5种酚类物质对中国白羽鹌鹑和中华蜜蜂的急性毒性

酚类物质作为一类主要的污染物,已引起国内外高度重视,但目前其对陆生生物的毒性研究较少。本试验探究了4-叔丁基苯酚、间甲酚、2-氯苯酚、2-甲酚、2,4-二氯苯酚这5种酚类物质对中国本土物种中国白羽鹌鹑和中华蜜蜂的急性毒性。在中国白羽鹌鹑的急性经口试验中,2-氯苯酚、2-甲酚的7 d的半致死浓度(7 d-LC50)分别为331 mg·kg~(-1)和413 mg·kg~(-1),其他3种酚类物质的7 d-LC50均大于限度值1 000 mg·kg~(-1);在中国白羽鹌鹑的急性饲喂试验中,5种酚类物质的8 d-LC50均大于限度值2 000 mg·kg~(-1);在中华蜜蜂的急性经口试验中,2-氯苯酚、2-甲酚和2,4-二氯苯酚的48 h-LC50分别为306 mg·L~(-1)、358 mg·L~(-1)和364 mg·L~(-1);在中华蜜蜂的急性接触试验中,2,4-二氯苯酚的48 h的半致死量(48 h-LD50)为2.6μg·蜂~(-1),其他4种酚类物质的48h-LD50均大于限度值100μg·蜂~(-1)。研究结果表明不同的酚类物质由于其结构不同亦表现出不同的毒性,甲酚的邻位取代比间位取代对中国白羽鹌鹑和中华蜜蜂的毒性更高,不同物种表现出了相似的规律性。5种酚类物质对我国本土物种中国白羽鹌鹑和中华蜜蜂毒性比对其他水生生物更敏感,存在良好的剂量效应关系。     

新型针状二氧化锰的制备、表征及其对土壤中有机物氧化性能研究

由化学法合成了一种新型类针状的二氧化锰(MnO2)材料,通过X射线衍射(XRD)、透射电镜(TEM)、比表面积测试(BET)、傅里叶转换红外光谱(FTIR)和X射线光电子能谱(XPS)等手段表征其结构特性,由MnO2对酚类有机物和医药类污染物的去除实验来评价其活性.结果表明,此材料为典型的δ-MnO2,其比表面积相对较大,为41m2·g-1,MnO2以MnO6八面体结构存在,Mn以MnO2形式存在.从MnO2对2-氯酚(2-CP)的去除及中间产物分析可知,MnO2对2-CP有较强的脱氯作用.另外,pH对2-CP的去除有较大影响.对酚类有机物和医药类污染物的去除实验考察发现,2,4-二氯酚(2,4-DCP)和2,4,6-三氯酚(2,4,6-TCP)的去除效率明显大于苯酚(Ph)和2-CP,而环丙沙星的去除与安替比林、布洛芬、苯妥英和苯海拉明相比更加容易,经过96h反应,去除率可达74%.     

Influence of combustion conditions on yields of solvent-extractable anhydrosugars and lignin phenols in chars: Implications for characterizations of biomass combustion residues

Anhydrosugars, such as levoglucosan and its isomers (mannosan, galactosan), as well as the solvent-extractable lignin phenols (methoxylated phenols) are thermal degradation products of cellulose/hemicellulose and lignin, respectively. These two groups of biomarkers are often used as unique tracers of combusted biomass inputs in diverse environmental media. However, detailed characterization of the relative proportion and signatures of these compounds in highly heterogeneous plant-derived chars are still scarce. Here we conducted a systematic study to investigate the yields of solvent-extractable anhydrosugars and lignin phenols in 25 lab-made chars produced from different plant materials under different combustion conditions. Solvent-extractable anhydrosugars and lignin phenols were only observed in chars formed below 350 °C and yields were variable across different combustion temperatures. The yields of mannosan (M) and galactosan (G) decreased more rapidly than those of levoglucosan (L) under increasing combustion severity (temperature and duration), resulting in variable L/M and L/(M + G) ratios, two diagnostic ratios often used for identification of combustion sources (e.g. hardwoods vs. softwoods vs. grasses). Our observations thus may provide an explanation for the wide ranges of values reported in the literature for these two ratios. On the other hand, the results of this study suggest that the ratios of the major solvent-extractable lignin phenols (vanillyls (V), syringyls (S), cinnamyls (C)) provide additional source reconstruction potential despite observed variations with combustion temperature. We thus propose using a property-property plot (L/M vs. S/V) as an improved means for source characterization of biomass combustion residues. The L/M-S/V plot has shown to be effective in environmental samples (soil organic matter, atmospheric aerosols) receiving substantial inputs of biomass combustion residues.     

Stability of the conjugated species of environmental phenols and parabens in human serum

In humans, the metabolism of environmental phenols may include the formation of conjugated species (e.g., glucuronides and sulfates), but the free species—not the conjugated forms—are considered biologically active. Therefore, information on the concentration of these free species in blood or urine could be helpful for risk assessment. Because conjugates could hydrolyze to their corresponding free forms during collection, handling, and storage of biological specimens, information on the temporal stability of the conjugates is of interest. Previously, we reported the temporal stability of urinary conjugates of several environmental phenols, but data on the stability of phenols' conjugated species in serum, albeit critical if concentrations of free and conjugated species are compared, are largely unknown. In the present study, we investigate the stability of the conjugates of four phenols—bisphenol A, benzophenone-3, triclosan, and 2,5-dichlorophenol—and two parabens—methyl paraben and propyl paraben—in 16 human serum samples for 30 days at above-freezing temperature storage conditions (4 °C, room temperature, and 37 °C). These conditions reflect the worst-case scenarios that could occur during the short-term storage of biological samples before their long-term storage at controlled subfreezing temperatures. We found that the percentage of the conjugated species of the four detected compounds (2,5-dichlorophenol, triclosan, and methyl and propyl parabens) in these serum specimens even when stored at 37 °C for at least 30 days did not vary significantly. These preliminary data suggest that the phenols' serum conjugates appear to be more stable than their corresponding urinary conjugates, some of which started to hydrolyze within 24 h under similar storage conditions. The reported stability of these conjugated species in human serum also suggests that the free species are unlikely to have resulted from the hydrolysis of their corresponding conjugates. This information could be important for interpreting the low concentrations of free phenol species detected in serum samples of nonoccupationally exposed populations. To our knowledge, this is the first study to report on the stability of conjugated species in serum, and as such requires replication.     

Biocatalytic amidation of carboxylic acids and their antinemic activity

A series of novel N-alkyl substituted amides, synthesized by enzyme catalysis, were evaluated against root-knot nematode, Meloidogyne incognita and found to have potential antinemic activity. The corresponding amides were prepared by the condensation of equimolar amounts of carboxylic acids with different alkyl amines in the presence of Candida antarctica lipase at 60–90°C in 16–20 h. The reactions were carried out in a non - solvent system without the use of any activating agents. All the products were obtained in appreciable amounts and the yields for different compounds varied between 77.4–82.3%. The synthesized compounds were characterized using spectroscopy techniques namely Infra Red (IR) and Nuclear Magnetic Resonance (NMR) (¹H and ¹³C). Nematicidal activity of synthesized amides was evaluated against J₂s of Meloidogyne incognita at 500, 250, 125 and 62.5 ppm concentrations after 24 h, 48 h and 72 h of exposure. Among all the tested compounds, N-propyl-butyramide, N-propyl-pentanamide and N-propyl-hexanamide were found to possess significant activity with LC₅₀ values of 67.46, 83.49 and 96.53 respectively. N-propyl-butyramide with LC₅₀ value of 67.46 ppm was found to be most active amide against J₂s of Meloidogyne incognita. The bioactivity study showed that an increase in alkyl chain significantly decreased the activity of amides against root-knot nematode.     

Assessing the steady-state [·NO<Subscript>2</Subscript>] in environmental samples

Based on available literature data of [NO₂ ⁻], steady-state [·OH], and ·OH generation rate upon nitrate photolysis in environmental aqueous samples under sunlight, the steady-state [·NO₂], could be calculated. Interestingly, one to two orders of magnitude more ·NO₂ would be formed in photochemical processes in atmospheric water droplets compared to transfer from the gas phase. The relative importance of nitrite oxidation compared to nitrate photolysis as an ·NO₂ source would be higher in atmospheric than in surface waters. The calculated levels of ·NO₂ could lead to substantial transformation of phenol into nitrophenols in both atmospheric and surface waters.     

Decolourization and removal of some organic compounds from olive mill wastewater by advanced oxidation processes and lime treatment

Background Olive mill wastewater (OMW) generated by the olive oil extracting industry is a major pollutant, because of its high organic load and phytotoxic and antibacterial phenolic compounds which resist biological degradation. Mediterranean countries are mostly affected by this serious environmental problem since they are responsible for 95% of the worldwide oliveoil production. There are many methods used for OMW treatment, such as adsorption, electro coagulation, electro-oxidation, biological degradation, advanced oxidation processes (AOPs), chemical coagulation, flocculation, filtration, lagoons of evaporation and burning systems, etc. Currently, there is no such economical and easy solution. The aim of this study was to evaluate the feasibility of decolourization and removal of phenol, lignin, TOC and TIC in OMW by UV/H₂O₂ (AOPs). The operating parameters, such as hydrogen peroxide dosage, times, pH, effect of UV and natural sunlight were determined to find the suitable operating conditions for the best removal. Moreover, there is no study reported in the literature related to the use of UV/H₂O₂ and lime together in OMW treatment. Methods OMW was obtained from an olive-oil producing plant (Muğla area of Turkey) which uses a modern production process. No chemical additives are used during olive oil production. This study was realised by using two different UV sources, while taking the time and energy consumption into consideration. These two sources were mercury lamps and natural sunlight. Before starting AOPs experiments, one litre of OMW was treated by adding lime until a pH of 7.00. Then, 100 ml was taken from each sample, and 1 to 10 ml of a 30% H₂O₂ (Riedel-deHaen) solution was added. These solutions in closed vessels were laid in the natural sunlight for a week and their compositions and colour changes were analysed daily by UV-Vis spectrophotometer. At the end of the one-week period, they were treated with lime. In this study, the effect of changes in the initial pH, times and H₂O₂ concentrations on removal was investigated. At the end of all experiments, changes in colour, phenol, lignin, TOC and TIC concentrations were analysed according to standard methods. Results and Discussion In the samples exposed to natural sunlight and having an H₂O₂/OMW ratio of 3 ml/100 ml, a significant colour removal was achieved approximately 90% of the time at the end of 7 days. When the same samples were treated with lime (pH: up to 7), 99% efficiency was achieved. When phenol and lignin removals were examined in the same concentration, phenol and lignin removal were found 99.5%, 35%, respectively. However, for maximum lignin removal, more use of H₂O₂ (10 ml H₂O₂/100 ml OMW) was found to be necessary. Under these conditions, it was found that lignin can be removed by 70%, but to 90% with lime, at the end of a seven-day period. Rate constants obtained in the experiments performed with direct UV were found to be much higher than those of the samples exposed to natural sunlight (k^a _lignin = 0.3883 ≫ k^b _lignin = 0.0078; k^a _phenol = 0.5187 ≫ k^b _phenol = 0.0146). Moreover, it should be remembered in this process that energy consumption may induce extra financial burden for organisations. Conclusions It was found, in general, that colour, lignin, total organic carbon and phenol were removed more efficiently from OMW by using H₂O₂ UV and lime OMW. Moreover, in the study, lime was found to contribute, both initially and after radical reactions, to the efficiency to a great extent. Recommendations and Perspectives Another result obtained from the study is that pre-purification carried out with hydrogen peroxide and lime may constitute an important step for further purification processes such as adsorption, membrane processes, etc.     

Retention of PCDDS and PCDFS in the liver of the rat and hamster after oral administration of a municipal incinerator fly ash extract

A single dose of an extract from 16 and 5 grams fly ash was administered orally to male rats and hamsters. In the rat 1,2,3,7,8‐PnCDD had the highest retention (41%) in the liver. The congener with the highest retention in the liver of the hamster was 2,3,4,7,8‐PnCDF (70.9%). In two oral multiple dose experiments with rats, highest liver retentions were found for 1,2,3,7,8‐PnCDD (51.7%) and 1,2,3,6,7,8‐HxCDD (59.8%). With the exception of 2,3,4,6,7‐PnCDF, all PCDDs and PCDFs retained in the liver of rat and hamster had a 2,3,7,8 chlorine substitution pattern. In both types of experiments with rats the retention of 2,3,7,8‐TCDF in the liver was very low, 1.1–2.8% of the total dose. In the liver of the hamster retention of 2,3,7,8‐TCDF was almost equal to that of 2,3,7,8‐TCDD, indicating that the hamster is probably metabolizing 2,3,7,8‐TCDF Jess efficiently than the rat. In all experiments 1,2,3,7,8‐PnCDD and 2,3,4,7,8‐PnCDF were retained in the liver more efficiently than 2,3,7,8‐TCDD. Based on first order pharmacokinetic calculations, it was found that the earlier published k_e value of 0.55 for 2,3,7,8‐TCDF in the liver of the rat was also applicable. Using the same calculations for 2,3,7,8‐TCDD (k_e = 0.029) a 30% difference was found between calculated and actual measurements, but calculated results were still within the 95% confidence limits of the actual measurements.     

Cosolvency. I. some non‐hydrogen bonding solutes with non‐hydrogen bonding solvents

The solubility data for a series of non‐hydrogen bonding, monosubstituted benzenes in binary mixtures of water and non‐hydrogen bonding cosolvents is presented. Good correlation between log solubility and fraction cosolvent is obtained, therefore the estimation of solubility in mixed solvents by a log‐linear relationship can be attained. Slight positive or negative deviations from predicted solubility values are seen at high volume fractions of cosolvents. These deviations are attributed to the cosolvent‐water interactions.     

基于区间活性数据的定量结构-活性关系

利用贝叶斯统计方法构建了基于区间活性数据的取代苯胺和苯酚类化合物对大型溞(Daphniamagna)24 h急性毒性的定量结构-活性关系模型,并与基于平均数和中位数的点估计活性数据的定量结构-活性关系模型进行了比较.结果表明,前者可以充分利用化合物的活性数据信息,模型具有更好的拟合效果与预测能力以及较宽的应用范围.基于区间活性数据的定量结构-活性关系模型可为生态风险评价等提供更加可靠的预测数据.