Isotope tracing of submarine groundwater discharge offshore Ubatuba, Brazil: results of the IAEA–UNESCO SGD project

Results of groundwater and seawater analyses for radioactive (³H, ²²²Rn, ²²³Ra, ²²⁴Ra, ²²⁶Ra, and ²²⁸Ra) and stable (D and ¹⁸O) isotopes are presented together with in situ spatial mapping and time series ²²²Rn measurements in seawater, direct seepage measurements using manual and automated seepage meters, pore water investigations using different tracers and piezometric techniques, and geoelectric surveys probing the coast. This study represents first time that such a new complex arsenal of radioactive and non-radioactive tracer techniques and geophysical methods have been used for simultaneous submarine groundwater discharge (SGD) investigations. Large fluctuations of SGD fluxes were observed at sites situated only a few meters apart (from 0 cm d⁻¹ to 360 cm d⁻¹; the unit represents cm³/cm²/day), as well as during a few hours (from 0 cm d⁻¹ to 110 cm d⁻¹), strongly depending on the tidal fluctuations. The average SGD flux estimated from continuous ²²²Rn measurements is 17 ± 10 cm d⁻¹. Integrated coastal SGD flux estimated for the Ubatuba coast using radium isotopes is about 7 × 10³ m³ d⁻¹ per km of the coast. The isotopic composition (δD and δ¹⁸O) of submarine waters was characterised by significant variability and heavy isotope enrichment, indicating that the contribution of groundwater in submarine waters varied from a small percentage to 20%. However, this contribution with increasing offshore distance became negligible. Automated seepage meters and time series measurements of ²²²Rn activity concentration showed a negative correlation between the SGD rates and tidal stage. This is likely caused by sea level changes as tidal effects induce variations of hydraulic gradients. The geoelectric probing and piezometric measurements contributed to better understanding of the spatial distribution of different water masses present along the coast. The radium isotope data showed scattered distributions with offshore distance, which imply that seawater in a complex coast with many small bays and islands was influenced by local currents and groundwater/seawater mixing. This has also been confirmed by a relatively short residence time of 1–2 weeks for water within 25 km offshore, as obtained by short-lived radium isotopes. The irregular distribution of SGD seen at Ubatuba is a characteristic of fractured rock aquifers, fed by coastal groundwater and recirculated seawater with small admixtures of groundwater, which is of potential environmental concern and has implications on the management of freshwater resources in the region.     

电感耦合等离子体质谱法在环境监测中的应用

针对ICP-MS技术的使用特点及其近年来在环境监测领域的应用进行综合阐述，并对ICP-MS技术的发展前景作出简单的评述。     

重量法测定含动、植物油和矿物油废水应注意的问题

废水监测中，用重量法测定污（废）水中的动、植物油和矿物油是常用方法之一。为了保证测试结果的准确性，减少误差，提高分析测试质量，作者以多年的实践经验结合塔里木油田采油厂生产污水和餐饮行业生活废水的测定，对测定两种不同含油类废水应注意的问题进行探讨。供同行在实际工作中参考。     

The aggregation pheromone ofIps duplicatus and its role in competitive interactions withI. typographus (Coleoptera: Scolytidae)

Summary Ips duplicatus withI. typographus co-inhabiting Norway spruce (Picea abies (L.) Karst.) would benefit from a pheromone blend distinct from that of the larger competitorI. typographus. GC-MS analysis showed thatI. duplicatus males feeding in the host produced ipsdienol (Id),cis-verbenol (cV),trans-verbenol (tV), myrtenol (Mt), andE-myrcenol (EM) and traces of 2-methyl-3-buten-2-ol (MB).I. duplicatus produced Id in approximately racemic form (48.9-54.5% (+)-(S)-isomer). The amounts of Id and EM released over a 9 day period had a maximum of 250 and 5 ng/h/male, respectively, on day 2. Exposure ofI. duplicatus males to myrcene and -pinene resulted in the production of small amounts of Id, cV, tV, Mt, andtrans-pinocarveol, but not of EM. In laboratory bioassays with walking beetles, the pheromone component Id alone was weakly attractive while EM was inactive, but in binary combination with Id strongly synergized attraction. A combination of EM and Id at a release rate equivalent to 100–200 males was more attractive in the field than 70 unmated males in a spruce log. The addition of myrcene ( a suggested pheromone precursor of Id) to Id did not enhance trap caches, while addition of EM increased catches > 10-fold. Subtracting EM from a blend of Id, EM, cV and MB drastically reduced trap catches while subtraction of cV or MB or both had no significant effect. Addition of EM over a wide concentration range to the synthetic pheromone ofI. typographus did not reduce the attraction of females of this species in the laboratory. A two-species pheromone interaction field test releasingI. typographus pheromone components (MB + cV) at 10–1000 male equivalents (ME) andI. duplicatus pheromone (Id + EM) at 0, 10–1000 ME in all possible combinations showed both positive intraspecific dose-response effects and an interspecific inhibition. Higher release rates of EM appeared to inhibitI. typographus, especially males. In a tree colonization model, the response of the two competing species to their respective pheromones show a good separation during the mass-attack with a small initial cross-attraction. It remains to be shown whether either of the two pheromone systems have in fact evolved in the present sympatry, or if they are an incidental effect of ancestry of these phylogenetically distantIps.     

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.     

深圳市秋季大气臭氧立体分布特征

利用大气O₃探测激光雷达在深圳市东部生态区和西部城区同步开展垂直观测,探究了2018年深圳市O₃立体分布在秋季光化学污染活跃期至冬季非活跃期的演变过程.结果表明：光化学反应活跃的10月,东部地面O₃浓度相对于西部地面高出约128%;地面向上至450m,O₃浓度在东部生态区发生快速降低,而在西部城区由于存在“滴定效应”,O₃浓度随高度升高而升高;450m~2km,东、西部O₃浓度均随高度升高而降低,西部城区O₃浓度水平超过东部生态区约30%;2km以上高空,东、西部O₃浓度趋同（70μg/m³）,并保持稳定,为具深圳市秋季O₃污染过程提供了较高的大气背景浓度.高污染期间,深圳市大气边界层内O₃浓度变化较为一致,西部高空的O₃区域传输作用更加显著.秋季至冬季光化学反应逐渐减弱,深圳市O₃浓度的水平和垂直空间差异逐渐减小,冬季的深圳市O₃污染基本受大气背景控制.     

核壳结构KNbO3@Co(OH)2的制备及其活化过一硫酸盐降解帕珠沙星的研究

制备了以KNbO₃为载体材料的Co（OH）₂复合材料并对其进行了详细的表征,分析了材料的组成成分、组成形态进而确定了其为核壳结构形貌的KNbO₃@Co（OH）₂.利用合成的样品作为催化剂活化过一硫酸盐（peroxymonosulfate,PMS）来降解帕珠沙星（pazufloxacin,PZF）,结果表明制备的催化剂对PZF的去除效率显著增加.讨论了不同初始PMS剂量对降解效率的影响,发现随着PMS增加可活化生成更多的硫酸根自由基（sulfate radicals,SO₄^·-）和羟基自由基（hydroxyl radicals,HO^·）来降解PZF,但继续增大PMS用量降解效率未见明显提升.酸性和中性pH值条件下利于反应活化PMS降解PZF,而碱性体系减缓反应,甚至强碱体系更易形成Co（OH）₂沉淀不利于反应体系中活性组分CoOH⁺的形成,大大抑制了催化性能.此外,在体系中加入淬灭剂叔丁醇（tert-Butanol,TBA）或者乙醇（ethanol,ETOH）进行自由基的淬灭实验,结果表明SO₄^·-自由基为体系降解PZF过程中主要贡献的自由基,而HO^·自由基的贡献较少.催化剂具有较好的稳定性5次循环之后仍能在10 min之内完全去除PZF.本研究提出了新的思路为制备其他载体的Co（OH）₂核壳结构提供参考依据,同时将该催化剂结合高级氧化技术应用到水体新兴有机污染物净化领域具有很好的应用前景.     

Pt-Sn/Al2O3蜂窝催化剂催化氧化C6烃

采用等体积分浸法制备Pt-Sn/Al₂O₃蜂窝催化剂（Pt含量仅为0.06wt%）.运用X射线衍射（XRD）、透射电镜（TEM）等技术对催化剂理化性质进行表征,并选取4种代表性C₆烃（苯、环己酮、环己烷和正己烷）对催化剂性能进行评价.活性评价试验中,Pt/Sn比为3/1催化效果最佳.此时4种C₆烃转化率达到90%的温度（T₉₀）较Pt催化剂均降低约20℃,其原因在于Sn可将Pt分割为较小的团簇提高Pt分散度.寿命评价试验以环己烷为例同Pt-Sn蜂窝催化剂连续运行720h,催化活性无明显变化,其原因在于,Sn可有效抑制其粒径增长;Pt₃Sn合金降低表面对C₆烃的吸附,减少催化剂表面积炭.     

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.