含锰废渣的氧化-活化再生回用工艺

为实现紫苏醛生产过程中二氧化锰（氧化剂）的循环利用,采用一种新型的氧化-活化工艺再生得到活性二氧化锰,即以紫苏醇合成紫苏醛过程中产生的含锰废渣为原料,首先采用氯酸钠氧化含锰废渣得到初级二氧化锰,然后使用高锰酸钾对初级二氧化锰进一步活化得到活性二氧化锰。实验表明,制取初级二氧化锰的最佳工艺条件为：反应时间为4h,反应温度为90～95℃,硫酸摩尔浓度为1.5 mol/L,氯酸钠加量为理论量的130%。制取活性二氧化锰的合适条件为：反应温度在60℃时,反应时间为1.5 h;反应温度在50℃时,反应时间为2.5 h。采用氧化-活化法再生的活性二氧化锰氧化紫苏醇,紫苏醛的产率可达52.8%,与使用电解二氧化锰氧化得到的紫苏醛的产率53.1%相当,而使用初级二氧化锰,紫苏醛的产率仅为14.9%。     

可见光响应型CuO/BiVO4的光催化活性研究

采用浸渍法制备了CuO/BiVO4光催化剂,通过X射线衍射(XRD)、热重/差示扫描量热(TG/DSC)和傅立叶红外光谱(FTIR)对其进行了表征,并在可见光照射下考察了其光催化氧化亚甲基蓝(MB)的动力学特性。结果表明,Cu的掺杂并未改变BiVO4的晶型结构;Cu(NO3)2/BiVO4在热处理(30～300℃)过程中,NO3-已经完全分解,Cu最终以CuO的形式存在于CuO/BiVO4光催化剂体系中;掺杂不同量Cu的CuO/BiVO4中的Cu2+/Bi+(摩尔比)实测值与理论值相近,该系列光催化剂的合成过程具有较高的可信度;在可见光照射下,CuO/BiVO4光催化降解MB反应符合表观一级反应动力学特征;当Cu2+/Bi+为0.050时,反应动力学速率常数(k)达到最高值(0.4334h-1),此时的k比单体BiVO4作用下的提高了1.04倍;由于异质结的存在,CuO/BiVO4与单体BiVO4相比,电子和空穴的利用率大大增加,使得CuO/BiVO4的光催化活性较单体BiVO4有了大幅度提高。     

4A沸石去除水中Pb2＋的研究

在静态条件下,研究了4A沸石对废水中Pb2＋的吸附性能,并探讨了影响吸附的因素。实验表明：当温度为30℃,废水pH为5～6,0．01g4A沸石对100mg／LPb2＋溶液10mL吸附20min,Pb2＋的去除率可达到99％以上。在实验研究条件下,4A沸石对Pb2＋的吸附符合Langmuir和Freundlich等温吸附方程,相关系数为0．9819和0．9998。经计算,4A沸石对Pb2＋的饱和吸附量为125mg／g。4A沸石吸附水中Pb2＋达到吸附平衡的时间较短;溶液pH值的变化对吸附效果影响不显著;温度从室温略微升高,Pb2＋的去除率略有增大。吸附在4A沸石上的Pb“可回收利用,处理后的4A沸石可以再生,且重复使用性能较好。     

磷酸活化植物基活性炭对水溶液中铅的吸附

以棉秆与互花米草为原料,采用磷酸活化法制备了低成本的植物基活性炭,通过静态实验研究了其对重金属铅的吸附性能。结果表明,在活化温度为500℃、活化时间为2 h条件下,制备的棉秆和互花米草活性炭比表面积为1 570m2/g和856 m2/g,含氧酸官能团含量分别为1.43 mmol/g和1.27 mmol/g。在25℃下,两种活性炭对重金属铅的Langmuir最大吸附量分别为119 mg/g和111 mg/g,吸附最佳pH为4.3,吸附平衡符合Freundlich方程,离子交换在吸附过程中发挥了重要作用。     

Metabolism of the Nonylphenol Isomer [Ring-U-14c]-4-(3′,5′-Dimethyl-3′-Heptyl)-Phenol by Cell Suspension Cultures of Agrostemma githago and Soybean

Abstract

The biotransformation of the nonylphenol isomer [ring-U-¹⁴C]-4-(3′,5′-dimethyl-3′-heptyl)-phenol (4-353-NP, consisting of two diastereomers) was studied in soybean and Agrostemma githago cell suspension cultures. With the A. githago cells, a batch two-liquid-phase system (medium/n-hexadecane 200:1, v/v) was used, in order to produce higher concentrations and amounts of 4-353-NP metabolites for their identification; 4-353-NP was applied via the n-hexadecane phase. Initial concentrations of [¹⁴C]-4-353-NP were 1 mg L^?1 (soybean), and 5 and 10 mg L^?1 (A. githago). After 2 (soybean) and 7 days (A. githago) of incubation, the applied 4-353-NP was transformed almost completely by both plant species to four types of products: glycosides of parent 4-353-NP, glycosides of primary 4-353-NP metabolites, nonextractable residues and unknown, possibly polymeric materials detected in the media. The latter two products emerged especially in soybean cultures. Portions of primary metabolites amounted to 19–22% (soybean) and 21–42% of applied ¹⁴C (A. githago). After liberation from their glycosides, the primary 4-353-NP metabolites formed by A. githago were isolated by HPLC and examined by GC-EIMS as trimethylsilyl derivatives. In the chromatograms, eight peaks were detected which due to their mass spectra, could be traced back to 4-353-NP. Seven of the compounds were side-chain monohydroxylated 4-353-NP metabolites, while the remaining was a (side-chain) carboxylic acid derivative. Unequivocal identification of the sites of hydroxylation/oxidation of all transformation products was not possible. The main primary metabolites produced by A. githago were supposed to be four diastereomers of 6′-hydroxy-4-353-NP (about 80% of all products identified). It was concluded that plants contribute to the environmental degradation of the xenoestrogen nonylphenol; the toxicological properties of side-chain hydroxylated nonylphenols remain to be examined.     

Parental phenols exposure and spontaneous abortion in Chinese population residing in the middle and lower reaches of the Yangtze River

Widespread use of phenols has led to ubiquitous exposure to phenols. In experimental animals, phenols increased resorptions, reduced live litter size and fetal body weights. However, there are limited epidemiological evidences of the relationships between exposure to phenols and pregnancy outcomes. We evaluated the associations between parental urinary levels of various phenols and spontaneous abortion in a Chinese population residing in the middle and lower reaches of the Yangtze River. A case-control study was conducted that included 70 case couples with medically unexplained spontaneous abortion and 180 control couples who did not have a history of spontaneous abortion and had at least one living child. Both parental urinary phenols were measured by ultra-high performance liquid chromatography-tandem mass spectrometry including bisphenol A (BPA), benzophenone-3 (BP-3), 2,3,4-trichlorophenol (2,3,4-TCP), pentachlorophenol (PCP), 4-n-octylphenol (4-n-OP) and 4-n-nonylphenol (4-n-NP). Compared with the low exposure group, there was an increased risk of spontaneous abortion with high paternal urinary PCP concentration [odds ratio (OR) = 2.09, 95% Confidence Interval (CI), 1.05–4.14], and maternal exposure to 4-n-OP and alkylphenol(s) also significantly increased the risk of spontaneous abortion (OR = 2.21, 95% CI, 1.02–4.80; OR = 2.81, 95% CI, 1.39–5.65, respectively). Our study firstly provides the evidence that paternal PCP exposure, maternal 4-n-OP and alkylphenol(s) exposure are associated with spontaneous abortion in humans.     

Fe3O4/Ag磁性纳米颗粒去除水中的铅离子

采用水相共沉淀法制备小尺寸磁性Fe₃O₄纳米颗粒,以没食子酸作为还原剂和表面修饰剂,还原Ag[(NH₃)₂]⁺制备出Fe₃O₄/Ag磁性纳米颗粒。研究该磁性纳米颗粒对水溶液中铅离子的吸附行为,研究结果表明,pH为7.0,吸附温度30℃时可得到最好的处理效果,铅的去除率可达99.7%以上,Fe₃O₄/Ag颗粒吸附行为符合二级动力学模型(R² > 0.99)。该磁性纳米颗粒经过多次再生处理后,仍具有很好的吸附效果,表明Fe₃O₄/Ag在水处理方面拥有良好的应用前景。     

Nitrous oxide and methane emission from a flooded rice field as influenced by separate and combined application of herbicides bensulfuron methyl and pretilachlor

Combination of divergent active principles to achieve broad-spectrum control is gaining popularity to manage the weed menace in intensive agriculture. However, such application could have non-target impacts on the soil processes affecting soil ecology and environmental interactions. A field experiment was conducted to investigate the impact of separate and combined applications of herbicides bensulfuron methyl and pretilachlor on the emission of N₂O and CH₄, and related soil and microbial parameters in a flooded alluvial field planted to rice cv Lalat. Single application of the herbicide bensulfuron methyl or pretilachlor resulted in a significant reduction of N₂O and CH₄ emissions while the combination of these two herbicides distinctly increased N₂O and CH₄ emissions. Cumulative N₂O emissions (kg N₂O-N) followed the order of bensulfuron methyl (0.35 kg ha⁻¹) < pretilachlor (0.36 kg ha⁻¹) < control (0.45 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% single dose (0.49 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% double dose (0.54 kg ha⁻¹). Cumulative CH₄ emissions (kg CH₄), on the other hand, followed the order of bensulfuron methyl (47.89 kg ha⁻¹) < pretilachlor (73.17 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% single dose (93.50 kg ha⁻¹) < control (106.54 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% double dose (124.67 kg ha⁻¹). The inhibitory effect of separate application of herbicides bensulfuron methyl 0.6% and pretilachlor 6.0% on N₂O emission was linked to lower mineral N, lower denitrifying and nitrifying activity and low denitrifier and nitrifier populations. Inhibitory effect on CH₄ emission, on the contrary, was linked to prevention in the drop of redox potential, lower readily mineralizable carbon (RMC) and microbial biomass carbon (MBC) contents as well as lower methanogenic and higher methanotrophic bacterial population. Admittedly, stimulatory effect of combined application of herbicides bensulfuron methyl 0.6% and pretilachlor 6.0% at double dose on N₂O and CH₄ emission was related to reversal of the identified indicators of inhibition. Results indicate that while individual application of herbicides bensulfuron methyl 0.6% or pretilachlor 6.0% can reduce N₂O and CH₄ emission from flooded soil planted to rice, their combined application at normal dose can keep the emission at a comparatively lower level with significantly higher grain yield as compared to the herbicides applied alone.     

TiO2纳米管催化降解4，4’-二溴联苯的影响因素和动力学研究

利用TiO2纳米管催化降解水中的4,4’-二溴联苯,对催化降解过程和影响因素进行研究。结果表明,TiO2纳米管对其有较高的催化降解效率且降解过程符合Langmuir—Hinshelwood动力学模式。不同光源、4,4’-二溴联苯的初始浓度、纳米管添加量和pH值对催化降解过程都有较大影响,其中pH值的影响最为明显。反应液在中性状态下的降解率明显低于pH=1或11的情况。在pH=1时,4,4’一二溴联苯的降解率达86％。