Kinetics and mechanisms of interaction of simazine with humic acids

Abstract

The adsorption of simazine on two fractions of hu‐mic acids of different molecular size was investigated at a pH range of 2.5 to 6.2. The amounts of the herbicide adsorbed decreased with increasing pH for both of the two humic acids fractions used and no adsorption was observed at pH 5.5. The adsorption capacity of fraction I (M_v >100,000) exceeded that of fraction IV (M_v < 4,000) over the entire pH region used. No appreciable changes in the adsorbed amounts were observed after 24 hours.

Continuous flow dialysis techniques were used to determine the extent of binding between simazine and dissolved humic acids. It was observed that 50% and 60% of simazine added were thus removed from the dialysis bags containing humic acids fractions I and IV,respectively. Higher amounts of simazine were adsorbed by the high molecular weight humic fraction. The adsorption processes involve ionic bonds between simazine and humic acids. In addition it is likely that hydrogen bonds and physical forces are also involved in the adsorption of simazine by humic acids.     

Comparative sorption,desorption and leaching potential of aminocyclopyrachlor and picloram

Sorption and desorption of aminocyclopyrachlor (6-amino-5-chloro-2-cyclopropylpyrimidine-4-carboxylic acid) were compared to that of the structurally similar herbicide picloram (4-amino-3,5,6-trichloro-2-pyridinecarboxylic acid) in three soils of differing origin and composition to determine if picloram data is representative of aminocyclopyrachlor behavior in soil. Aminocyclopyrachlor and picloram batch sorption data fit the Freundlich equation and was independent of concentration for aminocyclopyrachlor (1/n = 1), but not for picloram (1/n = 0.80–0.90). Freundlich sorption coefficients (K _f) for aminocyclopyrachlor were lowest in the eroded and depositional Minnesota soils (0.04 and 0.12 μmol ^(1–1/n) L^1/n kg^?1) and the highest in Molokai soil (0.31 μmol ^(1–1/n) L^1/n kg^?1). For picloram, K _f was lower in the eroded (0.28 μmol ^(1–1/n) L^1/n kg^?1) as compared to the depositional Minnesota soil (0.75 μmol ^(1–1/n) L^1/n kg^?1). Comparing soil to soil, K _f for picloram was consistently higher than those found for aminocyclopyrachlor. Desorption of aminocyclopyrachlor and picloram was hysteretic on all three soils. With regard to the theoretical leaching potential based on groundwater ubiquity score (GUS), leaching potential of both herbicides was considered to be similar. Aminocyclopyrachlor would be ranked as leacher in all three soils if t_1/2 was > 12.7 days. To be ranked as non-leacher in all three soils, aminocyclopyrachlor t_1/2 would have to be <3.3 days. Calculated half-life that would rank picloram as leacher was calculated to be ～15.6 d. Using the current information for aminocycloprachlor, or using picloram data as representative of aminocycloprachlor behavior, scientists can now more accurately predict the potential for offsite transport of aminocycloprachlor.     

Transesterification of hazelnut oil by ultrasonic irradiation

Ultrasonic irradiation is considered an effective way to increase mass transfer between immiscible liquid–liquid phases in a heterogeneous system leading to faster transesterification and higher yield and saving excess methanol and catalyst. In this study, the transesteri?cation of hazelnut oil with methanol and ethanol was performed in the presence of potassium hydroxide or sodium methoxide as a catalyst using two types of ultrasonic irradiation with a probe (20 kHz, 200 W) and a bath (35 kHz, 400 W); a conventional production method was also used. The reaction time, alcohol:oil molar ratio, catalyst type (KOH or NaOCH₃), and catalyst amount (wt.% of oil) were studied as experimental parameters. The highest methyl ester conversion was obtained as 98.12% by using ultrasonic probe at a 5:1 methanol:oil molar ratio with KOH 1 wt.% of oil as catalyst in 20-min reaction time at autogenous temperature. The application of ultrasonic irradiation by using a probe decreased the level of energy consumption, showing that this method may be a promising alternative compared with the conventional production method.     

Effects of a gradually increased load of fish waste silage in co-digestion with cow manure on methane production

This study examined the effects of an increased load of nitrogen-rich organic material on anaerobic digestion and methane production. Co-digestion of fish waste silage (FWS) and cow manure (CM) was studied in two parallel laboratory-scale (8 L effective volume) semi-continuous stirred tank reactors (designated R1 and R2). A reactor fed with CM only (R0) was used as control. The reactors were operated in the mesophilic range (37 °C) with a hydraulic retention time of 30 days, and the entire experiment lasted for 450 days. The rate of organic loading was raised by increasing the content of FWS in the feed stock. During the experiment, the amount (volume%) of FWS was increased stepwise in the following order: 3% – 6% – 13% – 16%, and 19%. Measurements of methane production, and analysis of volatile fatty acids, ammonium and pH in the effluents were carried out. The highest methane production from co-digestion of FWS and CM was 0.400 L CH4 gVS^?1, obtained during the period with loading of 16% FWS in R2. Compared to anaerobic digestion of CM only, the methane production was increased by 100% at most, when FWS was added to the feed stock. The biogas processes failed in R1 and R2 during the periods, with loadings of 16% and 19% FWS, respectively. In both reactors, the biogas processes failed due to overloading and accumulation of ammonia and volatile fatty acids.     

Effects of bulking agent addition on odorous compounds emissions during composting of OFMSW

The effects of rice straw addition level on odorous compounds emissions in a pilot-scale organic fraction of municipal solid waste (OFMSW) composting plant were investigated. The cumulative odorous compounds emissions occurred in a descending order of 40.22, 28.71 and 27.83 mg/dry kg of OFMSW for piles with rice straw addition level at ratio of 1:10, 2:10 and 3:10 (mixing ratio of rice straw to OFMSW on a wet basis), respectively. The mixing ratio of rice straw to OFMSW had a statistically significant effect on the reduction of malodorous sulfur compounds emissions, which had no statistically significant effect on the reduction of VFAs, alcohols, aldehydes, ketones, aromatics and ammonia emissions during composting, respectively. The cumulative emissions of malodorous sulfur compounds from piles with the increasing rice straw addition level were 1.17, 1.08 and 0.88 mg/dry kg of OFMSW, respectively. The optimal mixing ratio of rice straw to OFMSW was 1:5. Using this addition level, the cumulative malodorous sulfur compounds emissions based on the organic matter degradation were the lowest during composting of OFMSW.     

梯度淋洗离子色谱法同时测定雨水中12种有机酸和无机阴离子的研究

研究了用离子色谱梯度洗脱-抑制电导检测器同时分离12种有机酸和无机阴离子的规律和色谱务件,建立了最佳梯度程序.在所选实验务件下,方法对所测有机酸和无机阴离子的线性相关系数为0.9929～0.9998,相对标准偏差为4.2%～9.3%,加标回收率为91.4%～107.0%,最低检测限为0.0069～0.34mg/L.方法用于雨水样品的测定,结果令人满意.     

城市水环境PFAAs前驱体污染特征及健康风险

为揭示城市水环境中前驱体对全氟烷基酸（PFAAs）输入特征、分布格局及健康风险的影响,对南京城市污水处理厂出水、河流、湖泊、长江饮用水源地等水体进行了考察.利用HPLC-MS/MS及总可氧化前驱体法（TOP Assay）分析了17种PFAAs与其总可氧化前驱体的污染特征,并通过推演耐受剂量评估了饮水途径的健康风险商（HQ）.结果表明,污水处理厂出水中PFAAs浓度90.6～278ng/L,主要单体PFBS、PFHxA、PFOA占总浓度的63%;总可氧化前驱体浓度239～839pmol/L,PFBA前驱体含量最高.城市地表水中PFAAs浓度61.8～157ng/L,总可氧化前驱体浓度195～572pmol/L,PFBA、PFPe A、PFHxA3种全氟羧酸的前驱体含量最高,城市河流流经人口密集区后,PFAAs赋存浓度有所上升,但总可氧化前驱体浓度下降.饮用水源地中PFAAs浓度50.9～54.6ng/L,总可氧化前驱体浓度273～372pmol/L,以PFBA、PFPe A和PFHx A3种全氟羧酸的前驱体为主.相对高风险来源于PFOS的免疫毒性（HQ=0.024）以及PFOA的发育毒性...     

Essential versus potentially toxic dietary substances: a seasonal comparison of essential fatty acids and methyl mercury concentrations in the planktonic food web

We investigated seasonal variability of essential fatty acids (EFA) and methyl mercury (MeHg) concentrations in four size categories of planktonic organisms in two coastal lakes. MeHg concentrations increased significantly with increasing plankton size and were independent of plankton taxonomy. However, total EFA increased from seston to mesozooplankton, but decreased in the cladoceran-dominated macrozooplankton size-class. Analysis of EFA patterns revealed that linoleic, alpha-linolenic, arachidonic, and eicosapentaenoic acids increased with increasing zooplankton size, but docosahexaenoic acid (DHA) in the cladoceran-dominated macrozooplankton was generally lower than in seston. This consistent pattern demonstrates that cladocerans, although bioaccumulating MeHg, convey less DHA than similar-sized copepods to their consumers. It is thus evident that fish consuming cladocerans have restricted access to DHA, yet unrestricted dietary access to MeHg. Thus, the structure of planktonic food webs clearly affects the composition of EFA and regulates dietary supply of these essential nutrients, while MeHg bioaccumulates with increasing zooplankton size.     

Chronic copper exposure and fatty acid composition of the amphipod Dikerogammarus villosus: results from a field study

Field study allows assessment of long-term effects on fatty acid (FA) composition of organisms under chronic exposure to metals. One expected effect of copper is peroxidation of lipids and essentially polyunsaturated fatty acids (PUFA). FA analysis was established for the amphipod Dikerogammarus villosus subjected to different degrees of copper exposure (4–40 μg Cu L⁻¹). A previous study in our team showed that this species regulates its body Cu concentration (106–135 mg Cu kg⁻¹ dry weight). Despite the high capacity of bioaccumulation, the absence of a correlation between copper concentration in D. villosus and water prevents its use as bioindicator of copper pollution. Both sexes from the most polluted site showed the lowest total FA content, but the highest PUFA percent, mainly of the long-chained variety (C20–C22). Mechanisms leading to the prevention of lipid peroxidation in this species were discussed (metallothioneins and intracellular granules) and proposed with support from literature data.     

重庆典型岩溶区地下河中溶解态正构烷烃、脂肪酸来源、迁移及转化

为阐述青木关地下河中溶解态正构烷烃和脂肪酸的来源、迁移及转化研究,2013年7月31日、10月25日分别在青木关地下河入口、天窗和出口处进行采样,并利用气相色谱-质谱联用仪(GC-MS)对样品中溶解态正构烷烃、脂肪酸的组分进行定量分析.结果表明,7月和10月样品中溶解态正构烷烃、脂肪酸的平均含量分别为1 354、667 ng·L-1和24 203、2 526ng·L-1.溶解态正构烷烃和脂肪酸的含量随地下河运移距离的增加均呈降低的趋势;基于正构烷烃分子特征参数CPI、OEP、Paq和R(ΣC≤20含量与总量的百分比)发现7月青木关地下河中溶解态正构烷烃主要来源于细菌等微生物和藻类.10月主要来源于地表水生植物,但随着地下河运移距离的增加,藻类和细菌等微生物的贡献逐渐增大;溶解态脂肪酸C16:0比例最高,结合碳峰分布特征显示7月和10月水样中,藻类和细菌等微生物为地下河中溶解态脂肪酸的主要来源.