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.     

Diffusion pollution from livestock and poultry rearing in the Yangtze Delta,China

BACKGROUND: The Yangtze Delta is one of the most developed regions in China and includes Shanghai, eight cities in Jiangsu province and eight cities in Zhejiang province. Meat consumption in this region has increased with economic growth, and most of the consumed meat is produced locally. The water quality of surface waters has deteriorated in recent years. An example was the huge blue-green algae bloom in Tai Lake in late May 2007, which affected millions of people's daily drinking water. However, animal husbandry is considered to be one of the main pollution sources. METHODS: Pollutants (NH3-N, total phosphorus (TP), and total nitrogen (TN)) excreted by livestock and poultry, and the resultant COD (chemical oxygen demand) and BOD (biochemical oxygen demand), were estimated using two different methods based on different data sets. RESULTS: The number of livestock and poultry has remained stable in the Yangtze Delta over the four years from 1999 to 2002, with the average number of pigs, cattle, sheep and poultry being 21.1 M, 0.4 M, 7.7 M and 597.6 M, respectively. Pollutants in livestock and poultry excreta estimated by Method I were: 0.12 Mt NH3-N, 0.11 Mt TP and 0.29 Mt TN, resulting in COD and BOD of 1.34 Mt and 1.30 Mt, respectively, while the estimations based on Method II were: 0.18 Mt NH3-N, 0.15 Mt TP and 0.40 Mt TN, resulting in COD and BOD of 1.95 Mt and 1.80 Mt, respectively. DISCUSSION: Pollutants excreted annually by livestock and poultry in the Yangtze Delta are estimated to be: 0.17 Mt NH3-N, 0.16 Mt TP and 0.42 Mt TN, giving rise to a COD of 1.86 Mt and a BOD of 1.72 Mt. Approximately 25% of this pollution was estimated to enter water bodies, which means that the annual pollutant load is 43,700 t NH3-N, 39,400 tTP, 104,600t TN with a COD of 465,000 tand a BOD of 430,100 t. Pollutants from animal husbandry were similar in magnitude to those from industrial wastewater. Pigs produced the most pollution, followed by poultry, cattle and sheep. The pollution load from animal husbandry in the Yangtze Delta is about twice the average level of the whole of China. CONCLUSIONS: Domestic wastewater was the main pollution source in the Yangtze Delta, followed by pollution from raising livestock and poultry and from industrial wastewater. The pollution load in Shanghai and Jiaxing were the greatest, followed by 7 cities of Jiangsu province (except Suzhou) and other cities of Zhejiang province and Suzhou. Pigs and poultry produced about 90% of the total pollutants from animal husbandry. RECOMMENDATIONS AND PERSPECTIVES: The local governments, especially in Shanghai and Jiaxing, should focus their attention on the pollution produced by livestock and poulrry. Controlling pollution from pigs and poultry will have the greatest impact in this region. Control of pollution will be facilitated by the development of large-scale livestock and poultry farming units and a shift away from small scale husbandry.     

黄孢原毛平革菌处理染料废水过程中细胞结构损伤效应研究

利用透射电子显微镜观察分析白腐真菌(黄孢原毛平革菌)在处理染料废水活性艳红X-3B过程中,染料和盐度对黄孢原毛平革菌的细胞结构产生的毒性作用.结果表明:活性艳红X-3B染料对黄孢原毛平革菌产生生物毒性作用,且随着染料浓度的增加,细胞受损伤程度不断加深.加入100 mg/L的染料活性艳红X-3B后,黄孢原毛平革菌菌丝细胞形态发生变化,出现质壁分离现象;染料浓度进一步加大,菌丝细胞超微结构受到损伤逐渐严重.染料废水中的盐度对黄孢原毛平革菌细胞也会造成损伤,且损伤程度随盐度增大而增大.NaCl浓度为3 g/L时,菌丝细胞发生质壁分离;而当NaCl加入量高于8 g/L时,细胞膜受损,线粒体、细胞核呈现空泡化,表现为受到不可逆的损伤.染料和盐双因子对黄孢原毛平革菌细胞的损伤效应表现为其损伤程度与单因子作用一致,且染料的影响作用占主导.     

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.     

京津冀大气污染的时空分布与人口暴露

经济的快速发展和城市化导致京津冀地区的空气质量不断恶化,已经引起学术界广泛的关注.为了揭示近年来京津冀地区大气污染状况,本研究基于中国空气质量在线监测分析平台发布的PM_(2.5)、PM_(10)、SO_2、CO、NO_2和O_3_8 h_max长期监测数据,采用统计学的方法分析了2014—2018年京津冀13个市这6种污染物的时空变化特征,结合各城市人口数据,评估了在此背景下该地区PM_(2.5)和O_3_8 h_max的人口暴露风险.结果表明:京津冀地区PM_(2.5)、PM_(10)、SO_2、CO和NO_2近年来整体上呈下降趋势,而O_3_8 h_max则呈上升趋势.总体而言,PM_(2.5)、PM_(10)、SO_2、CO和NO_2表现为冬季最高、春秋季次之、夏季最低的特征,而O_3_8 h_max则表现为夏季春季秋季冬季的特点,并在月变化上呈倒"V"型,从1月份开始逐渐上升,在6月份达到峰值,而后又逐渐下降.空间上,PM_(2.5)、PM_(10)、SO_2、CO和NO_2呈现南高北低的分布特征,而O_3_8 h_max在2014—2016年呈现北高南低的分布特征,但在2017—2018年则呈现南高北低的分布特点.此外,京津冀北部地区PM_(2.5)的来源主要是一次气溶胶,而二次气溶胶是中部地区PM_(2.5)的主要来源.除秦皇岛、承德和张家口外,其他城市细粒子在颗粒物中占的比重较大.随着近年来PM_(2.5)浓度的降低,暴露于高浓度的PM_(2.5)中的人口比例逐年减少,但距离年平均浓度限值还相差很远.除2014年外,暴露在O_3浓度超标情况下的人口在2015—2017年逐渐上升.     

MnO2/Al2O3催化剂-微气泡臭氧体系催化降解喹啉及其机理

制备了纳米MnO₂,并以Al₂O₃为载体制备了掺杂型MnO₂/Al₂O₃颗粒催化剂.催化剂焙烧温度和时间分别为500℃和4 h、MnO₂质量分数为8%时,催化剂具有最高的臭氧催化氧化活性.SEM分析表明,纳米MnO₂均匀分布于Al₂O₃载体表面.MnO₂/Al₂O₃催化剂的比表面积（BET）为183.22 m²·g^-1,平均孔容为0.27 cm³·g^-1,平均孔径为4.87 nm.建立了MnO₂/Al₂O₃催化剂-微气泡臭氧催化反应体系,研究了该体系对喹啉的降解去除效果及其机理.臭氧微气泡的平均粒径为61.7 μm.微气泡臭氧投量为30 mg·L^-1时,反应60 min后喹啉去除率能达到95%以上;反应20 min后,MnO₂/Al₂O₃催化剂-微气泡臭氧体系对实际煤化工废水二级出水的TOC去除率可达到55%以上.以叔丁醇作为分子探针,证明了羟基自由基（·OH）氧化作用在臭氧微气泡催化氧化体系中对喹啉的降解起到主导作用.     

富营养化巢湖沉积物溶解性有机质光谱时空分布特征及其环境意义

通过紫外吸收光谱（UV-vis）和三维荧光光谱（3D-EEMs）,研究典型富营养化湖泊巢湖沉积物溶解性有机质（DOM）光谱时空分布特征.结果表明,巢湖表层沉积物DOM的a（254）含量为13.1~101.7 m^-1,平均值为（32.2±16.2）m^-1.其中,夏季沉积物a（254）的含量（（46.6±25.6）m^-1）要显著高于其它季节,且湖心区a（254）平均值和变异性均小于湖滨区.表层沉积物DOM的S_275~295值从春季到冬季上随时间呈明显上升趋势.沉积物DOM荧光强度在夏季最高,在垂直剖面上总体呈下降趋势.DOM组分以酪氨酸类蛋白质和溶解性微生物产物为主,各组分在空间分布上无明显差异.巢湖沉积物DOM荧光指数（FI）为2.56~4.89,腐殖化指数（HIX）为0.57~6.78,生物源指数（BIX）为0.31~1.54.巢湖沉积物DOM主要来自于生物源,藻的生长循环会显著影响富营养化湖泊沉积物DOM的来源和性质.     

O3-BAC深度处理工艺中细菌群落时空分布及动态变化规律

为弄清饮用水O₃-BAC深度处理工艺过程中细菌群落的时空分布和动态变化规律,本研究以我国南方某O₃-BAC深度处理工艺水厂为研究对象,采用NovaSeq6000高通量测序技术对夏季和冬季各工艺单元出水及滤砂和活性炭生物膜等细菌群落进行解析.结果表明,出厂水pH、浊度、COD_Mn、菌落总数等指标均满足《生活饮用水卫生标准》（GB5749-2006）的要求.夏季细菌群落多样性明显高于冬季,活性炭生物膜的细菌群落多样性高于滤砂生物膜;混凝沉淀、臭氧化和消毒是影响细菌群落多样性的主要工艺单元.水样和生物膜样品绝对优势菌门均为变形菌门（Proteobacteria）,且主要菌门组成大体相同,但细菌群落门水平相对丰度存在一定的时空差异,属水平上差异则更为明显.此外,检测到的条件致病菌属主要包括芽孢杆菌属（Bacillus）、不动杆菌属（Acinetobacter）、假单胞菌属（Pseudomonas）和分支杆菌属（Mycobacterium）,且其所占核心微生物OTUs数目不受季节性影响.水温和生物可降解溶解性有机碳（BDOC）是显著影响细菌群落分布的主要水质参数.以上研究结果表明,O₃-BAC深度处理工艺过程中细菌群落具有时空变化特性,并可为饮用水微生物安全保障提供支撑.     

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.