－二氯酚两种吸附质组成的混合溶液,ＨＡ对３,５－二氯酚的吸附量大于ＨＡ对４－氯酚的吸附量;     

Phenanthrene adsorption by soils treated with humic substances under different pH and temperature conditions

The mobility of phenanthrene (PHE) in soils depends on its sorption and is influenced by either the existing soil humus or exogenous humic substances. Exogenous humic acids (HAs) were added to soil to enhance the amount of soil organic carbon (SOC) by 2.5, 5.0, and 10.0 g kg⁻¹. PHE desorption of the treated soils was determined at two pH levels (3.0 and 6.0) and temperatures (15 and 25 °C). Soil PHE adsorption was related to pH and the type and quantity of added HAs. Humic acid (HA) and fulvic acid (FA) derived from peat had different effects on adsorption of PHE. Adsorption increased at first and then decreased with increasing quantity of exogenous FA. When the soil solution pH (in 0.005 M CaCl₂) was 4.5 or 3.0, the turning points were 2.5 g FA kg⁻¹ at pH 3.0 and 5 g FA kg⁻¹ at pH 4.5. When soil solution pH was 6, the amount of adsorbed PHE was enhanced with increasing exogenous HAs (HA or FA) and amount of adsorption by soil treated with FA was higher than with HA. Adsorption of PHE in the FA treatment at 10.0 g kg⁻¹ was lower than the controls (untreated soil or treatment with HAs at 0 g kg⁻¹) when the soil solution pH was 3.0. This suggests that FA adsorbed by soil was desorbed at low pH and would then increase PHE solubility, and PHE then combined with FA. PHE adsorption was usually higher under lower pH and/or lower temperature conditions. PHE sorption fitted the Freundlich isotherm, indicating that exogenous humic substances influenced adsorption of phenanthrene, which in turn was affected by environmental conditions such as pH and temperature. Thus, exogenous humic substances can be used to control the mobility of soil PAHs under appropriate conditions to decrease PAH contamination.     

赤霉酸暴露对SD大鼠青春期发育的影响

赤霉酸是目前国内外使用极其广泛的一种植物生长调节剂,但是针对其发育毒性的数据依然较少。本文探讨了赤霉酸暴露对SD大鼠青春期发育的影响。参考国内外环境内分泌干扰物危害的评价方法,将144只初断乳SD大鼠按体重随机分为4组,分别为对照组和1、10、100 mg·kg-1bw剂量组,采用经口灌胃方式对雄鼠连续染毒28 d,雌鼠连续染毒21 d。暴露结束后检测大鼠的体重、食物利用率、雄鼠包皮分离时间/雌鼠阴道开口时间、血清生化指标、脏器系数及组织病理学的变化。研究结果表明,与对照组相比,仅10和100 mg·kg-1bw剂量组雄鼠的肌酐水平显著升高(P<0.01),100 mg·kg-1bw剂量组雌鼠谷丙转氨酶水平有显著升高(P<0.01)。而与对照组相比,所有剂量组均未观察到大鼠的体重、食物利用率、雄鼠包皮分离时间/雌鼠阴道开口时间、脏器系数等指标有显著性差异的改变(P>0.05),组织病理学结果亦显示大鼠重要器官无损害性改变。因此,在本试验给予的剂量范围内赤霉酸染毒不会对SD大鼠青春期发育产生显著影响。     

腐殖酸对As(V)在覆铁砂介质中吸附行为的影响

对腐殖酸(HA)进行了成分分析及红外表征,并从HA浓度、pH值、As(Ⅴ)初始浓度等方面,研究了HA对As(Ⅴ)在覆铁砂介质中吸附行为的影响.结果表明,随着HA浓度的升高,总砷去除率逐渐降低.当HA浓度增加到25mg.l-1时,与不存在HA条件下相比,总砷去除率降低了12%左右.溶液pH值影响As(Ⅴ)的去除,pH值从6升高到8时,总砷去除率从52.1%降到了39%.其中的作用机理主要是HA与As(Ⅴ)在覆铁砂表面形成竞争吸附,HA争夺了As(Ⅴ)的吸附点位.此外,HA与Fe(Ⅲ)的络合作用也是导致覆铁砂对砷的去除率降低的一个重要原因.     

溶解性有机碳的主要组成对青鳉鱼铜急性毒性的影响

为揭示溶解性有机碳(DOC)的组成对生物配体模型(BLM)预测铜的生物毒性准确性的影响,研究了不同浓度黄腐酸(FA)、腐殖酸(HA)和两者不同浓度比例混合物影响铜对青鳉急性毒性。结果表明:在相同水质条件下,黄腐酸或腐殖酸浓度增加时,铜对青鳉的LC50均增加;两者共存时,当腐殖酸质量百分比从10%增至90%时,铜对青鳉的LC50也增加。当天然水中DOC的组成不确定时,可假设HA和FA的组成比例为1∶1,此时BLM预测铜对青鳉的LC50的偏差最小。     

Removal of clofibric acid from aqueous solution by polyethylenimine-modified chitosan beads

Polyethylenimine （PEI）-modified chitosan was prepared and used to remove clofibric acid （CA） from aqueous solution. PEI was chemically grafted on the porous chitosan through a crosslinking reaction, and the effects of PEI concentration and reaction time in the preparation on the adsorption of clofibric acid were optimized. Scanning electron microscopy （SEM） showed that PEI macromolecules were uniformly grafted on the porous chitosan, and the analysis of pore size distribution indicated that more mesopores were formed due to the crosslinking of PEI molecules in the macropores of chitosan. The PEI-modified chitosan had fast adsorption for CA within the initial 5 h, while this adsorbent exhibited an adsorption capacity of 349 mg· g^-1 for CA at pH 5.0 according to the Langmuir fitting, higher than 213 mg· g^-1 on the porous chitosan. The CA adsorption on the PEI- modified chitosan was pH-dependent, and the maximum adsorption was achieved at pH 4.0. Based on the surface charge analysis and comparison of different pharmaceu- ticals adsorption, electrostatic interaction dominated the sorption of CA on the PEI-modified chitosan. The PEI- modified chitosan has a potential application for the removal of some anionic rnicropollutants from water or wastewater.     

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.     

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.     

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。     

Effects of humic acid on residual Al control in drinking water treatment plants with orthophosphate addition

This study aimed to investigate the effects of humic acid (HA) on residual Al control in drinking water facilities that used orthophosphate addition. The results showed that adding orthophosphate was an effective method for residual Al control for the raw water without HA. When orthophosphate was added at 1.0 min before the addition of poly aluminum chloride (PACl), the concentrations of soluble aluminum (Sol-Al) and total aluminum (Tot-Al) residue were 0.08 and 0.086 mg·L^-1, respectively; both were reduced by 46% compared with the control experiment. The presence of HA would notably increase the residual Al concentration. For the raw water with 5 mg·L^-1 of HA, the concentrations of Sol-Al and Tot-Al increased from 0.136 and 0.174 mg·L^-1 to 0.172 and 0.272 mg·L^-1, respectively. For water with a HA concentration above 5 mg·L^-1, orthophosphate was ineffective in the control of residual Al, though there were still parts of orthophosphate were removed in coagulation. The amounts of Al removal were positively correlated with the solids freshly formed in coagulation. Similar to the raw water without HA, the best Al control was obtained with orthophosphate salt added at 1.0 min before PACl. HA concentrations in the raw water, solution pH, and the orthophosphate dosage suitable for residual Al control by orthophosphate precipitation were also investigated.     

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.     

土壤中腐殖酸对外源农用稀土生物可利用性的影响

采用盆栽实验方法,研究了腐殖酸对稀土元素在土壤-植物体系中的迁移、富集和生物可利用性的影响,结果表明,在试验土壤红壤中,稀土元素主要富集在小麦根部,加入低浓度的腐殖酸后,促进了小麦对稀土元素的吸收：而高浓度的腐殖酸则抑制小麦对稀土元素的吸收,腐殖酸浓度过高时,对小麦生长产生毒害作用,同时发现,小麦中叶绿素含量与小麦中稀土含量存在相关关系。     

碱性条件下胡敏酸吸附镉的特征研究

为了探讨胡敏酸在碱性条件下的吸附镉机理,了解碱性盐化土壤中镉污染机理和生态环境之间的关系,实验研究了胡敏酸在碱性条件吸附镉的特征。采用批吸附试验方法,研究不同Cd初始浓度、反应时间、不同pH和离子强度对胡敏酸吸附镉的影响,结果表明：胡敏酸具有较强吸附镉的能力,可以用Langmuir吸附模型和Temkin吸附模型很好地拟合其等温吸附过程（r分别为0.9809和0.9816）;在60 min内的快速反应阶段和60 min至6 h间的慢速反应阶段,胡敏酸对镉的吸附量分别为2.895 mg·g-1和3.342 mg·g-1,吸附反应平衡前6 h的动力学过程可以用Elovich方程进行很好的拟合（r为0.9285）;随着pH增加,吸附率表现出逐步增加趋势,并以pH为4.5和8.5为界,呈现两端增加速度快,中间增加慢的规律性;在较低浓度离子强度下,离子强度的增加促进胡敏酸吸附镉;而在高离子强度下,表现出相反的规律性;在相同的条件下,不同离子强度对胡敏酸吸附镉的影响大小为：氯化钙〉氯化镁〉氯化钾〉氯化钠。土壤在盐化的过程中,由于无机盐浓度的增加,增加了重金属离子的生物可利用性,加大了重金属离子的生态风险。     

草炭溶解态有机物质与Cu2+、Cd2+络合稳定性的研究

研究了由草炭提取的胡敏酸(HA)、富里酸(FA)、水溶解态有机物质(WSOM)的基团特征,分子量分布及其与Cu2+、Cd2+两种金属离子之间的络合稳定性。对HA、FA及WSOM的红外光谱研究显示三者的官能团组成相似,只是含量略有不同。固态13C-NMR对HA、FA及WSOM结构特征的描述以及水相凝胶色谱法对三种有机质样品的分子量及分子量分布的测定结果显示HA分子最大且含有大量的长链烷烃,而FA分子小得多,结构以碳水化合物及多糖为主,WSOM的分子量略低于FA,结构与FA相近。离子交换平衡法对三种有机质样品与Cu2+、Cd2+的络合配位数和稳定常数的测定结果显示两种介质条件下络合配位数(x)、络合稳定常数(logk)的次序均为:Cu2+>Cd2+;同一介质条件下,对不同有机质而言均满足:M-HA>M-FA>M-WSOM。     

荧光猝灭法测定菲、苊、芘与腐殖酸的结合常数

用荧光猝灭法测定了胡敏酸（Fluka）与苊、菲和芘相互作用的结合常数（KDOC），其lgKDOC值分别为4．4，4．48和4．89．用同样方法测得长江水生FA以及黑龙江水生FA和HA的KDOC之间有显著差别．HA的KDODC一般高于FA．黑龙江水生FA的KDOC高于长江．对同一来源的腐殖酸，三种多环芳烃的KDOC与KOW呈线性相关．