Catalytic degradation of toxic organic dye using an aluminum-doped Cu0.4Zn0.6-xAlxFe2O4 (x = 0.0, 0.2, 0.4, 0.6) spinel ferrite in a photo-Fenton system

Catalytic activity of spinel ferrite in breaking down toxic dye materials are promising due to their uniqueness. In this study, aluminum-doped copper zinc ferrite, Cu_0.4Zn_0.6-xAl_xFe₂O₄ (x = 0.0, 0.2, 0.4, 0.6), a catalyst for toxic dye degradation is synthesized through chemical co-precipitation route. The formation of the spinel ferrite catalyst is initially confirmed by Fourier transform infrared spectra, which shows the frequency of metal-oxygen bond vibration at 539 and 427 cm⁻¹ attributed to the tetrahedral and octahedral sites respectively. Higher intensity sharp peak of X-ray diffraction for (311) plane is the evidence for the phase purity and the formation of spinel ferrite. The crystallite size is found to decrease with the increase of Al³⁺ ion. The surface structure of the obtained particles is investigated using a scanning electron microscope. Analyses of the material's magnetic characteristics using a vibrating sample magnetometer (VSM) revealed that it is, in fact, a soft magnet, as evidenced by the loop of its hysteresis, which is narrow. The catalytic degradation of methylene blue dye under the mechanism of the photo-Fenton process is studied with the obtained spinel ferrites and the result is found to be as high as 96.5%. The process follows pseudo-second order kinetics and the Langmuir isotherm.     

Feasibility of honeycomb monolith supported sugar catalyst to produce biodiesel from palm fatty acid distillate (PFAD)

Carbon coated monolith was prepared by sucrose solution 65 wt.% via dip-coating method. Sulfonation of incomplete carbonized carbon coated monolith was carried out in order to synthesize solid acid catalyst. The textural structure characteristics of the solid acid catalyst demonstrated a low surface area and pore volume. Palm fatty acid distillate (PFAD), a by-product of palm oil refineries, was utilized as oil source in biodiesel production. The esterification reaction subjected to different reaction conditions was performed by using the sulfonated carbon coated monolith as heterogeneous catalyst. The sulfonation process had been performed by using vapour of concentrated H₂SO₄ that was much easier and efficient than liquid phase sulfonation. Total acidity value of carbon coated monolith was measured for unsulfonated sample (0.5 mmol/g) and sulfonated sample (4.2 mmol/g). The effect of methanol/oil ratio, catalyst amount and reaction time were examined. The maximum methyl ester content was 89% at the optimum condition, i.e. methanol/oil molar ratio (15:1), catalyst amount (2.5 wt.% with respect to PFAD), reaction time (240 min) and temperature 80 °C. The sugar catalyst supported on the honeycomb monolith showed comparable reactivity compared with the sugar catalyst powder. However, the catalyst reusability studies showed decrease in FFA% conversion from 95.3% to 68.8% after four cycles as well as the total acidity of catalyst dropped from the value 4.2 to 3.1 mmol/g during these cycles. This might be likely due to the leaching out of SO₃H group from the sulfonated carbon coated monolith surface. The leaching of active species reached a plateau state after fourth cycle.     

湖北省2008年初低温雨雪冰冻过程气候特征分析

2008年初，湖北省出现了严重的低温雨雪冰冻灾害，直接经济损失高达110亿元以上，有必要对灾害期间的气候特征进行系统、科学的分析和总结。对湖北省76个气象站2008年1月12日～2月3日气温、降水（雪）、日照以及低温持续日数等要素进行时空间差异分析及历史与同期比较，并选取10个代表站历史上所有低温雨雪天气过程，对其过程持续低温日数、最长连续雨雪日数、过程极端低温进行比较分析。结果表明：（1）此次过程的平均气温异常偏低，该省大部为-1～-2℃，比常年同期偏低4～6℃，为各站历史同期最低，其中主要是最高气温异常偏低所致，但极端低温并不低；（2）降雪过程频繁，雨雪量异常偏多；（3）低温冰冻持续时间长，该省大部在16～22 d，位于历史第一；（4）日照异常偏少。持续而稳定的大气环流异常形势是湖北省大范围低温雨雪天气的直接原因。     

EFFECTS OF ADJACENT AGRICULTURAL ACTIVITIES AND WATERSHED CHARACTERISTICS ON STREAM MACROINVERTEBRATE COMMUNITIES1

Benthic macroinvertebrate communities in streams adjacent to cornfields, streams where cows had unrestricted access, and reference locations without agriculture were compared to examine the effects of local land use and land use/land cover in the watershed. At each local site, macroinvertebrates and a variety of habitat parameters were measured upstream, adjacent, downstream, and farther downstream of the local land use. A geographic information system (GIS) was used to calculate drainage basin area, land use/land cover percentages in each basin, and the distance from sample sites to the stream source. Three‐way analysis of covariance (ANCOVA) tests with date, site type, and sampling location as main effects were used to explore differences in macroinvertebrate metrics using median substrate size, percent hay/pasture area, and stream depth as covariates. The covariates significantly improved model fit and showed that multiple contributing factors influence community composition. Local impacts were greatest at sites where cows had access, probably because of sedimentation and embeddedness in the substrate. Differences between the upstream and the adjacent and downstream locations were not as great as expected, perhaps because upstream recolonization was reduced by agricultural impacts or because of differences in the intensity or proximity of agriculture to riparian areas in the watershed. The results underscore the importance of both local and watershed factors in controlling stream community composition.     

Biological Activity in a Heavily Organohalogen-Contaminated River Sediment (8 pp)

Background, Aims and Scope Sediments of the Spittelwasser creek are highly polluted with organic compounds and heavy metals due to the discharge of untreated waste waters from the industrial region of Bitterfeld-Wolfen, Germany over the course of more than one century. However, relatively few data have been published about the chloroorganic contamination of the sediment. This paper reports on the content of different (chloro)organic compounds with special emphasis on polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F), and chlorobenzenes. Existing concepts for the remediation of Spittelwasser sediment include the investigation of natural attenuation processes, which largely depend on the presence of an intact microbial food web. In order to gain more insight in terms of biological activity, we analyzed the capacity of sediment microflora to degrade organic matter by measuring the activities of extracellular hydrolytic enzymes involved in the biogeochemical cycling of carbon, nitrogen, phosphorus and sulfur. Furthermore, the detection of physiologically active bacteria in the sediment, particularly of those known for their capability to reductively dehalogenate organochlorine compounds, illustrates the potential for intrinsic bioremediation processes. Methods PCDD/F and chlorobenzenes were analyzed by gas chromatography(GC)/mass spectrometry and GC/flame ionization detection, respectively. The activities of hydrolytic enzymes were determined from freshly sampled sediment layers using 4-methylumbelliferyl (MUF) or 7-amino-4-methylcoumarin-conjugated model compounds and kinetic fluorescence measurements. Physiologically active bacteria from different sediment layers were microscopically visualized by fluorescence in situ hybridization (FISH). Specific bacteria were identified by 16S rRNA gene amplification and sequencing. Results and Discussion The PCDD/F congener profile was dominated by dibenzofurans. In addition, the presence of specific tetra and pentachlorinated dibenzofurans supported the assumption that extensive magnesium production was one possible source for the high contamination. A range of other chloroorganic compounds, including several isomers of chlorobenzenes, hexachlorocyclohexane and 1,1,1-trichloro-2,2-bis (p-chloro-phenyl)ethane (DDT), was present in the sediment. Activities of extracellular hydrolytic enzymes showed a strong decrease in those sediment layers that were characterized by high contents of absorbable organic halogen (AOX), indicating disturbed organic matter decay. Interestingly, an abnormal increase of cellulolytic enzyme activities below the organochlorine-rich layers was observed, possibly caused by residual cellulose from discharges of sulfite pulping wastes. FISH revealed physiologically active bacteria in most sediment layers from the surface down to the depth of about 60 cm, including members of Desulfitobacterium (D.) and Sulfurospirillum. The presence of D. dehalogenans was confirmed by its partial 16S rRNA gene sequence. Conclusions Results of chemical sediment analyses demonstrated high loads of organochlorine compounds, particularly of PCDD/F. Several years after stopping the waste water discharge to Spittelwasser creek, this sediment remains a main source for pollution of the downstream river system by way of the ongoing mobilization of sediment during high floods. As indicated by our enzyme activity measurements, the decomposition potential for organic matter is low in organochlorine-rich sediment layers. In contrast, the comparably higher enzyme activities in less organochlorine-polluted sediment layers as well as the presence of physiologically active bacteria suggest a considerable potential for natural attenuation. Recommendations and Perspectives From our data we strongly recommend to explore the degradative capacity of sediment microorganisms and the limits for in situ activity towards specific sediment pollutants in more detail. This will give a sound basis for the integration of bioremediation approaches into general concepts to reduce the risk that permanently radiates from this highly contaminated sediment. Submission Editor: Dr. Henner Hollert (Henner.Hollert@urz.uniheidelberg.de)     

Split-hand/split-foot malformation with paternal mutation in the p63 gene

We report the prenatal diagnosis at 16 weeks' gestation of bilateral split-hand/split-foot malformation (SHSFM) with severe lobster claw deformity of hands and feet in a male fetus without associated malformations. A minor manifestation of SHSFM was present in the father with only mild bilateral foot involvement (syndactyly I–II; cleft II–III; left cutaneous syndactyly III–IV). Mutation analysis of the p63 gene on chromosome 3q27 showed a missense mutation 577A→G (predicting amino acid substitution K193E) in the father. This mutation has not been reported so far in SHSFM but resembles the previously reported 580A→G (predicting amino acid substitution K194E) in a family with SHSFM. Copyright © 2001 John Wiley & Sons, Ltd.     

Variation of leaf gland volatile oil within a population of sweet gale (Myrica gale) (Myricaceae)

Summary The leaf gland volatile oils of ten sweet gale plants from a Scottish population were extracted in early summer. The results differed notably from reports of other populations in respect of the sesquiterpenes, -elemenone and germacrone, which were major components of the volatile oil. Three dihydrochalcones were also detected in the volatile oil. Variation within the population existed, particularly with respect to the relative importance of germacrone. Five plants were resampled in late summer and exhibited a marked reduction in -elemenone, a lesser reduction in germacrone and changes in the proportions of some monoterpenes.     

华北区域点冬季二次有机气溶胶特征与影响因素

为探明二次有机气溶胶(SOA)的污染特征和影响因素,本研究于2018年11月—2019年1月对华北区域点(德州市郊区点)细颗粒物(PM_(2.5))的化学组成进行了在线测量,并分析了PM_(2.5)中有机碳(OC)、元素碳(EC)和水溶性离子组分的污染特征及PM_(2.5)与气象要素之间的相关性.结果表明,观测期间德州PM_(2.5)污染严重,平均质量浓度为(115.6±24.6)μg·m~(-3);其中,有机碳和元素碳是PM_(2.5)的主要成分,平均质量浓度分别为(8.2±5.8)μg·m~(-3)和(2.6±2.2)μg·m~(-3),占PM_(2.5)总质量的7.1%和2.2%;PM_(2.5)与风速呈负相关,与相对湿度呈正相关,与气温的相关性较差,偏北风对PM_(2.5)浓度影响较大.同时,本研究利用EC示踪OC/EC比值法对PM_(2.5)中的二次有机碳(SOC)进行了估算,通过估算得到的SOC结果表明,华北区域点冬季SOC是OC的重要组成部分,平均浓度为(4.0±2.9)μg·m~(-3),占OC的45.7%,SOC在白天占比较高(62.7%),早晚由于有局地生物质燃烧影响,SOC占比降低,约占OC的42.7%.本研究还分析了SOC生成的影响因素,分析了德州市冬季O_3、含水量、酸度与SOC的相关性.结果表明,SOC受臭氧浓度影响,但在白天和夜晚表现出不同的相关关系,可能存在不同的生成机制.最后,利用ISORROPIA模型估算了颗粒物的含水量和酸度,发现SOC在高含水量和低含水量下存在不同的关系,高含水量更能促进SOC生成;在高含水量下SOC与H~+具有显著相关性,但在低含水量下则不相关,表明颗粒物含水量较高、H~+浓度较高情况下液相酸催化反应可能对SOC具有重要贡献.     

MnFe2O4磁性纳米棒非均相Fenton催化降解水中四环素的研究

采用水热合成法成功制备出MnFe₂O₄磁性纳米棒（s-MnFe₂O₄）,并考察了商品化的Fe₃O₄、MnFe₂O₄和合成的s-MnFe₂O₄纳米棒这3种磁性纳米颗粒作为非均相Fenton催化剂降解水中四环素抗生素的性能.同时,采用X射线衍射（XRD）、透射电镜（TEM）、N₂吸附-脱附、振动样品磁强计（VSM）及X射线光电子能谱（XPS）等技术对催化剂的理化性质进行了表征.非均相Fenton催化降解四环素的结果表明,s-MnFe₂O₄具有最高的催化活性,反应180 min,四环素的去除率可以达到87.6%,TOC的去除率达到47.5%.自由基捕获试验证实了羟基自由基（·OH）是非均相Fenton氧化过程中的主要活性物种.s-MnFe₂O₄磁性纳米棒的高催化活性归因于其表面拥有较高含量的Mn³⁺和Fe²⁺物种,它们的存在能加速界面电子的转移效率,从而促进·OH的生成.合成的s-MnFe₂O₄催化剂具有良好的稳定性,循环使用6次,四环素的去除率仅从87.6%降低到80.2%,且氧化过程中活性组分的流失很少.