Heterogeneous photocatalytic degradation of diuron on zinc oxide: Influence of surface-dependent adsorption on kinetics, degradation pathway, and toxicity of intermediates

Heterogeneous photocatalytic reaction has been generally applied for degradation of toxic contaminants. Degradations of a compound using the same kind of catalyst that was synthesized differently are commonly found in literature. However, the reported degradation intermediates are normally inconsistent. This issue is especially important for the degradation of toxic compounds because intermediates may be more toxic than their parent compounds and understanding the reason is necessary if appropriate catalysts are to be designed. This work systematically compares the photocatalytic degradation of diuron, a toxic recalcitrant herbicide, on two forms of zinc oxide (ZnO), i.e., conventional particles with zinc- and oxygen-terminated polar surfaces as the dominating planes, and nanorods with mixed-terminated nonpolar surfaces. Experimental and theoretical results indicate that both the rate of reaction and the degradation pathway depend on the adsorption configuration of diuron onto the surface. Diuron molecules adsorb in different alignments on the two surfaces, contributing to the formation of different degradation intermediates. Both the aliphatic and aromatic sides of diuron adsorb on the polar surfaces simultaneously, leading to an attack by hydroxyl radicals from both ends. On the other hand, on the mixed-terminated surface, only the aliphatic part adsorbs and is degraded. The exposed surface is therefore the key factor controlling the degradation pathway. For diuron degradation on ZnO, a catalyst confined to mixed-terminated surfaces, i.e., ZnO nanorods, is more desirable, as it avoids the formation of intermediates with potent phytotoxicity and cytogenotoxicity.     

Tell the truth or not? The montero mechanism for emissions control at work

We experimentally test the truth-telling mechanism proposed by Montero (2008) for eliciting firms' abatement costs. We compare this mechanism with two well-known alternative allocation mechanisms, free and costly allocation of permits at the Pigouvian price. Controlling for the number of firms and the firms' maximal emissions, we find that, in line with the theoretical predictions, firms over-report their maximal emissions under free allocation of permits and under-report these under costly allocation of permits. Under Montero's mechanism, by contrast, firms almost always report their maximal emissions truthfully. However, in terms of efficiency, the difference between Montero's mechanism and costly allocation disappears with industries including more than one firm.     

Carbon nanotubes-incorporated MIL-88B-Fe as highly efficient Fenton-like catalyst for degradation of organic pollutants

CNTs were incorporated into MIL-88B-Fe to get a new Fenton-like catalyst (C@M). Fe(II) was introduced in C@M to get a fast initiation of Fenton-like reaction. Fe(II) content in C@M was related with oxygen-containing functional groups on CNTs. C@M shows efficient catalytic degradation of pollutants over a wide pH range. Iron-based metal organic frameworks have been verified to be efficient heterogeneous Fenton catalysts due to their open pore channels and highly uniform distribution of metallic centers. In these catalysts, however, the iron element is mainly in the form of Fe(III), which results in a process required to reduce Fe(III) to Fe(II) to initiate Fenton reaction. To address this problem, carbon nanotubes (CNTs) with electron-rich oxygen-functional groups on the surface were incorporated into the metal organic frameworks (MIL-88B-Fe) to improve Fe(II) content for an enhanced Fenton-like performance. The prepared CNT@MIL-88B-Fe (C@M) showed much stronger catalytic ability toward H₂O₂ than MIL-88B-Fe. The pseudo-first-order kinetic constant for phenol degradation by C@M (0.32 min^–1) was about 7 times that of MIL-88B-Fe, and even higher than or comparable to the values of reported heterogeneous Fenton-like catalysts. Moreover, the Fenton-like system could effectively degrade various kinds of refractory organic pollutants and exhibited excellent catalytic activity over a wide pH range (4–9). XPS analysis confirmed that Fe(II) content of the catalyst gradually increased with CNT loadings. Electron spin resonance analysis showed that the signal intensity (•OH) of C@M was much higher than MIL-88B-Fe, which was consistent with the degradation efficiency of pollutants. Furthermore, the Fe(II) content of the catalyst gradually increased along with the oxygen-functional group content of CNTs. The result demonstrated that oxygen-containing functional groups of CNTs have a significant impact on the enhanced catalytic performance of C@M. This study provides a new insight to enhance Fenton reaction by using nanocarbon materials.     

Alcohol is a predictor of mortality in motor vehicle collisions

IntroductionIt is well recognized that driving while intoxicated increases the probability of a motor-vehicle collision (MVC). The effect of alcohol on the chance of surviving the MVC is less clear. Method: Using data from the Fatality Analysis Reporting System (FARS) we conducted analyses for the outcome of mortality using alcohol and other variables as predictors. We also selected alcohol positive (AP) and alcohol negative (AN) persons from the same MVC and vehicle to control for confounding characteristics. Results: The odds ratio (OR) for mortality for alcohol positive drivers was 2.57, (p < 0.001 for all the following OR). Other harmful predictive factors were age OR 1.01 per year, vehicle age OR 1.05 per year, male sex OR 1.23, avoidance maneuver OR 1.09, speed related OR 2.89, rollover mechanism OR 2.75, and collision with a fixed object OR 6.70. Protective factors were proper restraint use – OR 0.19 and collision with another moving vehicle, OR 0.21. In the multivariate analysis the OR of mortality for AP vs AN was 1.46. Proper restraint use (OR 0.27) remained protective along with collision with another moving vehicle. When AP and AN persons from the same MVC and the same vehicle were compared, the adjusted OR’s for mortality were 1.46 and 2.08, respectively. Conclusions: Alcohol is an independent predictor of mortality in an MVC. Proper restraint use is the strongest protective factor. This finding allows a more complete understanding of the risks of driving while intoxicated, not only a higher probability of an MVC, but decreased survival once the MVC occurs. Practical Applications: Identification of alcohol as an independent predictor of mortality in an accident may improve risk assessment and influence drivers to avoid driving while intoxicated.     

Individual differences in the mechanisms underlying the onset and maintenance of paternal behavior and the inhibition of infanticide in the monogamous biparental California mouse,Peromyscus californicus

Virgin male Peromyscus californicus tend to behave infanticidally or nonparentally towards pups, whereas virtually all males exhibit parental behavior following birth of their own young. Most males (65–75%) living with their pregnant partner attacked or ignored unfamiliar pups and did not become parental (behave parentally) prior to birth of their young. However, a significant minority of males (34%) living with their partner became parental after just 24 h of postcopulatory cohabitation with the female and remained parental throughout their mate's pregnancy. Males that were infanticidal before the birth of their young became parental only after their young were born. The presence of the mother was necessary for the postpartum maintenance of paternal behavior and the inhibition of infanticide in males that were infanticidal prepartum. In contrast, males that were paternal prior to birth of their young continued to be paternal after birth, even in the absence of postpartum contact with the mother. Thus, different mechanisms are involved in the inhibition of infanticide and the onset and maintenance of paternal behavior. Correspondence to: D.J. Gubernick     

改性ACF－PAN吸附SO_2前后表面结构变化及机机理究

以自制ＰＡＮ－基聚丙烯腈活性碳纤维ＡＣＦ－ＰＡＮ（ＡＣＦ－活性碳纤维、ＰＡＮ－聚丙烯腈）和改性处理的ＡＣＦ－ＰＡＮ吸附ＳＯ_２，借助ＩＲ、ｘ－光电子能谱分析等研究ＡＣＦ－ＰＡＮ改性处理及吸附ＳＯ_２前后表面结构变化。结果表明：各型ＡＣＦ－ＰＡＮ吸附ＳＯ_２的活性中心为表面结构中的含氮官能团以及引入的金属氧化物，其吸附机理是活性氮催化或电子传递。     

苯酚及其氯代物对大型[氵蚤]的毒性效应和微观机理探讨

采用静态生物急性试验的方法，研究了5种酚类化合物对大型[氵蚤]的急性毒性效应，并利用正辛醇／水分配系数（Kow）对实验测得的毒性数值进行了统计分析，得到了有效的毒性估测模型。研究结果表明，大型[氵蚤]的幼溪接触不同化合物的不同浓度，活动会受到抑制，甚至死亡，苯酚、4-氯酚、2，4-二氯酚、2，3，4-三氯酚和五氯酚的48hEC50分别为9．15、4．64、4．40、1．92、0．37mg／L；根据化学物质对[氵蚤]类的毒性评价标准，这5种化合物都属高毒物质，其中五氯酚具有极高毒性。另外，五氯酚对大型[氵蚤]的致毒关键步骤不仅包括传输分配过程还有生化反应。     

Comparative studies of the Fe–UV, H2O2–UV, TiO2–UV/vis systems for the decolorization of a textile dye X-3B in water

The degradation of a common textile dye, Reactive-brilliant red X-3B, by several advanced oxidation technologies was studied in an air-saturated aqueous solution. The dye was resistant to the UV illumination (wavelength λ  320 nm), but was decolorized when one of Fe³⁺, H₂O₂ and TiO₂ components was present. The decolorization rate was observed to be quite different for each system, and the relative order evaluated under comparable conditions followed the order of Fe²⁺–H₂O₂–UV  Fe²⁺–H₂O₂ > Fe³⁺–H₂O₂–UV > Fe³⁺–H₂O₂ > Fe³⁺–TiO₂–UV > TiO₂–UV > Fe³⁺–UV > TiO₂–visible light (λ  450 nm) > H₂O₂–UV > Fe²⁺–UV. The mechanism for each process is discussed, and linked together for understanding the observed differences in reactivity.     

Investigation on mechanism of phosphate removal on carbonized sludge adsorbent

For the removal of phosphate (PO₄^3 -) from water, an adsorbent was prepared via carbonization of sewage sludge from a wastewater treatment plant: carbonized sludge adsorbent (CSA). The mechanism of phosphate removal was determined after studying the structure and chemical properties of the CSA and its influence on phosphate removal. The results demonstrate that phosphate adsorption by the CSA can be fitted with the pseudo second-order kinetics and Langmuir isotherm models, indicating that the adsorption is single molecular layer adsorption dominated by chemical reaction. The active sites binding phosphate on the surface are composed of mineral particles containing Si/Ca/Al/Fe. The mineral containing Ca, calcite, is the main factor responsible for phosphate removal. The phosphate removal mechanism is a complex process including crystallization via the interaction between Ca^2 + and PO₄^3 -; formation of precipitates of Ca^2 +, Al^3 +, and PO₄^3 -; and adsorption of PO₄^3 - on some recalcitrant oxides composed of Si/Al/Fe.     

Performance and mechanism of Cr(VI) removal by zero-valent iron loaded onto expanded graphite

Zero-valent iron (ZVI) was loaded on expanded graphite (EG) to produce a composite material (EG-ZVI) for efficient removal of hexavalent chromium (Cr(VI)). EG and EG-ZVI were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier-transform infrared (FTIR) spectroscopy and Brunauer–Emmett–Teller (BET) analysis. EG-ZVI had a high specific surface area and contained sub-micron sized particles of zero-valent iron. Batch experiments were employed to evaluate the Cr(VI) removal performance. The results showed that the Cr(VI) removal rate was 98.80% for EG-ZVI, which was higher than that for both EG (10.00%) and ZVI (29.80%). Furthermore, the removal rate of Cr(VI) by EG-ZVI showed little dependence on solution pH within a pH range of 1–9. Even at pH 11, a Cr(VI) removal rate of 62.44% was obtained after reaction for 1 hr. EG-ZVI could enhance the removal of Cr(VI) via chemical reduction and physical adsorption, respectively. X-ray photoelectron spectroscopy (XPS) was used to analyze the mechanisms of Cr(VI) removal, which indicated that the ZVI loaded on the surface was oxidized, and the removed Cr(VI) was immobilized via the formation of Cr(III) hydroxide and Cr(III)–Fe(III) hydroxide/oxyhydroxide on the surface of EG-ZVI.