Kinetics of redox cycling of iron coupled with fulvic acid

The kinetics of conversion of iron(III) (hydr)oxides to ferrous iron mediated by fulvic acid have been investigated in order to improve the understanding of the redox cycling of iron at the oxic-anoxic boundary in natural waters. Under the conditions similar to natural waters, fulvic acid is able to reduce the iron(III) (hydr)oxide. The kinetics of the reaction depend on the reactivity of iron(III) (hydr)oxides and the reducing power of the fulvic acid. The rate of reaction is 60 nm/h obtained under following conditions: total concentration of Fe(III) 1.0 × 10^–4 M, pH 7.5, fulvic acid 5 mg/L. The rate is considered as a net result of reduction and oxidation in the > Fe^III-OH/Fe(II) wheel coupled with fulvic acid. In a real natural water system, reductants other than fulvic acid may be of importance. The results obtained in the laboratory, however, provide evidence that the Fe(OH)₃(s)/Fe(II) redox couple is able to act as an electron-transfer mediator for the oxidation of natural organic substances, such as fulvic acid by molecular oxygen either in the absence of microorganisms or as a supplement to microbial activity.     

Biogeochemistry of iron in an acidic lake

In this paper, the fate of iron in Lake Cristallina, an acidic lake in the Alps of Switzerland, is discussed. A simple conceptual model is developed in order to explain the observed diel variation in dissolved iron(II) concentration. Biotite weathering provides reduced iron that is oxidized and subsequently precipitated in the lake. The amorphous Fe(III)hydroxide (FeOOH xH₂O), found in the sediments of Lake Cristallina, is an Fe(II) oxidation product. This oxygenation reaction is most probably catalyzed by bacteria surfaces, as indicated by the relatively high estimated oxidation rate compared to the oxidation rate of the homogeneous oxidation of inorganic Fe(II) species at the ambient pH of Lake Cristallina (pH 5.4 at 4 °C) and by the scanning electron micrograph pictures. Under the influence of light, these amorphous iron(III)hydroxide phases are reductively dissolved. The net concentration of Fe(II) reflects the balance of the reductive dissolution and the oxidation/precipitation reactions and tends to parallel the light intensity, leading to a diurnal variation in the Fe(II) concentration. The rate of the photochemical reductive dissolution of Lake Cristallina iron(III)hydroxides is greatly enhanced in situ and in the laboratory by addition of oxalate to the lake water.     

Study of inorganic ligand-chromium(III)-surface ternary complexes by ESR spectroscopy

Cr(III) sorbed at the solid/water interface of latex and hectorite was studied by ESR spectroscopy in the presence of different inorganic ligands. The ESR spectra of the surface obtained in the presence of selenite, phosphate and fluoride can be explained in terms of ternary surface complex formation. This is contrasted by the behaviour of sulfate and selenate ions which were found to have no effect on the ligand field of Cr(III), either in the adsorbed state or in solution.     

Application of the normalized surface magnetic charge model to UXO discrimination in cases with overlapping signals

This paper presents an application of the normalized surface magnetic charge (NSMC) model to discriminate objects of interest, such as unexploded ordnance (UXO), from innocuous items in cases when UXO electromagnetic induction (EMI) responses are contaminated by signals from other objects. Over the entire EMI spectrum considered here (tens of Hertz up to several hundreds of kHz), the scattered magnetic field outside the object can be produced mathematically by equivalent magnetic charges. The amplitudes of these charges are determined from measurement data and normalized by the excitation field. The model takes into account the scatterer's heterogeneity and near- and far-field effects. For classification algorithms, the frequency spectrum of the total NSMC is proposed and investigated as a discriminant. The NSMC is combined with the differential evolution (DE) algorithm in a two-step inversion procedure. To illustrate the applicability of the DE–NSMC algorithm, blind test data are processed and analyzed for cases in which signals from nearby objects frequently overlap. The method was highly successful in distinguishing UXO from accompanying clutter.     

A new technique for determining the surface level of salt marshes and other uncompacted sedimentary environments

The method described involves the use of an electro-optical distance measurer mounted on a theodolite. Observations are taken onto a series of acrylic reflectors, aligned at right angles to the line of sight, and slope distances and vertical and horizontal angles are recorded. From these data it is possible to obtain surface heights to an accuracy of ±0·5 cm at 200 m and to avoid any direct disturbance of the site under investigation.     

Assessment of alternative adsorption models and global sensitivity analysis to characterize hexavalent chromium loss from soil to surface runoff

We investigate our ability to assess transfer of hexavalent chromium, Cr(VI), from the soil to surface runoff by considering the effect of coupling diverse adsorption models with a two‐layer solute transfer model. Our analyses are grounded on a set of two experiments associated with soils characterized by diverse particle size distributions. Our study is motivated by the observation that Cr(VI) is receiving much attention for the assessment of environmental risks due to its high solubility, mobility, and toxicological significance. Adsorption of Cr(VI) is considered to be at equilibrium in the mixing layer under our experimental conditions. Four adsorption models, that is, the Langmuir, Freundlich, Temkin, and linear models, constitute our set of alternative (competing) mathematical formulations. Experimental results reveal that the soil samples characterized by the finest grain sizes are associated with the highest release of Cr(VI) to runoff. We compare the relative abilities of the four models to interpret experimental results through maximum likelihood model calibration and four model identification criteria (i.e., the Akaike information criteria [AIC and AIC_C] and the Bayesian and Kashyap information criteria). Our study results enable us to rank the tested models on the basis of a set of posterior weights assigned to each of them. A classical variance‐based global sensitivity analysis is then performed to assess the relative importance of the uncertain parameters associated with each of the models considered, within subregions of the parameter space. In this context, the modelling strategy resulting from coupling the Langmuir isotherm with a two‐layer solute transfer model is then evaluated as the most skilful for the overall interpretation of both sets of experiments. Our results document that (a) the depth of the mixing layer is the most influential factor for all models tested, with the exception of the Freundlich isotherm, and (b) the total sensitivity of the adsorption parameters varies in time, with a trend to increase as time progresses for all of the models. These results suggest that adsorption has a significant effect on the uncertainty associated with the release of Cr(VI) from the soil to the surface runoff component.     

From experimental plots to experimental landscapes: topography,erosion and deposition in sub‐humid badlands from Structure‐from‐Motion photogrammetry

In the last decade advances in surveying technology have opened up the possibility of representing topography and monitoring surface changes over experimental plots (<10 m²) in high resolution (~10³ points m^‐1). Yet the representativeness of these small plots is limited. With ‘Structure‐from‐Motion’ (SfM) and ‘Multi‐View Stereo’ (MVS) techniques now becoming part of the geomorphologist's toolkit, there is potential to expand further the scale at which we characterise topography and monitor geomorphic change morphometrically. Moving beyond previous plot‐scale work using Terrestrial Laser Scanning (TLS) surveys, this paper validates robustly a number of SfM‐MVS surveys against total station and extensive TLS data at three nested scales: plots (<30 m²) within a small catchment (4710 m²) within an eroding marl badland landscape (~1 km²). SfM surveys from a number of platforms are evaluated based on: (i) topography; (ii) sub‐grid roughness; and (iii) change‐detection capabilities at an annual scale. Oblique ground‐based images can provide a high‐quality surface equivalent to TLS at the plot scale, but become unreliable over larger areas of complex terrain. Degradation of surface quality with range is observed clearly for SfM models derived from aerial imagery. Recently modelled ‘doming’ effects from the use of vertical imagery are proven empirically as a piloted gyrocopter survey at 50m altitude with convergent off‐nadir imagery provided higher quality data than an Unmanned Aerial Vehicle (UAV) flying at the same height and collecting vertical imagery. For soil erosion monitoring, SfM can provide data comparable with TLS only from small survey ranges (~5 m) and is best limited to survey ranges ~10–20 m. Synthesis of these results with existing validation studies shows a clear degradation of root‐mean squared error (RMSE) with survey range, with a median ratio between RMSE and survey range of 1:639, and highlights the effect of the validation method (e.g. point‐cloud or raster‐based) on the estimated quality. Copyright © 2015 John Wiley & Sons, Ltd.     

Levels and distribution of tris-(2,3-dibromopropyl) isocyanurate and hexabromocyclododecanes in surface sediments from the Yellow River Delta wetland of China

The levels and distribution of tris-(2,3-dibromopropyl) isocyanurate (TBC) and hexabromocyclododecanes (HBCDs) of surface sediments in the Yellow River Delta wetland had been investigated. The concentrations of TBC and ∑ HBCDs ranged from 0.20 to 29.03 ng·g^? 1 dw and below limits of detections (LODs) to 20.25 ng·g^? 1 dw. The average composition profile of three HBCDs isomers were 10.1%, 6.1% and 83.8% for α-, β- and γ-HBCD, respectively. Moreover, correlation analysis indicated there are similar sources among three isomers and positive correlations between total organic carbon (TOC) content and concentrations of TBC and HBCDs. The mass inventory of TBC,α-, β-, γ-HBCD, ΣHBCDs in surface sediments of Yellow River Delta wetland were estimated about 725.50, 72.76, 44.29, 548.34, 665.39 kg. Therefore, further investigations on potential human health and environmental risk assessments of TBC and HBCDs were needed.     

Ambient noise surface wave tomography of the Makran subduction zone,south-east Iran:Implications for crustal and uppermost mantle structures

Seismic ambient noise of surface wave tomography was applied to estimate Rayleigh wave empirical Green's functions(EGFs) and then to study crust and uppermost mantle structure beneath the Makran region in south-east Iran.12 months of continuous data from January 2009 through January 2010,recorded at broadband seismic stations,were analyzed.Group velocities of the fundamental mode Rayleigh wave dispersion curves were obtained from the empirical Green's functions.Multiplefilter analysis was used to plot group velocity variations at periods from 10 to 50 s.Using group velocity dispersion curves,1-D vs velocity models were calculated between several station pairs.The final results demonstrate significant agreement to known geological and tectonic features.Our tomography maps display low-velocity anomaly with SW-NE trend,comparable with volcanic arc settings of the Makran region which may be attributable to the geometry of Arabian Plate subducting beneath the overriding the Lut block.The northward subducting Arabian Plate is determined by high-velocity anomaly along the Straits of Hormuz.At short periods(20 s),there is a sharp transition boundary between low- and high-velocity transition zone with the NW trending at the western edge of Makran which is attributable to the Minab fault system.     

Removal of Cr(VI) by Zero‐valent,Iron‐encapsulated Alginate Beads

Zero‐valent, iron‐encapsulated alginate beads were synthesized and were applied for the removal of Cr(VI) from aqueous solutions. The effects of several important parameters including solution pH, contact time, initial concentration and reaction temperature on Cr(VI) removal levels were investigated in batch studies. An initial solution pH of 1.0 was seen to be most favorable for Cr(VI) removal. The removal process was quick and almost 80% of the removal was attained within 60 min. The kinetic data followed the second‐order equation well. The Cr(VI) removal was almost reaction temperature‐independent and decreased with an increase in Cr(VI) initial concentration. The removal of Cr(VI) by iron‐encapsulated alginate beads was found to be significantly higher than that of non‐encapsulated alginate beads.     

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.     

Removal of water‐surface reflection effects with a temporal minimum filter for UAV‐based shallow‐water photogrammetry

The recent development of structure‐from‐motion (SfM) and multi‐view stereo (MVS) photogrammetry techniques has enabled semi‐automatic high‐resolution bathymetry using aerial images taken by consumer‐grade digital cameras mounted on unmanned aerial vehicles (UAVs). However, the applicability of these techniques is sometimes limited by sun and sky reflections at the water surface, which render the point‐cloud density and accuracy insufficient. In this research, we present a new imaging technique to suppress the effect of these water‐surface reflections. In this technique, we order a drone to take a short video instead of a still picture at each waypoint. We then apply a temporal minimum filter to the video. This filter extracts the smallest RGB values in all the video frames for each pixel, and composes an image with greatly reduced reflection effects. To assess the performance of this technique, we applied it at three small shallow‐water sites. Specifically, we evaluated the effect of the technique on the point cloud density and the accuracy and precision of the photogrammetry. The results showed that the proposed technique achieved a far denser point cloud than the case in which a randomly chosen frame was used for each waypoint, and also showed better overall accuracy and precision in estimating water‐bottom elevation. The effectiveness of this new technique should depend on the surface wave state and sky radiance distribution, and this dependence, as well as the applicability to large areas, should be investigated in future research. Copyright © 2018 John Wiley & Sons, Ltd.     

区域闪电活动对地面相对湿度的响应

全球闪电活动表现出明显的地域差异,温度和湿度是造成这种差异的基本气象因素.本文利用美国全球水资源和气候中心提供的1995～2002年全球闪电资料和NCEP气象再分析资料,研究了区域闪电密度对地面相对湿度(RH)的响应.发现在平均相对湿度RH73%的经度带里,闪电密度与RH呈负相关;在RH>74%的赤道地区闪电活动与RH呈负相关, 而在RH<72%的中高纬地区闪电密度与RH呈正相关.得到结论：当地面相对湿度过大时,相对湿度的增加不利于闪电活动的发生;而当相对湿度较小时,相对湿度的增加有利于闪电活动的发生.地面相对湿度的临界值域约为72%～74%.此结论在不同经、纬度的几个典型区域均得到了验证,并探讨了过大的相对湿度抑制闪电活动发生的可能原因.     

Synthesis,Mechanism, and Performance Assessment of Zero‐Valent Iron for Metal‐Contaminated Water Remediation: A Review

Recently, increased industrial and agriculture activities have resulted in toxic metal ions, which has increased public concern about the quality of surface and groundwater. Various types of physical, biological, and chemical approaches have been developed to remove surface and groundwater metal ions contaminants. Among these practices, zero‐valent iron (ZVI) is the most studied reactive material for environmental clean‐up over the last two decade and so. Although ZVI can remove the contaminants even more efficiently than any other reactive materials. However, low reactivity due to its intrinsic passive layer, narrow working pH, and the loss of hydraulic conductivity due to the precipitation of metal hydroxides and metal carbonates limits its wide‐scale application. The aim of this work is to document properties, synthesis, and reaction mechanism of ZVI for the treatment of metal ions from the surface and groundwater in recent 10 years (2008–2018). So far, different modified techniques such as conjugation with support, bimetal alloying, weak magnetic field, and ZVI/oxidant coupling system have been developed to facilitate the use of ZVI in various environmental remediation scenarios. However, some challenges still remain to be addressed. Therefore, development and research in this field are needed to overcome or mitigate these limitations.     

Mobilisation and transport of dissolved organic carbon and iron in peat catchments—Insights from the Lehstenbach stream in Germany using generalised additive models

During the last decades, increasing exports of both dissolved organic carbon (DOC) and iron were observed from peat catchments in North America and Europe with potential consequences for water quality of streamwater and carbon storages of soils. As mobilisation and transport processes of DOC and iron in peat catchments are only partly understood, the purpose of this study was to elucidate these processes in an intensively monitored and studied system. Specifically, it was hypothesised that dissimilatory iron reduction in riparian peatland soils mobilises DOC initially adsorbed to iron minerals. During stormflow conditions, both DOC and iron will be transported into the stream network. Ferrous iron may be reoxidised at redox interfaces on its way to the stream, and subsequently, ferric iron could be transported together with DOC as complexes. To test these hypotheses, generalised additive models (GAMs) were applied to 14 years of weekly time series of discharge and concentrations of selected solutes measured in a German headwater stream called Lehstenbach. This stream drains a 4.19‐km² forested mountain catchment; one third of which is covered by riparian peatland soils. We interpreted results of different types of GAM in the way that (a) iron reduction drove the mobilisation of DOC from peatland soils and that (b) both iron and DOC were transported as complexes after their joint mobilisation to and within the steam. It was speculated that low nitrate availability in the uppermost wetland soil layer, particularly during the growing season, promoted iron reduction and thus the mobilisation of DOC. However, the influence of nitrate on the DOC mobilisation remains relatively uncertain. This influence could be further investigated using methods similar to the GAM analysis conducted here for other catchments with long‐term data as well as detailed measurements of the relevant species in riparian wetland soils and the adjacent stream network.     

From alkali basalt to phonolite in hand-size samples: vapor-differentiation effects in the Bouzentès lava flow (Cantal, France)

The Bouzentès lava flow is a 20-m-thick alkali basalt flow emplaced during the last stage of formation of the Cantal stratovolcano at 4.2 Ma. Its upper part has 1- to 20-cm-thick vesicle-rich segregation sheets which recur every 0.1–2 m. These horizontal veins are hawaiitic in composition. They are characterized by hypertrophic development of their minerals (‘pegmatoids’) and by glassy phonolitic segregation vesicles. Internal differentiation within the Bouzentès lava flow was triggered by an unusually high water content, as suggested by pre-emptive iddingsite alteration of olivine phenocrysts. The proposed model of formation of the segregation sheets includes the upward motion of diapirs of residual melt plus addition of vapor from the bottom of the central liquid lens to the base of the upper solidified crust of the cooling lava flow. Olivine settling appears to have been inhibited or at least retarded by upward migration of melt plus vesicles. Most of the features observed in Bouzentès recall the internal differentiation processes usually described within thick Hawaiian lava lakes. The segregation vesicles are believed to result from an increase of gas solubility in residual melt during the crystallization process.