Revisiting natural and laboratory electron spin resonance (ESR) dose response curves of quartz from Chinese loess

Natural and laboratory ESR dose response curves (DRCs) of [AlO₄/h]⁰ and [TiO₄/M⁺]⁰ were investigated for samples of quartz from the Luochuan loess-palaeosol master section, Chinese Loess Plateau. The natural and laboratory DRCs show a clear divergence above ∼1000 Gy, with much lower D₀ values and saturation levels observed for the natural DRCs, which is in agreement with the previous study by Tsukamoto et al. (2018). Young (<15 ka) samples from Luochuan and Jingbian – another site of the Chinese Loess Plateau, together with two modern samples of Chinese loess, were used to investigate the residual signals of [AlO₄/h]⁰ and [TiO₄/M⁺]⁰ centres. Our results are in line with published studies and show that the significant residual signals corresponding to several tens to hundreds of Gy are present in both Al and Ti centres. These need to be taken into account before laboratory DRC construction. ESR pulse annealing experiments performed on samples irradiated with different doses show an apparent dose-dependent thermal instability of [AlO₄/h]⁰ and [TiO₄/M⁺]⁰, with the signals for higher doses decaying faster with increasing temperature. We attribute the change in D₀ with preheat reported in Tsukamoto et al.2018, as well as the difference between laboratory and natural DRCs, to this apparent dose-dependent thermal instability of the signals. The saturation level of the natural DRC, being the result of reaching the equilibrium between filling of the traps and emptying them due to thermal decay, is therefore additionally affected at higher doses, due to the increased thermal instability. The inability to recreate in the laboratory the same response to irradiation as the one observed in nature questions the accuracy of dating samples beyond ∼1000 Gy.     

Investigation on age and genesis of silcretes in Queensland (Australia)–Preliminary results

Silcretes from Queensland (Australia) were dated by means of the electron spin resonance dating technique. The results range from 1.5 to 10.8 million years; therefore, these silcretes were formed between the upper Miocene and the early Pleistocene. For a conclusive interpretation of the data geochemical and thin section analyses were also carried out. ESR dating of silcretes for the first time offers a direct approach to a chronostratigraphic framework of the genesis of these duricrusts, and of the palaeoclimatic events attributed to them.     

Dating of Japanese Quaternary tephras by ESR and luminescence methods

Electron spin resonance (ESR) and red thermoluminescence (RTL) methods were applied to quartz of eight Japanese Quaternary tephras ranging from 30 to 900 kyr, which have independent ages from other dating methods. The ESR ages were consistent for younger samples, while those from the Ti–Li center are older than those for the Al center for older samples. RTL ages are consistent with the age references and are roughly consistent with Al center ages. The dose response of the Ti–Li center after heating at 260 °C for 15 min implies that thermally unstable component is created in Ti–Li center by irradiation, leading to possible overestimations in the dose values.     

ESR dating of optically bleached quartz grains from Plio-Pleistocene to Holocene coastal dune deposits (Wilderness-Knysna area,South Africa): a comparison with luminescence

Five Plio-Pleistocene to Holocene aeolian quartz samples from the coastal dune deposits of the Wilderness-Knysna area (South Africa) previously dated by OSL were selected for ESR dating. Samples were processed following the Multiple Centre approach and using the Multiple Aliquot Additive dose method. Aluminium (Al) and Titanium (Ti) signals were systematically measured in all samples.Our study shows that ESR results obtained for Middle Pleistocene to Holocene samples may be strongly impacted by (i) the presence of a significant high frequency noise in the ESR spectra acquired for the Ti signals and (ii) the choice of the fitting function employed. In particular, if not taken into account, very noisy spectra can lead to a significant overestimation of the true ESR intensity measured for the Ti–H signal. These sources of uncertainty are however not sufficient to remove the ESR age overestimations. Consequently, our results indicate that the Al and Ti ESR signals of these quartz samples have not been fully reset during their aeolian transport.While this work contributes to improve our understanding of the ESR method applied to quartz grains, and especially of the potential and limitations of the Ti signals, it also provides additional baseline data to illustrate the existing variability among quartz samples of different origins or sedimentary context. Our results are consistent with previous studies by confirming that the Ti–H signal shows the best potential for the evaluation of low dose values (<100 Gy for these samples), whereas it becomes inappropriate for the higher dose range, and the Ti–Li–H (option D sensu Duval and Guilarte, 2015) should be used instead.Beyond the methodological outcome, this ESR dating study also provides a useful addition to the existing chronology of the aeolian deposits in this region. In particular, new (and possibly) finite numerical age results were obtained for the two oldest samples, constraining the aeolianite landward barrier dune and the coversand formations to the MIS 10-8 and Pliocene, respectively.     

Direct scanning tunneling microscope (STM) observation of Cr(III) complexes on hematite (001) surfaces

Scanning tunneling microscopy (STM) is used to observe, at the atomic scale, Cr(III) adsorbed to hematite (001) surfaces from aqueous solution. The Cr(III) adsorbates are relatively immobile, but estimated activation energies for surface self-diffusion are lower than those for water or hydroxyl substitution in aqueous Cr(III). Possible causes are effects of STM imaging (artifacts), high ligand-substitution rates for adsorbed species, or participation of substrate Fe (III) ligand exchange. STM imaging of suitable aqueous surface complexes is shown to be feasible, and constitutes a new way to study the relationships between microscopic and macroscopic chemical behavior of adsorbed species in aqueous systems.     

Investigating the effect of diagenesis on ESR dating of Middle Stone Age tooth samples from the open-air site of Lovedale,Free State,South Africa

Teeth are usually targeted for dating archaeological sites because they are less prone to dissolution, in comparison with bones. However, despite this apparent resistance, teeth do undergo diagenesis, which needs to be accounted for in order to obtain accurate ages. In particular, the uptake of trace elements such as uranium in dental tissues needs to be considered for dose rate determination when dated using electron spin resonance (ESR). Characterising the mineralogy and structural integrity of samples prior to dating may thus provide important information related to their state of preservation, especially in the case of teeth whose U content can significantly affect the dose rate.In this study, we dated five teeth of small-sized bovids using combined ESR/U-series dating. They were collected at the Middle Stone Age site of Lovedale, located in the central interior of South Africa. Micromorphology provided sedimentary context to the samples, which were recovered from a layer of gravel rich in faunal remains. Using cathodoluminescence, laser-induced fluorescence, Fourier transform infrared spectroscopy and Raman micro-spectroscopy we assessed the degree of preservation of the enamel. Results reveal that carbonate hydroxyapatite underwent post-depositional alteration, based on its molecular structure and elemental composition. Although the teeth all originate from the same layer and were sampled in the same 1-m square and at a similar elevation, U-content in the enamel differs highly from one tooth to the other, with values ranging from 1.7 to 29.6 ppm. These values are correlated with equivalent doses (D_e) from 228 to 923 Gy and are consistent with variations in crystallinity determined with vibrational spectroscopy. We also investigated the possible saturation of the ESR signal, by repeating measurements with microwave power values from 1 to 20 mW.Despite such diversity in U-content, the ages calculated assuming an early uptake of U all fall within the same range, from 63 ± 8 ka to 68 ± 15 ka and may only represent a minimum estimate.     

On the interest of using the multiple center approach in ESR dating of optically bleached quartz grains: Some examples from the Early Pleistocene terraces of the Alcanadre River (Ebro basin,Spain)

The present work reports the first numerical ages obtained for the two highest fluvial terraces (Qt1 and Qt2) of the Alcanadre River system (Northeastern Spain) representing the earliest remnants of Quaternary morphosedimentary fluvial activity in the Ebro basin. ESR dating method was applied to optically bleached quartz grains and both the Al and Ti centers were measured, in accordance with the Multiple Center approach. The results are overall in good agreement with the existing preliminary chronostratigraphic framework and our interpretation indicate that terraces Qt1 and Qt2 have an ESR age of 1276 ± 104 ka and 817 ± 68 ka, respectively. These data provide some chronological insights on the beginning of the fluvial sedimentary processes in a scenario of incision maintained over Quaternary in the Ebro Basin. These are among the first numerical ages obtained for such high terraces in the Iberian Peninsula.Our results demonstrate the interest of using the Multiple Center approach in ESR dating of quartz, since the two centers provide complementary information, i.e. an independent dose control. The overall apparent consistency between the ESR age estimates and the existing preliminary chronostratigraphic framework may be considered as an empirical evidence that the Ti–Li center may actually work for Early Pleistocene deposits, whereas the Ti–H center shows some clear limitations instead. Finally, these results demonstrate the interest of using ESR method to date Early Pleistocene fluvial terraces that are usually beyond the time range covered by the OSL dating method.     

铁（氢）氧化物介导的溶解性有机质、无机磷的固定及相互作用研究进展

铁(氢)氧化物介导的溶解性有机质(DOM)和无机磷(DIP)的固定在水生态系统中普遍存在,对碳、磷元素的生物地球化学循环有重要的影响.铁(氢)氧化物主要通过吸附和共沉淀两种过程固定DOM和DIP,且铁(氢)氧化物、DOM和DIP三者存在复杂的相互作用.本文主要从铁(氢)氧化物对DOM和DIP的固定,铁(氢)氧化物、DOM和DIP之间的相互影响等方面综述了相关研究进展,梳理了铁(氢)氧化物、DOM和DIP在吸附和共沉淀过程中的相互作用机制与影响因素.DOM的存在会通过占据铁(氢)氧化物表面吸附点位、络合、抑制铁水解沉淀等途径影响铁(氢)氧化物对DIP的固定;且不同机制与DOM的不同性质如分子大小、芳香组分、羧基官能团含量等有关.而DIP的存在会改变铁(氢)氧化物对DOM的固定分馏过程,改变溶液中DOM的组分和性质.在明晰三者相互作用基础上,探讨了铁(氢)氧化物介导的DOM和DIP的固定过程对湖泊内源磷释放和碳埋藏的可能影响,并对未来的研究方向进行了展望.     

Stability of arsenopyrite and As(III) in low-temperature acidic solutions

Arsenopyrite is one of the most important pri-mary arsenic mineral. In the Eh-pH diagram of the As-O2-S-H2O system, if the total arsenic concentration (TAs) is taken to be 0.75 mg/L, the total sulfur con-centration, 32 mg/L, the temperature, 25℃and the pressure, one atmosphere pressure for the discrimina-tion of arsenic species, it may be found that under hy-pergene conditions, arsenopyrite is a moderately stable mineral. Only in the strongly alkaline and reducing environment can arsenopy…     

Assessing the impact of land use change on hydrology by ensemble modeling (LUCHEM) III: Scenario analysis

An ensemble of 10 hydrological models was applied to the same set of land use change scenarios. There was general agreement about the direction of changes in the mean annual discharge and 90% discharge percentile predicted by the ensemble members, although a considerable range in the magnitude of predictions for the scenarios and catchments under consideration was obvious. Differences in the magnitude of the increase were attributed to the different mean annual actual evapotranspiration rates for each land use type. The ensemble of model runs was further analyzed with deterministic and probabilistic ensemble methods. The deterministic ensemble method based on a trimmed mean resulted in a single somewhat more reliable scenario prediction. The probabilistic reliability ensemble averaging (REA) method allowed a quantification of the model structure uncertainty in the scenario predictions. It was concluded that the use of a model ensemble has greatly increased our confidence in the reliability of the model predictions.     

风垂直切变对大气静力适应过程的影响——第三部分:能量转换

基于前两部分的研究,第三部分从能量转换的角度揭示了风垂直切变对大气静力适应过程的影响.研究显示,对非静态等温大气,初始时刻加以有效势能和有效弹性势能的强迫后,风垂直切变改变了适应过程中扰动能量在各能量形式中的分配比例,这种作用随扰动尺度和时间的变化有显著差异,系统尺度越小影响越显著.比较东风急流模型和西风急流模型显示,负的风切变应力使得四类扰动能量谱随系统尺度的变化趋于平缓,使得微尺度和小尺度(中尺度)系统中扰动垂直动能(扰动水平动能)的比例随时间减小,正的风切变使得扰动能量谱随系统尺度的变化显现跳跃的特征,使得中尺度(微尺度和小尺度)系统中扰动垂直动能(扰动水平动能)的比例随时间减小.风垂直切变引起的动量通量输送是扰动能量与基本气流能量之间交换的通道,当风切变应力和动量输送方向相同时,风垂直切变使得能量向基本态转移,维持基本气流,削弱扰动能量,缩短静力适应过程的周期;当风切变应力和动量输送方向相反时,风垂直切变作用相反;此作用随着扰动尺度的变化差异明显.     

Response Surface Approach for the Bisorption of Ag(I) by Macrofungus Pleurotus platypus

Response surface methodology (RSM) employing the three‐level Box–Behnken factorial design was used to optimize the biosorption of Ag(I) by the macrofungus Pleurotus platypus. The initial Ag(I) concentration (100–300 mg/L), pH (3.0–9.0), and biomass dosage (1.0–5.0 g/L) were chosen as the process variables for the optimization. A coefficient of determination (R²) value (0.99), model F value (234.18), and its low p‐value (F < 0.0001) along with the lower value of coefficient of variation (2.44%) indicated the fitness of response surface quadratic model during the present study. At the optimum pH (6.0), initial metal concentration (220 mg/L), and biomass dosage (3.0 g/L), the model predicted 46.7 mg/g Ag(I) uptake and an experimental 46.77 mg/g Ag(I) uptake by P. platypus was obtained. This is the first report on Ag(I) sorption by P. platypus using statistical experimental design employing RSM which may be helpful towards the treatment of industrial effluent containing silver.     

巢湖表层沉积物中多环芳烃分布特征及来源

于2010年,采用野外采样调查、色谱分析与统计比较的方法,研究巢湖表层沉积物中27个采样点中多环芳烃(PAHs)分布特征及污染来源.结果表明:巢湖表层沉积物中检测出的14种优控PAHs总浓度为116.0~2832.2 ng/g(DW),平均值为898.9±791.0 ng/g(DW).多环芳烃组成主要以5~6环PAHs为主,占总量的32%~58%.沉积物中总有机碳含量与PAHs总量呈现良好相关性.利用蒽/(蒽+菲)与苯并[a]蒽/(苯并[a]蒽+屈)比值法对PAHs来源进行解析得出,巢湖表层沉积物中PAHs主要来源为燃烧源.与国内其它水体PAHs含量对比表明,巢湖沉积物中PAHs污染处于中等水平.生态风险评估得出南淝河表层沉积物中PAHs存在生态风险,其它采样点表层沉积物中PAHs生态风险均较低.     

Removal of Selenium by Adsorption onto Granular Activated Carbon (GAC) and Powdered Activated Carbon (PAC)

The present work involves the study of Se(IV) adsorption onto granular activated carbon (GAC) and powdered activated carbon (PAC). The adsorbents are coated with ferric chloride solution for the effective removal of selenium. The physico-chemical characterization of the adsorbents is carried out using standard methods, e. g., proximate analysis, scanning electron microscopy (SEM), fourier transform infrared spectroscopy (FTIR), thermo-gravimetric (TGA) and differential thermal analysis (DTA), etc. The FTIR spectra of the GAC and PAC indicate the presence of various types of functional groups, e. g., free and hydrogen bonded OH groups, silanol groups (Si-OH), alkenes, and CO group stretching from aldehydes and ketones on the surface of adsorbents. Batch experiments are carried out to determine the effect of various factors such as adsorbent dose (w), initial pH, contact time (t), and temperature (T) on the adsorption process. The optimum GAC and PAC dosage is found to be 10 g/L and 8 g/L, respectively, for Se(IV) removal with C₀ = 100 mg/L. The percent removal of Se(IV) increases with increasing adsorbent concentration, while removal per unit weight of adsorbent increases with decreasing adsorbent concentration. Se(IV) adsorption onto both the GAC and PAC adsorbents is high at low pH values, and decreases with increased initial pH. The results obtained are analyzed by various kinetic models. The parameters of pseudo-first order, pseudo-second order kinetics, and Weber-Morris intra particle kinetics are determined. It is seen that the sorption kinetics of Se(IV) onto GAC and PAC can be best represented by the pseudo-second order kinetic model.     

Optimization and Characterization of Tl(I) Adsorption onto Modified Ulmus carpinifolia Tree Leaves

Ulmus carpinifolia tree leaves were successfully used to remove Tl(I) from aqueous solution in a batch system. In order to improve the uptake capacity of sorbent, it was modified by various chemical agents such as NaOH, HNO₃, NH₃, NaCl, NaHCO₃, and CaCl₂. Among the modifiers, NaCl was the best. Equilibrium behavior of sorbent with Tl(I) was examined by the several isotherms. Considering modified U. carpinifolia equilibrium data fitted well to the Langmuir model with maximum capacity of 54.6 mg/g. The other isotherms such as: Freundlich and Dubinin‐Redushkevich (D‐R) models were also examined. The central composite design (CCD) was successfully employed for optimization of biosorption process. An empirical model was given through using response surface methodology. Also its validation was recognized by using relevant statistical tests such as ANOVA. The optimum conditions of biosorption: pH, m (amount of sorbent) and C (initial concentration) were found to be 7.9, 11.4 g/L, and 8.8 mg/L, respectively. On the other hand thermodynamic parameters: ΔG, ΔH, and ΔS were evaluated: the obtained results show that biosorption process was spontaneous and exothermic. Eventually, FT‐IR analysis confirmed that the main functional groups of sorbent have been involved through the biosorption process.     

陇东黄土高原下垫面不均匀性指标的建立及其对大孔径闪烁仪(LAS)观测感热通量的影响

目前定量研究下垫面不均匀性对大孔径闪烁仪(LAS)、涡动相关仪(ECS)观测感热通量差异的影响还比较少.本文利用黄土高原庆阳观测站2012年6、7月典型晴天两主风向范围E-SE和SW-W的陆面过程数据,在建立了下垫面不均匀性定量化指标的基础上,分析了下垫面不均匀性与地表温度变率的关系及其对LAS、ECS观测感热通量差异的影响.结果表明:庆阳站下垫面不均匀性大小η和地表温度变率г具有很好的相关性,相关系数达到0.566以上,证明了新建立指标的合理性.下垫面不均匀性大小η和LAS、ECS观测的感热通量差异HLAS-HECS具有很好的一致性,相关系数达到0.634.下垫面不均匀性对LAS和ECS的感热通量差异影响显著,下垫面越不均匀LAS和ECS测量的感热通量差异越大.对两主风向分别进行分析,在E-SE风向范围η和HLAS-HECS的相关系数为0.430,HLAS和HEC拟合的线性趋势系数为1.279,在SW-W风向范围η和HLAS-HECS的相关系数为0.680,HLAS和HEC拟合的线性趋势系数为1.297.下垫面不均匀性的影响程度越大,LAS和ECS观测的感热通量差异越大.     

宝昌地震台面波震级MS与宽频带面波震级MS (BB)对比分析

选取2016—2017年宝昌地震台记录的全球220次M_S≥6.0地震,对所选地震的面波震级重新量取,为更好实现单台新旧震级的“无缝”对接,进行了面波震级M_S与宽频带面波震级M_S（BB）的对比研究。结果表明,大多数地震的宽频带面波震级M_S（BB）比面波震级M_S总体偏大,且M_S（BB）与M_S的线性相关程度较高。     

Removal of Ni(II) from Aqueous Solutions by Nanoscale Magnetite

Magnetite nanoparticles were applied to remove Ni(II) from aqueous solutions as a function of pH, contact time, supporting electrolyte concentration, and analytical initial Ni(II) concentration. The highly crystalline nature of the magnetite structure with diameter of around 10 nm was characterized with transmission electron microscopy (TEM) and X‐ray diffractometry (XRD). The surface area was determined to be 115.3 m²/g. Surface chemical properties of magnetite at 25°C in aqueous suspensions were investigated. The point of zero charge (pHzpc) was found to be 7.33 and the intrinsic acidity constants (${\rm p}K_{{\rm a}1}^{{\rm s}} $ and ${\rm p}K_{{\rm a}2}^{{\rm s}} $ ) were found to be 9.3 and 5.9, respectively. The surface functional groups were investigated with Fourier transform‐infrared spectroscopy (FTIR) as well. Batch experiments were carried out to determine the adsorption kinetics and mechanism of Ni(II) by these magnetite nanoparticles. The adsorption process was found to be pH dependent. In NaCl solutions, Ni(II) adsorption increased with increasing ionic strength while in NaClO₄ solutions, Ni(II) adsorption exhibited little dependence on the ionic strength of the solution. The adsorption process better followed the pseudo‐second order equation and Freundlich isotherm.     

Analysis of community structure of a microbial consortium capable of degrading benzo(a)pyrene by DGGE

A microbial consortium was obtained by enrichment culture of sea water samples collected from Botan oil port in Xiamen, China, using the persistent high concentration of a mixture of polycyclic aromatic hydrocarbons enrichment strategy. Denaturing gradient gel electrophoresis (DGGE) was used to investigate the bacterial composition and community dynamic changes based on PCR amplification of 16S rRNA genes during batch culture enrichment. Using the spray-plate method, three bacteria, designated as BL01, BL02 and BL03, which corresponded to the dominant bands in the DGGE profiles, were isolated from the consortium. Sequence analysis showed that BL01, BL02 and BL03 were phylogenetically close to Ochrobactrum sp., Stenotrophomonas maltophilia and Pseudomonas fluorescens, respectively. The degradation of benzo(a)pyrene (BaP), a model high-molecular-weight polycyclic aromatic hydrocarbon (HMW PAH) compound was investigated using individual isolates, a mixture of the three isolates, and the microbial consortium (BL) originally isolated from the oil port sea water. Results showed that the order of degradative ability was BL > the mixture of the three isolates > individual isolates. BL degraded 44.07% of the 10 ppm BaP after 14 days incubation, which showed the highest capability for HMW PAH compound degradation.Our results revealed that this high selective pressure strategy was feasible and effective in enriching the HMW PAH-degraders from the original sea water samples.     

Surface lowering of limestone pavement as determined by cosmogenic (36Cl) analysis

Determination of the rate and total amount of limestone pavement surface lowering is a critical issue in developing models of regional landscape change in limestone terrain. Erratic‐capped pedestals have frequently been used for this purpose but problems concerning definition and measurement of pedestal height, and the absence of a secure timeframe for erratic emplacement, have resulted in conflicting interpretations. We have used cosmogenic (³⁶Cl) to establish the emplacement age of erratic boulders and the total amount of pavement surface lowering at sites in northwest England. Since erratic emplacement at 17.9 ka the limestone pavement has been lowered by 22–45 cm (average: 33 ± 10 cm), assuming lowering was continuous. Although indicating some spatial heterogeneity, the results contrast with earlier reported values based on the measurement of pedestal heights and inferred age for deglaciation. We consider that changes in climate and the character and duration of regolith covers to have been important influences in promoting surface lowering. It is argued that nivation (chemical and mechanical snow‐related processes) associated with several cool/cold periods is likely to have played an important role in surface lowering. Complicating factors associated with surface lowering (thickness and longevity of snow and regolith covers) are identified but as yet cannot be quantified. Copyright © 2012 John Wiley & Sons, Ltd.