Degassing of H/He, CFCs and SF6 by denitrification: Measurements and two-phase transport simulations

The production of N₂ gas by denitrification may lead to the appearance of a gas phase below the water table prohibiting the conservative transport of tracer gases required for groundwater dating. We used a two-phase flow and transport model (STOMP) to study the reliability of ³H/³He, CFCs and SF₆ as groundwater age tracers under agricultural land where denitrification causes degassing. We were able to reproduce the amount of degassing (R² = 69%), as well as the ³H (R² = 79%) and ³He (R² = 76%) concentrations observed in a ³H/³He data set using simple 2D models. We found that the TDG correction of the ³H/³He age overestimated the control ³He/³He age by 2.1 years, due to the accumulation of ³He in the gas phase. The total uncertainty of degassed ³H/³He ages of 6 years (± 2 σ) is due to the correction of degassed ³He using the TDG method, but also due to the travel time in the unsaturated zone and the diffusion of bomb peak ³He. CFCs appear to be subject to significant degradation in anoxic groundwater and SF₆ is highly susceptible to degassing. We conclude that ³H/³He is the most reliable method to date degassed groundwater and that two-phase flow models such as STOMP are useful tools to assist in the interpretation of degassed groundwater age tracer data.     

The structure of the fire fighting foam surfactant Forafac®1157 and its biological and photolytic transformation products

For several decades, perfluorooctane sulfonate (PFOS) has widely been used as a fluorinated surfactant in aqueous film forming foams used as hydrocarbon fuel fire extinguishers. Due to concerns regarding its environmental persistence and toxicological effects, PFOS has recently been replaced by novel fluorinated surfactants such as Forafac®1157, developed by the DuPont company. The major component of Forafac®1157 is a 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB), and a link between the trade name and the exact chemical structure is presented here to the scientific community for the first time. In the present work, the structure of the 6:2 FTAB was elucidated by ¹H, ¹³C and ¹⁹F nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry. Moreover, its major metabolites from blue mussel (Mytilus edulis) and turbot (Scophthalmus maximus) and its photolytic transformation products were identified. Contrary to what has earlier been observed for PFOS, the 6:2 FTAB was extensively metabolized by blue mussel and turbot exposed to Forafac®1157. The major metabolite was a deacetylated betaine species, from which mono- and di-demethylated metabolites also were formed. Another abundant metabolite was the 6:2 fluorotelomer sulfonamide. In another experiment, Forafac®1157 was subjected to UV-light induced photolysis. The experimental conditions aimed to simulate Arctic conditions and the deacetylated species was again the primary transformation product of 6:2 FTAB. A 6:2 fluorotelomer sulfonamide was also formed along with a non-identified transformation product. The environmental presence of most of the metabolites and transformation products was qualitatively demonstrated by analysis of soil samples taken in close proximity to an airport fire training facility.     

Changes in TcpA gene frequency explain 2,4,6-trichlorophenol degradation in mesocosms

Soils are often polluted by chlorophenols in timber production areas in the northern hemisphere. The tcpA gene encodes the first step of 2,4,6-trichlorophenol (246-TCP) degradation. We tested tcpA gene frequency in three natural pristine soils with different 246-TCP degradation capacity. Gene tcpA frequency increased more in spiked than non-spiked 10-L pails containing coniferous humus soil with high degradation capacity, in contrast to soils where degradation was slower. As the soil in each mesocosm originated from a spatially separate field plot, changes in tcpA gene frequency affected 246-TCP degradation over a range of soil origins. This indicates that the abundance of and changes in tcpA gene frequency could be utilized in estimating the efficacy of natural attenuation and biostimulation treatments in controlled conditions.     

Development and application of LC–APCI–MS method for biomonitoring of animal and human exposure to imidacloprid

Imidacloprid (IMI) is a relatively new neuro-active neonicotinoid insecticide and nowadays one of the largest selling insecticides worldwide. In the present study a LC–APCI–MS based method was developed and validated for the quantification of imidacloprid and its main metabolite 6-chloronicotinic acid (6-CINA) in urine and hair specimens. The method was tested in biomonitoring of intentionally exposed animals and subsequently applied for biomonitoring of Cretan urban and rural population.     

Radiation Effects on Blends of Poly(ε-Caprolactone) and Diatomites

Poly(-caprolactone) (PCL) was blended with diatomaceous earth (diatomite) and irradiated with -rays to introduce cross-linking between PCL molecules or both components. The unwashed diatomite containing a little of a volatile component showed high efficiency of introduction of cross-linking, whereas that with no volatile component showed low efficiency of introduction of cross-linking. Elongational viscosity, melt viscosity, and modulus of PCL/diatomite blend irradiated at various doses were significantly improved. Enzymatic degradation of the PCL/diatomite blend became faster than that of the PCL, though that of the blend irradiated became slower.     

Morphophysiological Rearrangements in Fish in Response to Pollution (in the Light of S.S. Shvarts' Theory)

The results of a study on morphophysiological variation in fish inhabiting a subarctic lake exposed to chronic industrial pollution are described using an example of cisco, Coregonus lavaretus. It is shown that indices of the heart, liver, kidneys, gills, and fatness in these fish are increased significantly and have retained increased values for the past 20 years. The observed changes are analyzed on the basis of biochemical data. The results of studies on the dynamics of hematological parameters in fish are used for characterizing the development of toxicosis. Adaptive rearrangements associated with an increase in the metabolic rate and the activation of protective systems in the fish are explained in the context of S.S. Schvarts' concept. The idea is proposed that the additional energy cost of detoxification may be responsible for morphophysiological variation in fish under conditions of water pollution.     

钠盐量影响下DD6单晶高温合金的高温热腐蚀规律研究

目的 开展镍基单晶高温合金DD6在950 ℃下的热盐腐蚀试验(95%Na2SO4+5%NaCl)，探明涂盐量和涂盐方式(周期涂盐和单次涂盐)对DD6高温热腐蚀的影响规律和机理。方法 结合扫描电子显微镜、X射线能量色散谱、X射线衍射等设备，对不同涂盐量及涂盐方式下DD6的表面及横截面形貌进行观察分析，分析不同涂盐量和涂盐方式下DD6的高温热腐蚀机理。结果 DD6在950 ℃下主要发生碱性熔融热腐蚀，同时伴随氧化、硫化和氯化等过程。高温热腐蚀使得DD6合金表面生成的保护性氧化膜被熔融态的腐蚀介质破坏，导致O、S、Cl等外部元素通过氧化膜的缺陷进入DD6基体中，在合金的亚表面发生内氧化、内硫化以及内氯化反应，横截面上出现明显的腐蚀层，其主要由氧化物以及硫化物组成。随着热腐蚀的进行，DD6表面物质发生了剥蚀，沉积盐量的增加导致剥蚀现象越加严重，合金内部致密的组织结构也被破坏，横截面上出现了大量孔洞、裂纹等缺陷。在相同涂盐量下，周期涂盐法使得DD6的腐蚀程度高于单次涂盐法。结论 DD6高温热腐蚀行为与涂盐量及涂盐方式密切相关，相同涂盐方式下，涂盐量越大，DD6热腐蚀更加严重。涂盐量一定时，周期涂盐法使得DD6的热腐蚀剧烈程度大于单次涂盐法，且DD6在上述热腐蚀条件下均发生剥蚀破坏。     

云南不同量级降雨下的降雨侵蚀力特征分析

为研究云南省及5个子区域年降雨侵蚀力和各量级降雨侵蚀力的时空变化特征,基于云南120个站点近43a逐日降水资料,利用Man-Kendall趋势检验、Morlet连续复小波变换分析等方法进行系统分析。结果表明:各区域大雨侵蚀力在年降雨侵蚀力中起主导作用;年内各月降雨侵蚀力滇西北基本以大雨侵蚀力为主,其余区域干季以中雨侵蚀力为主,雨季以大雨侵蚀力为主;各量级降雨侵蚀力表现出降雨量级越大,季节性越强,集中程度越高的特征;各区域中雨侵蚀力相对变化呈减少趋势,其余量级降雨侵蚀力变化趋势以减居多;暴雨侵蚀力相对变化程度最强,大雨和中雨侵蚀力相对较缓;滇西北年降雨侵蚀力、大雨和中雨侵蚀力以9a左右时间尺度为主震荡周期,其余区域主震荡周期多为18~21a左右,暴雨侵蚀力主震荡周期在各区域存在一定差异。     

Bi2MoO6/纳米棒ZnO异质结对MB的可见光-压电协同降解性能研究

采用水热法合成了一系列不同负载率的Bi₂MoO₆/纳米棒ZnO复合光催化剂.通过XRD、FT-IR、SEM、TEM、XPS、UV-Vis、EPR和PL等分析技术对合成的样品进行表征.在光/超声波条件下,以亚甲基蓝（MB）为目标降解物评价其压电-光催化性能.结果表明：Bi₂MoO₆/ZnO纳米棒（BZ-0.6）的降解速率常数约为ZnO传统光催化的9.25倍,其性能提升的主要原因在于ZnO的压电效应与Bi₂MoO₆/ZnO界面形成的异质结的耦合,有效地促进了电子和空穴的分离和转移.此外,同实验条件下,循环利用5次后Bi₂MoO₆/ZnO复合光催化剂降解率仍保持良好的稳定性.