Orange G degradation by heterogeneous peroxymonosulfate activation based on magnetic MnFe2O4/α-MnO2 hybrid

Wastewater containing an azo dye Orange G (OG) causes massive environmental pollution, thus it is critical to develop a highly effective, environmental-friendly, and reusable catalyst in peroxymonosulfate (PMS) activation for OG degradation. In this work, we successfully applied a magnetic MnFe₂O₄/α-MnO₂ hybrid fabricated by a simple hydrothermal method for OG removal in water. The characteristics of the hybrid were investigated by X-ray diffraction, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, Fourier transform infrared spectroscopy, Brunauer–Emmett–Teller method, vibrating sample magnetometry, electron paramagnetic resonance, thermogravimetric analysis, and X-ray photoelectron spectroscopy. The effects of operational parameters (i.e., catalytic system, catalytic dose, solution pH, and temperature) were investigated. The results exhibited that 96.8% of OG degradation was obtained with MnFe₂O₄/α-MnO₂(1:9)/PMS system in 30 min regardless of solution pH changes. Furthermore, the possible reaction mechanism of the coupling system was proposed, and the degradation intermediates of OG were identified by mass spectroscopy. The radical quenching experiments and EPR tests demonstrated that SO₄^{• ̶}, O₂^{• ̶}, and ¹O₂ were the primary reactive oxygen species responsible for the OG degradation. The hybrid also displayed unusual stability with less than 30% loss in the OG removal after four sequential cycles. Overall, magnetic MnFe₂O₄/α-MnO₂ hybrid could be used as a high potential activator of PMS to remove orange G and maybe other dyes from wastewater.     

甲基橙在镧掺杂二氧化钛表面的吸附研究

以钛酸丁酯为原料,采用溶胶-凝胶法成功制备了一系列La^3＋-TiO2光催化剂。通过XRD对催化剂进行了表征,XRD光谱结果表明所制得的TiO2光催化剂晶型结构为锐钛矿型。考察了pH值对甲基橙在纯TiO2光催化剂表面的吸附以及掺杂量对吸附的影响,通过紫外-可见光吸收光谱分析得出碱性或中性条件下的吸附较好。镧（La^3＋）掺杂量的TiO2对甲基橙的吸附实验表明,La^3＋的掺杂显著提高了甲基橙在TiO2催化剂表面的吸附能力,随着La^3＋掺杂量的增加,吸附能力逐渐增强。     

A concept model to estimate the potential distribution of the Asiatic citrus psyllid (Diaphorina citri Kuwayama) in Australia under climate change—A means for assessing biosecurity risk

Increasing global temperatures as a result of climate change are widely considered inevitable for Australia. Despite this, the specific effects of climate change on Australian agriculture are little studied and the effects on agricultural pests and diseases are virtually unknown. In this paper we consider the impact of climate change on the Asiatic citrus psyllid (Diaphorina citri Kuwayama [Hemiptera: Psyllidae]); one of two known vectors of huanglongbing (citrus greening); a debilitating disease which is caused in Asia by a phloem-limited bacterium ‘Candidatus Liberibacter asiaticus’ (α-Proteobacteria). D. citri does not occur in Australia, but if introduced would pose a major threat to the viability of the Australian citrus industry and to native Citrus species. This paper presents an approach developed to understand how climate change may influence the behaviour, distribution and breeding potential of D. citri. Here we developed and describe an initial dynamic point model of D. citri biology in relation to its citrus host and applied it to a scenario of increasing temperatures, as indicators of climate change, on a continental scale. A comparison between model outputs for the three time frames considered (1990, 2030 and 2070) confirms that increasing temperatures projected under climate change will affect the timing and duration of new citrus growth (flush) necessary for psyllid development throughout Australia. Flushing will start progressively earlier as the temperature increases and be of shorter duration. There will also be a gradual southward expansion of shorter durations of the occurrence of flush. Increasing temperatures will impact on D. citri both directly through alteration of its temperature dependant development cycle and indirectly through the impact on the host flushing cycle. For the whole of Australia, a comparison between model outputs for the three scenarios considered indicates the seasonality of D. citri development will change to match changes in citrus flush initiation. Results indicate that the risk of establishment by D. citri is projected to decrease under increasing temperatures, mainly due to shortened intervals when it can feed on new leaf flushes of the host. However, the spatially heterogeneous results also suggest that regions located on the southern coastline of Australia could become more suitable for D. citri than projected under current temperatures. These results confirm the value of a linked host-pest approach as based on D. citri climatic requirements alone the model would have accounted only for shorter development periods and predicted an increased risk of potential distribution.     

电芬顿氧化法处理酸性橙Ⅱ模拟废水

为分解酸性橙Ⅱ分子结构中的偶氮键和萘环,提高酸性橙Ⅱ废水的可生化性,采用电芬顿氧化法处理质量浓度为300mg/L的酸性橙Ⅱ模拟废水,研究了不同电流密度对电芬顿系统处理效率的影响.结果表明,在不同电流密度条件下,模拟废水ρ(CODCr)由377.8 mg/L快速降至276.9 mg/L时,消耗的电量分别为300 C(10.0 mA/cm2)、810 C(7.5 mA/cm2)、2 190 C(5.0mA/cm2)和1 710 C(2.5 mA/cm2),说明在高电流密度条件下,电芬顿反应器能够高效快速地分解酸性橙Ⅱ,同时消耗最低的电量.电芬顿系统处理出水的紫外可见光谱检测结果表明,在较高电流密度(7.5 mA/cm2)条件下,电芬顿系统仅需要10 min就能够基本完全分解酸性橙Ⅱ分子结构中的偶氮键和萘环,提高废水的可生化性.      

碳纳米管活化过一硫酸盐降解金橙G过程及动力学

采用碳纳米管(CNT)作为固体活化剂,活化过一硫酸盐(PMS)氧化降解偶氮染料金橙G(OG).结果表明,CNT活化PMS降解OG的效果要比活性炭(GAC)好,45 min可使OG的脱色率达到99%;并研究了CNT活化PMS降解OG的机制及反应过程的动力学,发现CNT活化PMS产生的自由基主要是SO_4~-·,活化场所在CNT的表面.通过对CNT/PMS体系降解OG的主要影响因素(温度、OG初始浓度、CNT投加量、PMS浓度、初始pH)进行一级动力学拟合.最后通过紫外可见光谱分析,发现OG在479 nm和330 nm处吸收峰强度明显减少,表明OG分子中偶氮键及萘环结构均一定程度被破坏;且CNT/PMS降解体系对染料OG具有一定矿化率.     

Azo-dyes photocatalytic degradation in aqueous suspension of TiO2 under solar irradiation

The photodegradation of two common and very stable azo-dyes, i.e. methyl-orange (C₁₄H₁₄N₃SO₃Na) and orange II (C₁₆H₁₁N₂SO₄Na), is reported. The photocatalytic oxidation was carried out in aqueous suspensions of polycrystalline TiO₂ irradiated by sunlight. Compound parabolic collectors, installed at the “Plataforma Solar de Almería” (PSA, Spain) were used as the photoreactors and two identical reacting systems allowed to perform photoreactivity runs for the two dyes at the same time and under the same irradiation conditions. The disappearance of colour and substrates together with the abatement of total organic carbon content was monitored. The main sulfonate-containing intermediates were found to be in lower number in respect to those obtained under artificial irradiation. In particular there were no more evidence of the presence of hydroxylated transients. The dependence of dye photooxidation rate on: (i) substrate concentration; (ii) catalyst amount; and (iii) initial pH was investigated. The influence of the presence of strong oxidant species (H₂O₂, S₂O₈²⁻) and some ions (Cl⁻, SO₄²⁻) on the process was also studied.     

Residual congener pattern of dioxins in human breast milk in southern Vietnam

This study evaluated residual congener patterns of dioxin/furan (=PCDD/DF) related to tactical herbicides aerially sprayed over the regions of southern Vietnam through Operation Ranch Hand. The study focused on Cam Chinh (CC) commune, Quang Tri province (an area sprayed with tactical herbicides), and the Cam Phuc (CP) commune, Ha Tinh province (a non-sprayed area). Breast milk samples for analysis were collected in September 2002 and July 2003 from lactating primiparous and multiparous mothers born after the war (<31 years old). We found the levels of each congener in the CC commune were higher than in the CP commune, and determined specificity in the PCDD/DF congener pattern in CC commune samples by cluster analysis. The congener pattern is characterized by higher (the hexa-, the hepta-, and the octa-) chlorinated PCDD/DFs; this appears to be the same profile as that presented by pentachlorophenol (PCP), rather than 2,4,5-trichlorophenoxy acid (2,4,5-T) contaminated with 2,3,7,8-TCDD. A GC/MS study in the 1970s detected the chlorophenols 2,4-di and 2,4,6-trichlorophenol in some Agent Orange samples, which contained, like PCP, a wide variety of PCDD/DF congeners. In this context, it may be expected that certain tactical herbicides contaminated with various chlorophenol impurities, have a unique congener pattern when compared with pure 2,4,5-T formulations.     

气相色谱法测定柑橘和土壤中螺螨酯残留

以丙酮为提取剂,二氯甲烷为萃取剂,采用弗罗里硅土柱净化,气相色谱-电子捕获检测器测定柑橘和土壤中的螺螨酯残留,优化了样品前处理条件。方法在0.141μg/L～5.65 mg/L范围内线性良好,最低检出限为0.003 5 mg/kg,空白样品在0.050 mg/kg、0.500 mg/kg、1.00 mg/kg 3个添加水平上的平均回收率为82.2%～110%,平行测定的RSD为2.6%～9.8%。     

Methyl Orange removal by a novel PEI-AuNPs-hemin nanocomposite

A novel poly(ethyleneimine)/Au nanoparticles/hemin nanocomposite(PEI-AuNPs-Hemin)acting for Methyl Orange(MO) removal has been synthesized. PEI-AuNPs was prepared firstly and it was then linked to hemin through the coupling between carboxyl groups in hemin and amino groups in PEI without the activation of carboxyl groups. The high reactivity and stability of AuNPs contributed greatly in the formation of the amido bonds in the nanocomposite. Fourier transform infrared spectroscopy, transmission electron microscopy and UV–visible spectroscopy were used to characterize the PEI-AuNPs-Hemin.Results show that PEI-AuNPs-Hemin has strong adsorption for MO. Adsorption and degradation experiments were carried out at different p Hs, nanocomposite concentrations and UV irradiation times. Removal of MO in acidic solutions was more effective than in basic solutions. The real-time study showed that the MO degradation with the nanocomposite under UV irradiation was a fast process. In addition, the photocatalytic degradation mechanism was proposed. The study suggests that the PEI-AuNPs-Hemin may have promising applications in environmental monitoring and protection.     

Enhanced Co-Metabolism of TCDD in the Presence of High Concentrations of Phenoxy Herbicides

Chemical residue studies were conducted from 1977-1987 on sites where spills of Agent Orange had occurred in the Herbicide Storage Sites at the Naval Construction Battalion Center, Gulfport, Mississippi, and on Johnston Island, Central Pacific Ocean. The soil persistence time of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) was significantly decreased when in the presence of massive amounts of phenoxy herbicides (> 62,000 microg of herbicide/g of soil). Although microbial populations doubled in the most highly contaminated sites, fungal species diversity decreased. The dominant fungal species that appeared to be associated with the metabolism of the residues were of the genera Penicillium, Mucor, and Fusarium. TCDD level decreased from a mean high of 180 ng/g (ppb) to less than 1 ng/g of soil over a ten-year period.