Metals in vineyard soils of the Penedès area (NE Spain) after compost application

The application of organic wastes to improve soil physical characteristics in mechanized vineyards planted after land levelling is becoming a common practice in Mediterranean areas. It may be useful as an additional source of organic matter and nutrients, but these wastes could also have negative effects due to their metal content. The aim of the study was to evaluate the influence of compost application on soil metal contents in mechanized vineyard soils of the Spanish Mediterranean area, where this practice is repeated every three years. The study was carried out in a ten-year-old vineyard where the main soil type is Typic Calcixerept. Composted cattle manure was applied in alternate rows, at a rate of 40 Mgha(-1) dry-weight. Nine sampling points were located along the slopes of two plots: a levelled plot prepared for mechanization with large soil disturbance movements within the plot, and a plot of undisturbed soil. At each location, soil samples were taken in both treated and untreated soils. Total concentrations (digestion with aqua regia) and the extractable DTPA (Diethylene-triaminepentacetic)-CaCl2-TEA (Triethanolamine) fractions of Cu, Zn and Mn were analyzed in each sample. For Cu and Zn, the initial concentration was higher in the undisturbed plot. In both cases, total Cu and total Zn were positively affected by manure input and the concentration in treated soils was significantly higher than in untreated soil. For Mn, the initial concentration was higher in disturbed soils than in undisturbed ones, and although in both scenarios the concentrations increased with manure, no significant differences were found between treated and untreated soils. The extractable fraction also increased in treated versus untreated soils, although for Cu and Mn the extractable/total metal ratio was similar in treated and untreated soils. After one compost application, total metal contents increased significantly, particularly for Zn. Most of those metals are accumulated in the soil, due to the soil characteristics.     

铁铜双金属有机骨架MIL-101(Fe,Cu)活化双氧水降解染料性能

针对非均相芬顿传质效率低和Fe（Ⅲ）Fe（Ⅱ）转化慢导致活性低等问题,采用溶剂热法制备铁铜双金属有机骨架材料[MIL-101（Fe,Cu）],并研究了材料界面性质、催化降解染料（亚甲基蓝）性能以及活化催化机制.结果表明,MIL-101（Fe,Cu）晶体结构完整且呈三维八面体形状;比表面积和平均孔径分别为667.2 m² ·g^-1和1.9 nm,可充分暴露反应活性位点.MIL-101（Fe,Cu）在广谱pH范围可活化H₂ O₂高效降解亚甲基蓝.当pH=5、反应20 min,MIL-101（Fe,Cu）/H₂ O₂对20 mg ·L^-1亚甲基蓝的去除率为100%,较MIL-101（Fe）/H₂O₂和单独H₂ O₂分别提高43.1%和88.9%.自由基猝灭实验与反应前后铁和铜价态变化结果表明,羟基自由基（·OH）是MIL-101（Fe,Cu）/H₂ O₂催化降解亚甲基蓝的主要活性物种;Cu（Ⅱ）掺杂引入新的活性位点,且Cu（Ⅱ）/Cu（Ⅰ）循环和Fe（Ⅲ）/Fe（Ⅱ）循环可协同产生·OH,进而提高催化效率.MIL-101（Fe,Cu）作为新型非均相类芬顿催化剂,无需复杂pH调节即可获得良好催化效果,在工业废水处理上具有较好地应用前景.     

Synergistic effects of Cu species and acidity of Cu-ZSM-5 on catalytic performance for selective catalytic oxidation of n-butylamine

In this work, a series of Cu-ZSM-5 catalysts with different SiO₂/Al₂O₃ ratios (25, 50, 100 and 200) were synthesized and investigated in n-butylamine catalytic degradation. The n-butylamine can be completely catalytic degradation at 350°C over all Cu-ZSM-5 catalysts. Moreover, Cu-ZSM-5 (25) exhibited the highest selectivity to N₂, exceeding 90% at 350°C. These samples were investigated in detail by several characterizations to illuminate the dependence of the catalytic performance on redox properties, Cu species, and acidity. The characterization results proved that the redox properties and chemisorption oxygen primarily affect n-butylamine conversion. N₂ selectivity was impacted by the Brønsted acidity and the isolated Cu²⁺ species. Meanwhile, the surface acid sites over Cu-ZSM-5 catalysts could influence the formation of Cu species. Furthermore, in situ diffuse reflectance infrared Fourier transform spectra was adopted to explore the reaction mechanism. The Cu-ZSM-5 catalysts are the most prospective catalysts for nitrogen-containing volatile organic compounds removal, and the results in this study could provide new insights into catalysts design for VOC catalytic oxidation.     

Effects of Na+ on Cu/SAPO-34 for ammonia selective catalytic reduction

Copper-exchanged chabazite (Cu/CHA) catalysts have been found to be affected by alkali metal and alkaline earth ions. However, the effects of Na⁺ ions on Cu/SAPO-34 for ammonia selective catalytic reduction (NH₃-SCR) are still unclear. In order to investigate the mechanism, five samples with various Na contents were synthesized and characterized. It was observed that the introduced Na⁺ ion-exchanges with H⁺ and Cu^2 + of Cu/SAPO-34. The exchange of H⁺ is easier than that of isolated Cu^2 +. The exchanged Cu^2 + ions aggregate and form “CuAl₂O₄-like” species. The NH₃-SCR activity of Cu/SAPO-34 decreases with increasing Na content, and the loss of isolated Cu^2 + and acid sites is responsible for the activity loss.     

Mulberry-silkworm food chain--a templet to assess heavy metal mobility in terrestrial ecosystems

Assessment of the food chain mobility of heavy metals inthe natural ecosystem receives more attention nowadays. Inthe present study, mulberry-silkworm food chain has beenfocused as a templet to assess the biomobility of heavymetals in soil-higher plant-insect hierarchy. Both in thecase of Cd and Cu treatments, higher mobility wasobserved in the level-1 (soil–root) followed by level-3(leaf–larva), level-4 (larvae–faecal) and level-2(root–leaf). Consequently, roots accumulated more amountsof Cd and Cu, with a limited transport to the leaves.Among the two metals (Cd and Cu) tested, in the plant,the transfer potential of Cd exceeds that of Cu. Whereasin the case of leaf–larval transfer, Cu precedes overCd. Accumulation of Cd and Cu in all the levels (1–4)tested showed a concentration dependent increase, except inthe level 4 (larva–faecal) of Cd treatment where adeclining trend was noticed.     

微波消解-原子吸收光度法测定土壤中铜锌铅镉镍铬

用微波消解－原子吸收光度法测定土壤中铜，锌，铅，镉，镍和铬。通过硝酸－氢氟酸－过氧化氢体系消解液对土壤样品消解，选择出微波最佳消解条件。对硝酸－盐酸－过氧化氢体系消解液和硝酸－氢氟酸－过氧化氢体系消解液进行消解对比试验，发现前者不能将土壤样品完全消解，后者能将样品消解完全，但需将消解液中剩余的酸赶尽，否则测定结果将明显偏低。微波消解土壤与传统电热消解相比，操作简便快速，可提高工作效率。     

Effect of temperature on single and competitive adsorptions of Cu(II) and Zn(II) onto natural clays

This study conducted a combined adsorption-sequential extractionanalysis (CASA), by which five phases (i.e., exchangeable, carbonate, Mn-Oxide, organic, and Fe-Oxide phases) of adsorbed heavy metals were analyzed, to investigate temperature effects on single and competitive adsorptions of Zn(II) and Cu(II) ontonatural clays. In the case of single adsorption of Zn, the exchangeable phase adsorption decreased from 65 to 40%, but thecarbonate phase adsorption increased from 30 to 40%, with an increase in temperature from 15 to 55 °C. However, in itscompetitive adsorption with Cu, Zn was mostly present in the exchangeable phase (over 90%), and with an increase in temperature, the exchangeable phase adsorption decreased only 10%. In the case of Cu, over 50% among the total amount of adsorption was present in the carbonate phase in both cases ofsingle and competitive adsorptions. The carbonate phaseadsorption of Cu increased from 56 to 61% and from 60 to 66% in single and competitive adsorptions, respectively, with atemperature increase. These results show that in the case of Zn,the major mechanism of retention in natural clay soils might beexchangeable phase adsorption, especially in the case of competitive adsorption with Cu. However, in the case of Cu, the major mechanism might be carbonate phase adsorption, which is known to be a more immobile phase than exchangeable phase adsorption. It seems that the adsorption of Zn and Cu onto natural clays is an endothermic reaction, which represents thatthe adsorption equilibrium constants and capacities increase with a temperature increase, with the exception of exchangeablephase adsorption.     

金属铁还原降解2,4-二硝基甲苯的实验研究

研究了金属铁对2,4-二硝基甲苯(2,4-DNT)的还原降解情况.实验结果表明,2,4-DNT的还原降解与溶液初始pH值、初始浓度和溶解氧等因素有关.氯离子能消除金属铁的钝化现象.金属铁表面附载的铜对2,4-DNT的还原降解具有催化作用.     

植物多酚物质原位钝化污染土壤重金属的研究Ⅱ.对土壤Cu环境行为和生物活性的影响动态

通过室内好气培养和生物盆栽试验研究了缩合类植物多酚L和Y以及 8 羟基喹啉在污染红壤和潮土中的降解动态及其对土壤Cu环境行为的影响 .结果表明植物多酚在两周内降解相对较快 ,而 8 羟基喹啉则难以降解 .与空白相比 ,Cu污染土壤中施用植物多酚后土壤水溶性Cu显著下降 ,钝化Cu的效果次序为 :8 羟基喹啉 >多酚Y >多酚L .随着植物多酚的降解 ,土壤Cu被释出 ,其水溶性Cu浓度与残留在土壤中多酚浓度 (以DOC浓度表示 )呈负相关关系 ,尤其在潮土上更为明显 ,而pH与水溶性Cu没有相关性 .试验还发现 ,钝化剂施用后 ,小麦体内的Cu含量降低 ,因此 ,植物多酚是钝化重金属污染土壤的良好选择     

长江中下游海相三叠系膏盐层与铜(金)、铁矿床

长江中下游海相三叠系膏盖层中含有很大比例的大、中型铜（金）、铁、多金属矿床。膏盐层不仅是铜（金）、铁矿床的主要赋矿层位之一，而且是部分成矿金属的矿源层；膏盐层还为燕山期岩浆提供部分钠质、钾质及挥发组分，影响岩浆演化的方向，改变了含矿流体的性质；另外，从岩体和矿床中金属硫化物中流同位素重硫成分的增高，说明在成者、成矿过程中，膏盐层是硫的供应者之一。因此膏盐层与铜（金）、铁、多金属矿床之间存在着特殊的成因联系。