Effect of natural aquatic humic substances on the photodegradation of bisphenol A

The photochemical degradation of bisphenol A (BPA) was studied in the presence of natural humic substances from different origins under simulated solar irradiation. BPA underwent insignificant direct photolysis in neutral water, but rapid photosensitized degradation in four humic substances solutions via pseudo-first-order reaction occurred. The photo-degradation rate of BPA was insensitive to the different initial BPA concentrations and was inhibited in aerated solution compared with the deoxygenated medium. The reactive oxygen species (ROS) such as ·OH and ¹O₂ produced from excitation of humic substances under irradiation was determined from the quenching kinetic experiment using molecular probe. The five main intermediate photoproducts of BPA in Nordic lake fulvic acid (NOFA) were tentatively identified using gas chromatography/mass spectrometer (GC/MS). Based on the identification of ROS and the analysis of photoproduct formation, the possible phototransformation pathways of BPA were proposed, involving the direct photolysis due to the energy transfer from the triplet state humic substance (³HS*) to BPA molecules and hydroxyl radical addition and oxidation as well.     

Effect of humic acids on the Fenton degradation of phenol

We show that the degradation of phenol by Fe(III) and hydrogen peroxide is faster in the presence of humic acids. This is most likely due to faster reduction of Fe(III)-humate complexes by H₂O₂/HO₂^·/O₂^–· when compared with Fe(III)-H₂O complexes. The fact that humic acids, a major class of naturally occurring compounds, favour the Fenton reaction has great relevance in the field of water and soil decontamination, where organic compounds usually have a negative effect. Furthermore, it adds insight into the self-depuration processes of natural aquifers.     

表面活性剂和金属离子对新农药硫肟醚光解的影响

硫肟醚[O-(3-苯氧苄基)-2-甲硫基-1-(4-氯苯基)丙基酮肟醚]是我国研制成功的具有自主知识产权的一种新型杀虫剂.在室内紫外光(λ254 nm)照射下研究了几种表面活性剂和金属离子对硫肟醚在水溶液中光解的影响.试验结果表明,当土温80(Tween80)、十二烷基苯磺酸钙(ABS-Ca)、蓖麻油聚氧乙烯醚(BY)、三氯化铁(FeCl_3)、硫酸铜(CuSO_4)和无水硫酸镁(MgSO_4)分别与硫肟醚以1:1的比例混合后,硫肟醚的光解速率发生了不同程度的改变.ABS-Ca对硫肟醚在水溶液中的光解速率表现出显著的光猝灭降解效应,蓖麻油聚氧乙烯醚类表面活性剂BY对硫肟醚在水溶液中的降解表现出一定程度的光敏化作用.而吐温80对硫肟醚在水体中光解速率的影响则随照光时间而改变,当照光时间小于40 min时,表现为光敏化降解作用,大于40 min时可延缓硫肟醚的光解进程,表现出光猝灭作用.Fe~(3+)使硫肟醚在水溶液中的光解速率增快,表现出明显的光敏化降解效应,而Cu~(2+)和Mg~(2+)使硫肟醚在水体中的光解速率减慢,表现为较强的光猝灭降解作用.硫肟醚在含Tween80、ABS-Ca、BY、FeCl_3、CuSO_4和MgSO_4水溶液中的光解半衰期分别为21.63、34.42、15.29、9.85、43.95和32.20 min,而在不含任何农药化肥的纯净水中的光解半衰期为22.30 min.     

Nitrite and nitrate induced photodegradation of monolinuron in aqueous solution

Here we evidenced the photo-induced degradation of monolinuron, a phenylurea herbicide, through the 300–450 nm light excitation of nitrite and nitrate species. The degradation pathways were compared to those obtained under direct photolysis at 254 nm. When using NO₃^– and NO₂^– as photoinducers, hydroxyphenyl-substituted photodegradation products were found to be formed specifically through the involvement of OH° radicals. NO^– and NO₂-phenyl substituted compounds were also observed as a result of the production of NO° and NO₂° radicals. Half-lives of monolinuron in aqueous solutions were measured in various conditions of concentrations of substrate and inducer, oxygen content and pH.     

Strong adsorption of DNA molecules on humic acids

Analysing soil microbial communities is often hampered by DNA adsorption on soil organic compounds such as humic acids. However the role of humic acids in DNA adsorption and stability in soils remains controversial. To characterize DNA–humic acid interactions, we studied DNA adsorption on two commercially available humic acids and a soil humic acid extracted from an Andosol. Desorption of the adsorbed DNA using 4 different solutions—distilled water, 0.1 M NaCl, 0.1 M sodium phosphate buffer (pH 6.0), and 1% sodium dodecyl sulfate solution—was also studied to understand the mechanism of DNA adsorption on humic acids. Here, we show that humic acids play an important role in DNA adsorption to soils. DNA molecules were adsorbed on the humic acids, with adsorption increasing proportionally with the DNA concentrations in the solution. The adsorption on all humic acid samples was fitted with Freundlich equation, and the parameters obtained from the equation indicated a high affinity between the humic acids and DNA molecules. The total amount of DNA desorbed by the 4 solutions was less than 2% of the total DNA adsorbed on all the humic acids. The results demonstrate that DNA molecules are able to bind strongly to humic acids by ligand binding, hydrophobic interaction, aggregation, or precipitation.     

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.     

腐殖酸对铜的吸附与解吸特征

采用铜离子选择电极研究了铜在腐殖酸两组分(富里酸FA、胡敏酸HA)中的吸附-解吸特征,以及介质pH对这种吸附-解吸的影响。结果表明,腐殖酸对铜的吸附量为FA>HA,吸附强度为HA>FA,解吸量FA-Cu>HA-Cu。腐殖酸两组分对铜的吸附,当介质pH为4.00～7.00时,很好地符合Langmuir等温吸附方程;当pH<4.0时,符合Freundlich方程。FA、HA与铜作用的条件稳定常数与介质pH有关,pH提高则条件稳定常数增大;但在低pH段和高pH段,其增长规律不一致,当4.00相似文献   

Effects of humic acid fractions with different polarities on photodegradation of 2,4-D in aqueous environments

Four fractions (A, B, C, and D) of humic acids (HAs) were separated based on the polarity from weak to strong. UV-vis absorption and Fourier transform infrared spectroscopy (FTIR) analysis show that the fractions C and Dpossessedmore aromatic C=C content. The influences of HAs and their fractions on the photolysis were investigated by the photodegradation of 2,4-D solutions under simulated solar light irradiation. The degradation rate of 2,4-D was found to decrease in the presence of bulk HAs or their fractions especially at high HAs concentration. The fractions of strong polarity C and D retarded the degradation rate more than the fractions of weak polarity A and B. This could be attributed to the different absorption intensity of the four HAs fractions in the order of D ? C > A > B, and the stronger π-π electron donor-acceptor interactions between the strong polar fractions and 2,4-D.     

施氮对植物生长、硝态氮累积及土壤硝态氮残留的影响

施用N肥可提高叶类蔬菜的产量,但施用过量也会造成土壤N污染。为了研究当年施肥量对作物硝态氮累积及土壤无机氮残留量的影响,采用土壤盆栽试验,研究了5个施氮水平下3种叶类蔬菜(油菜、小白菜、菠菜)的生长、硝态氮累积和土壤硝态氮残留的变化。结果表明,施氮过高抑制了植物的生长,其中对菠菜的抑制作用最强。3种蔬菜硝态氮累积对施N的反应不同,油菜在施N0.40g时硝态氮含量达到最高,为N1742.2μg·g-1FW;小白菜在0.60g最高,为N1635.6μg·g-1FW;而菠菜则在0.80g最高,为N865.2μg·g-1FW。施N量与土壤硝态氮残留量之间呈显著正相关关系,说明施氮量越高土壤中硝态氮的残余就越大,对土壤的污染就越严重。     

Photodegradation of the pure and formulated alpha-cypermethrin insecticide gives different products

Alpha-cypermethrin is a broad-spectrum insecticide widely used in the treatment of rice crops, mainly commercialized as a CONTEST^® formulation. The photodegradation of alpha-cypermethrin and of the commercial formulation has not yet been systematically investigated in paddy water under natural conditions. Here, paddy water solutions of alpha-cypermethrin and CONTEST^® formulation at 5.0 mg L^?1 were irradiated under simulated sunlight for 10 days. Hydrolysis experiments were carried out on the same solutions preserved in the dark. Analysis by ultra-high-performance liquid chromatography–tandem mass spectrometry was developed for the identification of photodegradation products. Results show that degradation of pure alpha-cypermethrin and the formulation counterpart produces both common and different photodegradation products. Five out eleven photodegradation products were identified for the first time, in particular three in the alpha-cypermethrin paddy water solution and four in the formulation. Our findings underline the importance of carrying out photodegradation experiments directly on the commercial formulation, since degradation products could be different from the pure insecticide.     

Suppression of inhibition of substrate photodegradation by scavengers of hydroxyl radicals: the solvent-cage effect of bromide on nitrate photolysis

In this paper we show that bromide scavenges the ^·OH radicals formed upon photolysis of nitrate, before they leave the solvent cage. Bromide can thus inhibit the in-cage recombination between ^·OH and ^·NO₂. The consequence is an increased generation of ^·NO₂ and nitrite and of Br₂ ^?· + ^·OH, compared to ^·OH alone in the absence of bromide. We show that this effect compensates for the lower reactivity of Br ₂ ^?· compared to ^·OH toward certain organic substrates, e.g. phenol and tryptophan. Our findings could lead to a deep revision of the present views of the role of bromide in saltwater photochemistry.     

合成腐殖酸氧化还原能力与光学性质探究

本文以合成商业腐殖酸Aldrich humic acids(AHA)与国药化学试剂腐殖酸(TJHA)为研究对象,与铁氰化钾反应测定不同浓度AHA与TJHA还原前后氧化还原能力.研究发现,原态和还原态的HA均能向铁氰化钾传递电子,还原后两种HA的氧化还原能力均大于其原态的氧化还原能力.原态和还原态TJHA的单位碳电子转移数(原态1.49 meq·g C-1;还原态20.95 meq·g C-1)均大于AHA(原态0.52 meq·g C-1;还原态1.75 meq·g C-1).同时随着HA浓度的增加,两种HA的原态与还原态单位碳电子转移数均逐渐降低(AHA:0.91—0.52 meq·g C-1;TJHA:13.57—1.49 meq·g C-1),而AHA单位体积电子转移数目逐渐增大(0.002—0.072 meq·L-1),TJHA单位体积电子转移能力无明显变化.这是由于在HA与铁氰化钾电子转移体系中,氧化还原能力的高低与腐殖酸中氧化还原官能团数量和分布有关,与HA粒径大小,分子质量也有关系.进一步通过E465,E4/E6值表明两种HA E465值与浓度呈明显正线性关系,E4/E6值与浓度呈对数增加趋势.三维荧光分析发现,HA还原后,激发/发射(Ex/Em)峰出现蓝移,相对荧光强度降低,说明HA还原的过程中有π—π*的断裂.进一步对HA荧光测定发现TJHA中具有更多数量的氧化还原官能团而AHA中氧化还原官能团种类相对丰富.     

Photoreactivity of humic substances: relationship between fluorescence and singlet oxygen production

Humic substances are natural compounds abundantly present in the environment. They play a significant role in the natural attenuation of pollution in surface water due to their capacity to generate reactive species upon solar light excitation. Finding physico chemical parameters related to this property would be of a great help in the prediction studies of the organic pollutants fate. In this work, we investigated relationships between the ability of the humic substances to produce singlet oxygen and their fluorescence properties. For this, a series of sixteen humic acids, fulvic acids, and water-extractable organic matter from soils were studied. The steady-state singlet oxygen concentrations in the irradiated humic substances solutions were measured by monitoring the loss of furfuryl alcohol added as a singlet oxygen scavenger. The emission spectra of the sixteen samples were also recorded. Values of the steady-state singlet oxygen concentrations and the emission intensities showed significant variations among the humic samples and a parallel increase. Thus, here we demonstrate that the rate of singlet oxygen production and the emission intensity of the humic samples are correlated, the best correlation being obtained for emission wavelengths between 500 and 580 nm. This correlation which was never reported until now can be used to estimate the singlet oxygen-production capacity of the humic substances based on their fluorescent properties.     

无机离子对左旋葡聚糖光降解的影响

左旋葡聚糖(LG)被广泛作为生物质燃烧的示踪剂.然而,近年来研究表明左旋葡聚糖在大气中不稳定而会发生光降解.此外,对于大气中含量较高的SO₄^2-、NO₃-、NO₂-无机离子对LG光解的影响罕有报到.为此,本文模拟了液相中SO₄^2-、NO₃-、NO₂-对LG光氧化行为的影响.结果表明,Na2SO₄、NaNO₃、NaNO₂条件下LG光解速率常数分别为0.208、0.182、0.165 min^-1,均低于对照组(0.266 min-1),这表明无机离子的存在会减缓LG光降解速率.此外,这3种无机离子对LG光解产物中的低分子脂肪酸分布,甲酸/乙酸(C1/C2)比率均有重要的影响.其中,SO₄^2-存在下产物中戊二酸较多、NO₃-存在下产物中甲酸较多、NO₂-存在下产物中乙酸较多;NO₂-存在下产物中的C1/C2比率小于1与一般二次源中的C1/C2比率不一致,这表明由单一反应引起的C1/C2并不总是大于1.这些结果对于我们深刻理解大气液相中的有机物转化具有重要的参考价值.     

Experimental study of chromium adsorption on minerals in the presence of phthalic and humic acids

The effect of phthalic acid (benzene 1,2 dicarboxylic acid), a surrogate compound for natural organic matter, and of humic acid, on the adsorption of chromium to the surface of minerals was observed. In ternary systems involving phthalic acid, chromium(III) adsorption decreases on clays, probably because of aqueous Cr(III)-phthalate complexation, preventing ionic-exchange. Phthalic acid was also found to reduce chromium(VI) adsorption onto alumina, because of a competitive effect. In ternary systems involving humic acid, Cr(III) adsorption is increased in the low pH range because of the formation of surface ternary complex S-L-Cr(III) and is decreased in the high pH range because of aqueous Cr(III)-humate complexation.     

长江水体分散颗粒物对对乙酰氨基酚光降解的影响

研究了药物对乙酰氨基酚在长江水体颗粒物表面的吸附及颗粒分散体系中的光降解规律,探讨了体系pH、颗粒物浓度及加入柠檬酸、草酸、腐殖酸对对乙酰氨基酚光降解的影响.结果表明,对乙酰氨基酚在颗粒物表面的吸附符合Langmuir型吸附等温式,分散颗粒物可以促进对乙酰氨基酚的光降解,光降解符合一级反应动力学规律;pH=9时光降解速率最快;加入草酸、柠檬酸可以加快对乙酰氨基酚的光降解,而腐殖酸则抑制其光降解.     

Effects of water quality on the coagulation performances of humic acids irradiated with UV light

The presence of humic acid in drinking water treatment has received significant attention in recent years because of its adverse effects on the removal of many pollutants in coagulation. In this paper, the effects of water quality including pH, turbidity, alkalinity, and hardness on the removal of humic acid were investigated in a UV light hybridized coagulation process. Our results suggested that UV light radiation could effectively improve the removal rate of humic acid in coagulation under both neutral and basic conditions, and the variations of the selected water quality parameters had little adverse effect on the function of UV light. After UV light radiation, the removal rate of the nitro-humic acid (NHA) increased from 20% to 60% in coagulation, and increased further to 75% and 85% for the raw waters with 10.0 NTU kaolin and 100 mg·L^-1 hardness, respectively. In addition to NHA, the removal rates of the humic acid extracted from peat coal (PHA) and the humic acid provided by Japan metals and chemicals company (JHA) in coagulation were also improved, both in the range of 80%–90% after undergoing UV light radiation. By changing the radiation location from prior to coagulation to the flocculation process, similar experimental results were obtained. The formation of positive charged sites after UV light radiation was considered to be the primary factor that led to an enhanced removal of the humic acid in coagulation.     

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.