水滑石与磷酸银可见光催化剂的活性对比研究

本文合成了具备水滑石结构(LDH)的Zn-Cr LDH、Zn-Ti LDH以及Ag3PO43种半导体光催化剂,并对它们的催化性能进行对比研究。XRD和SEM分析表明,Zn-Cr LDH、Zn-Ti LDH具有层状结构而Ag3PO4呈纳米球状结构。UV-Vis分析表明,Ag3PO4和Zn-Cr LDH能够吸收可见光(>420 nm)。在可见光照射与添加AgNO3作为电子受体的条件下,Zn-TiLDH几乎没有光催化活性,而Ag3PO4的光催化活性高于Zn-Cr LDH。Ag3PO4在光解水实验中180 min内氧气产量约1.2mL,而Zn-Cr LDH约为0.65 mL。光催化降解有机污染物实验中,在Ag3PO4催化作用下,120 min内亚甲基蓝(MB)被完全降解,在240 min内46%的对硝基酚(PNP)被降解,而Zn-Cr LDH相应的去除率分别为61%和27%。     

微量元素对牛粪低温厌氧发酵的影响

为考察较低温度(<17℃)条件下添加微量金属元素对厌氧发酵产气量的影响,在发酵底物TS(含固率)为10%下采用10 L玻璃瓶作反应器,以牛粪为原料,向厌氧生物反应器中分别添加MnSO4、FeSO4·7H2O、电解锰渣,分析了厌氧消化系统运行过程中的产气量、COD(化学需氧量)和pH的变化。结果表明,锰元素能促进低温下牛粪的厌氧发酵,加速反应启动。当添加6 g MnSO4、100 g电解锰渣时,单位质量VS产气率分别为0.26 mL/g和0.64 mL/g,添加6 g FeSO4·7H2O与空白对照组均未见明显产气。     

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。     

盐析分相微萃取—高效液相色谱法测定水中含氯除草剂

采用盐析分相微萃取—高效液相色谱法同时测定水中3种含氯除草剂,建立并优化了反相离子对液相色谱条件,考察了萃取剂种类、盐析剂的种类和加入量及试样pH对萃取效果的影响。对氯苯氧乙酸、2,4-二氯苯氧乙酸和2,4-滴丁酯的质量浓度在0.1~100.0mg/L内与色谱峰面积呈良好的线性关系,相关系数不低于0.9992。平均回收率分别为96.29%、79.16%和70.21%,相对标准偏差小于5.3%。该方法操作简便、绿色环保,适合于水中含氯除草剂的测定。     

Changes in TcpA gene frequency explain 2,4,6-trichlorophenol degradation in mesocosms

Soils are often polluted by chlorophenols in timber production areas in the northern hemisphere. The tcpA gene encodes the first step of 2,4,6-trichlorophenol (246-TCP) degradation. We tested tcpA gene frequency in three natural pristine soils with different 246-TCP degradation capacity. Gene tcpA frequency increased more in spiked than non-spiked 10-L pails containing coniferous humus soil with high degradation capacity, in contrast to soils where degradation was slower. As the soil in each mesocosm originated from a spatially separate field plot, changes in tcpA gene frequency affected 246-TCP degradation over a range of soil origins. This indicates that the abundance of and changes in tcpA gene frequency could be utilized in estimating the efficacy of natural attenuation and biostimulation treatments in controlled conditions.     

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.     

Relationships between anaerobic consortia and removal efficiencies in an UASB reactor degrading 2,4 dichlorophenol (DCP)

To gain more insight into the interactions between anaerobic bacteria and reactor performances (chemical oxygen demand-COD, 2,4 dichlorophenol-2,4 DCP removals, volatile fatty acid-VFA, and methane gas productions) and how they depended on operational conditions the microbial variations in the anaerobic granular sludge from an upflow anaerobic sludge blanket (UASB) reactor treating 2,4 DCP was studied. The study was composed of two parts. In the first part, the numbers of methanogens and acedogens in the anaerobic granular sludge were counted at different COD removal efficiencies. The relationships between the numbers of methanogens, the methane gas production and VFA production were investigated. The COD removal efficiencies increased to 74% from 30% while the number of total acedogens decreased to 10 from 30 cfu ml(-1). The number of total methanogens and acedogens varied between 11 x 10(3) and 10 x 10(9)MPN g(-1) and 10 and 30 cfu ml(-1) as the 2,4 DCP removal efficiencies were obtained between 60% and 99%, respectively. It was seen that, as the number of total acedogens decreased, the COD removal efficiencies increased. However, the number of total methanogens increased as the COD removal efficiencies increased. Correlations between the bacterial number and with the removal efficiencies obtained in different operational conditions were investigated. From the results presented in this paper a high correlation between the number of bacteria, COD removals, methane gas percentage, 2,4 DCP removals and VFA was observed. In the second part, methanogen bacteria in the anaerobic granular sludge were identified. Microbial observations and biochemical tests were applied to identify the anaerobic microorganisms from the anaerobic granular sludge. In the reactor treating 2,4 DCP, Methanobacterium bryantii, Methanobacterium formicicum, Methanobrevibacter smithii, Methanococcus voltae, Methanosarcina mazei, Methanosarcina acetivorans, Methanogenium bourgense and Methanospirillum hungatei were identified.     

Influence of Na2S on the degradation kinetics of CCl4 in the presence of very pure iron

This paper presents the results of kinetic studies to investigate the effect of FeS film formation on the degradation rate of CCl(4) by 99.99% pure metallic iron. The film was formed by submersing metallic iron grains in an oxygen free HCO(3)(-)/CO(3)(2-) electrolyte solution. When the grains had reached a quasi steady-state value of the corrosion potential, Na(2)S((aq)) was injected. Upon injection, a microm thick poorly crystalline FeS film formed immediately on the iron surface. Over time, the iron became strongly corroded and both the FeS film and the metallic iron grains began to crack leading to exposure of bare metallic iron to the solution. The effect of the surface film on the degradation rate of CCl(4) was investigated following four periods of aging, 1, 10, 30, and 60 days. Relative to the controls, the 1-day sulfide-aged iron showed a substantial decrease in rate of degradation of CCl(4.) However, over time, the rate of degradation increased and surpassed the degradation rate obtained in the controls. It has been proposed that CCl(4) is reduced to HCCl(3) by metallic iron by electron transfer. The FeS film is substantially less conducting than the bulk iron metal or non-stoichiometric magnetite and from the results of this study, greatly decreases the rate of CCl(4) degradation relative to iron that has not been exposed to Na(2)S. However, continued aging of the FeS film results in breakdown and stress-induced cracking of the film, followed by dissolution and cracking of the iron itself. The cracking of the bulk iron is believed to be a consequence of hydrogen embrittlement, which is promoted by sulfide. The increase in CCl(4) degradation rate, as the FeS films age, suggests that the process of hydrogen cracking increases the surface area available for charge transfer.     

单甲脒饱和蒸气压的测定和估算

用气体的法测单甲脒在１５,２５,３５和４５℃时的饱和蒸气分别为０．２０２,０．５５４６,１．９５,６．２９Ｐａ;亨利常数计算值分别为６．３０×１０＾－４,１．６７×１０＾－３,５．６８×１０＾０－３和１．７８×１０＆－２,根据Ｃｌａｕｓｉｕｓ Ｃｌａｐｅｙｒｏｎ方程求出单甲脒在常温下气化热为８９．２ｋＪ．ｍｏｌ＾－１。