毒死蜱农药环境行为研究

研究了毒死蜱农药在环境中的水解、土壤吸附和土壤消解行为。实验结果表明，毒死蜱在水体中降解较慢，半衰期为 ２５．６ ｄ；土壤具有较强的吸持毒死蜱农药的能力；该农药在土壤中的消解也较慢。     

TiO2对毒死蜱在土壤表面光降解的催化作用

以太阳光为光源研究了TiO2用量、毒死蜱初始浓度、土壤厚度对毒死蜱在土壤中的光解行为的影响.结果表明:毒死蜱的光解符合准一级动力学方程,且随添加TiO2用量从0 mg·kg-1增加到200 mg·kg-1,毒死蜱的一级光解动力学常数也增大,其中最快的降解速率是最慢的1.51倍.在含有TiO2的土壤中,添加浓度相对较低的情况下,毒死蜱的降解较快;毒死蜱在不同厚度土壤中的光解速率不同,土壤厚度较大的情况下.毒死蜱的半衰期也比较大.     

黄铁矿对水体中腐殖酸的吸附特性

选择富里酸(fulvic acid,FA)和胡敏酸(humilic acid,HA)作为吸附对象,通过铁矿物吸附筛选实验,以黄铁矿(pyrite)为吸附剂研究其对水体中两种典型腐殖酸(humic acid)的吸附特性.利用X射线衍射(XRD)、扫描电子显微镜(SEM)、X-射线光电子能谱(XPS)、红外光谱(IR)、纳米粒度及电位(Zeta)分析仪和比表面仪(BET)对黄铁矿进行组成及结构表征.考察了腐殖酸溶液p H、离子强度和温度等条件对黄铁矿吸附的影响.结果表明,黄铁矿是层状结构,吸附腐殖酸后,在黄铁矿表面形成了大小均匀的分子簇,且黄铁矿晶粒尺寸减小了约10 nm;黄铁矿对FA、HA的最大吸附量分别为11.8 mg·g-1和13.1 mg·g-1.随着p H增加,黄铁矿对腐殖酸的吸附量均表现为先增大后减小;离子强度(NaCl)对吸附的影响较小;随着温度升高,其吸附量不断增大.两种腐殖酸吸附数据与Langmuir吸附模型拟合良好且其吸附动力学规律均符合二级动力学模型,热力学研究表明,黄铁矿吸附两种腐殖酸均属于自发进行的吸热反应.     

毒死蜱对紫金山森林土壤酶活力及微生物毒性影响研究

毒死蜱是有机磷类农药,对乙酰胆碱酯酶具有抑制作用,在农业虫害防治中应用广泛。为掌握毒死蜱对森林土壤酶活力和土壤微生物生态效应,选择紫金山森林土作为受试土壤,采用室内培养法,研究了毒死蜱对土壤蔗糖酶、脲酶、酸性磷酸酶和过氧化氢酶,以及土壤呼吸强度和氮素硝化作用的影响。结果表明:试验期间,1.25 mg a.i.·kg-1、12.5 mg a.i.·kg-1和125 mg a.i.·kg-1毒死蜱对土壤脲酶、酸性磷酸酶总体表现为抑制作用;对土壤蔗糖酶和过氧化氢酶的影响与暴露剂量和暴露时间有关,在60 d时,Z1低剂量处理组(1.25 mg a.i.·kg-1)蔗糖酶和过氧化氢酶可恢复,Z100高剂量处理组(125 mg a.i.·kg-1)抑制作用不能解除。试验初期,毒死蜱对土壤呼吸强度有一定刺激作用随后逐渐恢复;对土壤氮硝化作用影响表现为先促进后抑制,且抑制作用有长期影响。由此可知,毒死蜱使用对紫金山森林土的土壤酶活性和土壤微生物产生毒性效应,具有一定生态风险。     

三峡库区消落带土壤对Cu(Ⅱ)、Zn(Ⅱ)的吸附特征

以三峡库区消落带紫色土为对象,采用平衡吸附法研究了Cu(Ⅱ)、Zn(Ⅱ)在紫色土中的吸附特征,分析了紫色土对重金属的吸附能力.结果表明:(1)随着加入Cu(Ⅱ)、Zn(Ⅱ)浓度增高,紫色土对Cu(Ⅱ)、Zn(Ⅱ)的吸附量增大,碱性紫色土对Cu(Ⅱ)、Zn(Ⅱ)的吸附量最高分别为1499.5 mg.kg-1、2845.4 mg.kg-1;(2)土壤中有Cu(Ⅱ)、Zn(Ⅱ)的专性吸附位点,在两者共存的条件下存在竞争吸附,Cu(Ⅱ)的竞争吸附能力大于Zn(Ⅱ),其各自的最大吸附量小于单一离子条件下的吸附量,碱性、中性、酸性紫色土Cu(Ⅱ)最大吸附量的下降幅度分别是14.5%、15.2%、15.9%,Zn(Ⅱ)的最大吸附量下降幅度分别为31.7%、28.1%、25.7%;(3)共存阳离子类型及浓度影响紫色土有效Cu(Ⅱ)、Zn(Ⅱ)含量,随着阳离子的加入,碱性紫色土的有效Cu(Ⅱ)含量增加,酸性紫色土减少,而3种紫色土的有效Zn(Ⅱ)含量均增加.消落带土壤淹水后,水体中Cu(Ⅱ)及其他阳离子的存在使土壤对Zn(Ⅱ)的吸附力降低,造成Zn(Ⅱ)污染的环境风险增加.     

外源硅对土壤镉吸附特性的影响

通过吸附等温试验,研究了不同加入量的硅对两种水田土壤吸附镉特性的影响。实验中调节介质的pH值至中性,从而消除了因硅酸盐的加入对土壤pH产生的影响。结果表明:在硅的加入量相同时,pH值较低的土壤对镉的吸附量要低于pH值较高的土壤;镉的加入质量浓度为0～50mg·L-1时,应用Freundlich方程拟合土壤对镉的吸附等温线效果最好;外源硅的加入量在0～120mg·L-1范围内时,随硅的加入量的增加土壤对镉的吸附量会有不同程度的降低。由此推断,对于以往研究发现的外源硅能够降低土壤镉的有效性、缓解植物的镉毒害作用,并非是促进了土壤对镉的吸附,而是可能存在着其他机制,这有待于进一步研究。     

三江平原湿地土壤磷的吸附与解吸研究

采用恒温培养法研究了三江平原典型沼泽湿地表层土壤中磷的吸附与解吸行为及其动力学过程。结果表明:湿地土壤对磷的自然释放量有限(1.89～13.25mg·kg-1),对磷酸盐具有较强的吸附能力,吸附量与土壤本身理化性质及水中磷酸盐初始质量浓度有关,其吸附/解吸平衡浓度(EPC0)在0.034~0.161mg·L-1之间。研究区域湿地表层土壤磷的吸附解吸特征趋于一致,吸附过程表现为快慢两种反应。六种动力学方程都能很好的拟合土壤磷吸附动力学过程,其中以langmuir型方程的拟合性最好,Evolich方程次之。     

牛粪生物炭对紫色土吸附-解吸腐殖酸的影响

通过探讨牛粪生物炭对紫色土吸附-解吸腐殖酸的影响,以减少紫色土腐殖酸的流失、提高腐殖酸利用率,为提高龙川江流域紫色土肥力提供理论依据.采用土培实验,用Langmuir和Freundlich模型、Lagergren准一级和Lagergren准二级动力学方程,研究了不同添加比例牛粪生物炭(BC、CK、1%、3%、5%)对腐殖酸的吸附与解吸的影响.采用扫描电镜、BET等方法分析牛粪生物炭的表面结构以及比表面积,来探讨牛粪生物炭对紫色土吸附和解吸HA的影响机理.结果表明,牛粪生物炭对紫色土等温吸附HA过程符合Langmuir模型,动力学模型符合Lagergren准二级动力学方程;各处理对紫色土等温吸附-解吸HA过程有明显的影响,CK对HA的吸附量和吸附率最低,解吸率最高;5%对HA的吸附量、吸附率和解吸量最高.同时,各处理对紫色土吸附-解吸HA动力学也有明显的影响,在前12 h,吸附速率逐渐增加,随后吸附逐渐达到平衡,吸附过程以化学吸附为主.各处理方法相比,5%更有利于吸附HA,防止HA流失.     

水浮莲干体对甲基橙的吸附研究

研究了水浮莲干体对模拟染料废水中甲基橙(MO)的吸附行为,考察吸附时间、溶液初始pH值、水浮莲干体用量和MO初始质量浓度等因素对MO吸附的影响.结果表明,在MO溶液初始pH值为5.5、初始质量浓度为25 mg·L-1条件下,添加12.5g·L-1粒径为0.250～0.425 mm的水浮莲干体,于25℃条件下以120 r·min-1振荡吸附90 min后,MO吸附率可达72.1％.酸性环境有利于MO吸附;一定范围内,水浮莲干体用量的增加以及MO初始浓度的升高都会导致吸附率升高.水浮莲干体对MO的吸附过程更符合Freundlich吸附等温方程,Lagergren准二级动力学方程更适合模拟其吸附动力学行为.随温度升高,MO平衡吸附量呈减少趋势.水浮莲干体及浸出液中Cr、Ni、Cu、As、Cd和Pb含量远低于GB 5085.3-2007 《危险废物鉴别标准浸出毒性鉴别》中的限量值,因此将水浮莲干体作为新型吸附剂应用于染料废水处理,不会导致二次污染.     

腐殖酸对U(Ⅵ)的吸附机理研究

通过静态吸附实验,研究了腐殖酸(HA)对U(Ⅵ)的吸附特征,考查了腐殖酸在不同试验条件对U(Ⅵ)吸附的影响.试验结果表明:吸附过程在1.5 h后达到动态平衡;最佳吸附剂用量为2.0 g·L~(-1);随着U(Ⅵ)的初始浓度增大,腐殖酸对U(Ⅵ)的吸附效果不断降低,最大K_d值在铀的初始浓度为20 mg·L~(-1)时获得;溶液中Ca~(2+)、CO■对U(Ⅵ)的吸附有很强的的抑制作用,影响程度随着离子浓度的增加而增大;腐殖酸对U(Ⅵ)吸附过程符合Langmuir等温吸附方程和准二级动力学模型.     

软脂酸和硬脂酸对铜绿微囊藻生长的抑制作用

研究了软脂酸和硬脂酸对产毒铜绿微囊藻Microcystis aeruginosa生长的抑制效应,比较了长链饱和脂肪酸抑藻的构效关系。选用的藻种是购于中国科学院水生生物研究所的产毒铜绿微囊藻Microcystis aeruginosa FACHB-912,且实验藻种处于对数生长期。软脂酸和硬脂酸在藻液中的4种最终质量浓度为：30、60、90和120mg·L-1。实验周期为6d,每天定时定量取藻液,测量A（650nm）,叶绿素a含量,藻蓝蛋白含量。实验结束后,采用SPSS（13.0版本）软件和DPS（7.05版本）分析加入这2种脂肪酸的藻液的3个指标与空白对照之间的差异显著性。结果表明,2种饱和脂肪酸的4种质量浓度对产毒铜绿微囊藻均有显著的抑制作用,浓度越大,抑藻效果越明显。其中,2种饱和脂肪酸在相同浓度的条件下,软脂酸比硬脂酸的抑制作用要明显。实验技术方面有2个创新点：①因为长链饱和脂肪酸无法溶于蒸馏水,实验采用乙醇来溶解脂肪酸。②因为溶于乙醇的长链饱和脂肪酸溶液无法用高压灭菌锅灭菌,实验采用微孔滤膜对脂肪酸溶液进行灭菌。     

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.     

Structure of aldobiouronic acid and glucuronic acid from Agathis australis degraded gum polysaccharide

Agathis australis gum on acid hydrolysis with sulphuric acid yielded L-arabinose and D-galactose in 1:4 molar ratio with traces of L-fucose. The components of aldobiouronic acid and glucuronic acid were obtained by graded hydrolysis of degraded gum polysaccharide. The derivatives of aldobiouronic acid was obtained as methyl ester methyl glycoside.     

Adsorption selectivity of salicylic acid and 5-sulfosalicylic acid onto hypercrosslinked polymeric adsorbents

Both bottle-point and column-feeding experiments involving different solutes and sorbents were carried out to investigate the adsorption selectivity and separation performance of salicylic acid and 5-sulfosalicylic acid. Their adsorption isotherms onto such hypercrosslinked polymeric adsorbents as NDA-100 and NDA-99 could be well described by the Freundlich equations whose characteristics describe extrathermic and favorable adsorption processes. The adsorption towards NDA-100 mainly depended on the π-π interaction, while that towards NDA-99 was extremely influenced by the static-electric interaction. Additionally, the adsorptive capacity of salicylic acid on NDA-99 decreased while it increased on NDA-100 with the presence of 5-sulfosalicylic acid in the adsorptive environment as the competitive component. Comparatively, the adsorption capacity of 5-sulfosalicylic acid decreased on both resins with salicylic acid as the competitive component. In fact, the difference in the interaction between adsorbent and adsorbate resulted in the straight antagonism on the effective adsorption sites on the adsorbent. In conclusion, the adsorption selectivity of salicylic acid onto NDA-100 was obviously larger than that onto NDA-99 with the existence of 5-sulfosalicylic acid in the adsorptive environment. A satisfactory separation and recovery of tested solutes in aqueous phase could be foreseeably achieved by the sequencing adsorption technique involving NDA-100 as well as NDA-99.     

Remediation of acid mine drainage

Environmental Chemistry Letters - Acid mine drainage induced by the mining industry causes environmental and economic issues. Acid mine drainage contains mainly metals such as Fe, Al, Cu, Ca, Mg,...     

A novel proton-gradient-transfer acid complexes as an efficient and reusable catalyst for fatty acid esterification

In this work, a series of novel proton-gradient-transfer acid complexes (PGTACs) were developed. Their physicochemical properties, including thermal stability, melting point, and Hammett acidity, were measured. The effects of catalyst loading, reaction temperature, and substrate expansion on the catalytic performance were systematically studied. It is found that the combination of bidentate N-heterocycle and H2SO4 (1:2 M ratio) could form simultaneously N–H covalent bond and N…H hydrogen bond, which makes the PGTACs excellent catalysts integrate the advantages of strong acids (high catalytic activity) and ionic liquids (phase separation) in the esterification reaction. Moreover, these PGTACs can be reused by convenient phase separation without obvious diminution of catalytic activity. It is concluded that these PGTACs are potential alternative candidates for esterification reaction in the process of industrial catalysis.     

柠檬酸存在下酸性土壤中铝溶解动力学的初步研究

用一次平衡法研究了柠檬酸存在下砖红壤和红壤中铝的溶解动力学并与高岭石的结果进行比较，结果表明土壤铝的溶解速率比高岭石中的大得多，这主要因为土壤中交换态铝和无定形氧化铝的溶解速率较快，而粘土矿物中铝的溶解速率比较缓慢。红壤中硅、铝释放量的比较证明了这一假设，反应41．5h，硅的释放量仅为铝的8％。48h内铝的溶解动力学曲线可分为3个阶段：0-30min的快反应阶段，主要是土壤交换态铝和结晶不良的氧化铝的溶解；30-120min的较快反应阶段，主要是铝氧化物的溶解；120min后的慢反应阶段，主要是氧化铝和粘土矿物中铝的溶解。     

模拟酸雨对酸性土壤铝溶出及其形态转化的影响

研究了我国南方酸沉降区主要土壤类型在模拟酸雨影响下，土壤中铝离子释放及铝形态转化的特点。结果表明，酸雨淋洗造成土壤中铝离子释放，酸雨pH值越低，铝离子释放量越大；酸雨淋洗还造成土壤中铝形态发生变化，酸雨pH越低，土壤中羟基态铝和腐殖质铝含量愈低，交换态铝含量越高，土壤中铝对植物和生态系统的危害性也越大。     

Salicylic acid to decrease plant stress

Pollution and climate change degrade plant health. Plant stress can be decreased by application of salicylic acid, an hormone involved in plant signaling. Salicylic acid indeed initiates pathogenesis-related gene expression and synthesis of defensive compounds involved in local resistance and systemic acquired resistance. Salicylic acid may thus be used against pathogen virulence, heavy metal stresses, salt stress, and toxicities of other elements. Applied salicylic acid improves photosynthesis, growth, and various other physiological and biochemical characteristics in stressed plants. Salicylic acid antagonizes the oxidative damaging effect of metal toxicity directly by acting as an antioxidant to scavenge the reactive oxygen species and by activating the antioxidant systems of plants and indirectly by reducing uptake of metals from their medium of growth. We review here the use of exogenous salicylic acid in alleviating bacterial, fungal, and viral diseases, heavy metal toxicity, toxicity of essential micronutrients, and salt stress.     

不同耐铝型小麦品种苹果酸分泌差异与有机酸代谢关系研究

铝胁迫下不同耐铝型植物有机酸分泌存在显著差异,有机酸主要在三羧酸循环途径中产生,但目前有机酸分泌差异与有机酸代谢关系还不是很清楚。以耐铝型小麦Triticum aestivum L.品种ET8和铝敏感型小麦品种ES8为材料,研究了铝胁迫对不同耐铝小麦品种根内源苹果酸含量及磷酸烯醇式丙酮酸脱氢酶（PEPC）,柠檬酸合成酶（CS）和苹果酸脱氢酶（MDH）等酶活性的影响。结果表明：铝处理（0、25、50、100μmol.L-1）对内源苹果酸含量无显著影响,相同处理条件下ET8和ES8间亦无显著差异,分别为每根尖（0.48±0.01）、（0.46±0.03）、（0.57±0.02）、（0.52±0.02）nmol和（0.45±0.02）、（0.51±0.09）、（0.51±0.11）、（0.54±0.04）nmol;同无铝处理相比,50或100μmol.L-1铝处理显著促进ET8和ES8根尖细胞PEPC活性升高,但各铝浓度处理对CS和MDH活性无显著影响;相同处理条件下ET8和ES8根尖细胞PEPC,CS和MDH 3种酶活性均无显著差异。综上所述,铝胁迫下不同耐铝小麦品种根苹果酸分泌差异与内源苹果酸含量及有机酸代谢无关。