Determining individual mineral contributions to U(VI) adsorption in a contaminated aquifer sediment: A fluorescence spectroscopy study

The adsorption and speciation of U(VI) was investigated on contaminated, fine grained sediment materials from the Hanford 300 area (SPP1 GWF) in simulated groundwater using cryogenic laser-induced U(VI) fluorescence spectroscopy combined with chemometric analysis. A series of reference minerals (montmorillonite, illite, Michigan chlorite, North Carolina chlorite, California clinochlore, quartz and synthetic 6-line ferrihydrite) was used for comparison that represents the mineralogical constituents of SPP1 GWF. Surface area-normalized K_d values were measured at U(VI) concentrations of 5 × 10⁻⁷ and 5 × 10⁻⁶ mol L⁻¹ that displayed the following affinity series: 6-line-ferrihydrite > North Carolina chlorite ≈ California clinochlore > quartz ≈ Michigan chlorite > illite > montmorillonite. Both time-resolved spectra and asynchronous two-dimensional (2D) correlation analysis of SPP1 GWF at different delay times indicated that two major adsorbed U(VI) species were present in the sediment that resembled U(VI) adsorbed on quartz and phyllosilicates. Simulations of the normalized fluorescence spectra confirmed that the speciation of SPP1 GWF was best represented by a linear combination of U(VI) adsorbed on quartz (90%) and phyllosilicates (10%). However, the fluorescence quantum yield for U(VI) adsorbed on phyllosilicates was lower than quartz and, consequently, its fractional contribution to speciation may be underestimated. Spectral comparison with literature data suggested that U(VI) exist primarily as inner-sphere complexes with surface silanol groups on quartz and as surface U(VI) tricarbonate complexes on phyllosilicates.     

六价铬污染模拟含水层的注入型黄原胶凝胶阻截屏障试验研究

由于工业废物的不合理排放,大量的重金属污染物Cr(Ⅵ)进入地下环境,严重威胁着人类健康和生态环境。Cr(Ⅵ)在地下水环境中高度易迁移的特性,造成其污染修复上的困难,亟待一种绿色、经济、有效的阻截方式提高地下水对Cr(Ⅵ)的阻控能力。研究利用焦亚硫酸钠原位还原地下水中的Cr(Ⅵ),产生Cr³⁺作为黄原胶交联剂,形成凝胶阻截屏障,探究了各类成分对凝胶时间、黏度变化的影响及凝胶屏障对含水层的阻截效果,得到如下结论：(1)在Cr(Ⅵ)质量浓度达到200 mg/L的体系中,质量分数0.4%的黄原胶溶液在1.5 h内即可形成具有一定机械强度的凝胶;(2)凝胶具有耐盐性,适用于常见含水层,2.5～5 g/L的Na⁺和K⁺对凝胶起促进作用;(3)注入型凝胶阻截屏障能够大幅降低中砂介质的渗透系数至1×10^-7 cm/s,满足地下水阻截需求。注入型凝胶屏障的形成无需引入有害物质,阻截结束后注入型屏障可经生物作用自然降解,不会长期改变含水层水力条件。研究成果可为Cr(Ⅵ)污染地下水中凝胶阻截屏障的构筑提供理论基础。     

A geochemical study of redox behavior of As in a contaminated aquifer from Sonargaon, Central Bangladesh

The Bengal Basin has been exposed to the most serious As problem in the world. Although it has been agreed well among many researchers that the contamination has been induced by natural geochemical process, detailed mechanisms are still under debate. Arsenic is easily soluble into groundwater as pentavalent arsenate and trivalent arsenite. Their adsorption behavior for various solid phases, particularly for Fe oxyhydroxide （FeOOH）, is different. Thus speciation of As in solid phase is essential to examine the process of contamination. However, few studies have been done about As speciation in sediment due to its analytical difficulty. In this study, we applied XANES （X-ray adsorption near the edge structure） spectroscopy to determine oxidation states of As and Fe, and investigate As behavior along change in redox condition. We studied the Sonargaon area located 25 km southeast of Dhaka. Sediment core samples were collected from one site in the area up to the depth of 100 m using penetration-drilling method. The samples were packed into oxygen impermeable film with deoxidizer on site,     

Reduction of U(VI) to U(IV) on the surface of magnetite

To increase the understanding of uranium transport in the environment and in the presence of steel corrosion products, the interaction of U(VI) with natural magnetite has been studied. Sorption studies have been carried out using X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS). The XPS results clearly indicate the reduction of U(VI) to U(IV) on the surface of magnetite facilitated by electron transfer between the Fe and U, leading to a coupled oxidation of Fe(II) to Fe(III).     

Light transmission method to explore the migration and distribution of Cr(VI) in a sandy aquifer

The migration and distribution of contaminants in heterogeneous aquifers are mostly investigated through numerical simulations. They are rarely examined through experimental simulations because of sampling difficulties. In this study, we used the light transmission method (LTM) to explore the migration and distribution of hexavalent chromium [Cr(VI)] in homogeneous sandy aquifers with or without a low-permeability bottom and lens (heterogeneous aquifer). Experimental phenomena were observed via images obtained with a high-power light source. The migration distances of pollution plume were also monitored. Under heterogeneous conditions, low-permeability aquifer materials considerably inhibited the migration of Cr(VI) and altered the Cr(VI) migration rate of horizontal and vertical plumes spread to a certain extent. Common horizontal and vertical migration curve equations in all three conditions were also obtained through distance–time curve fitting. The difference between high- and low-concentration zones was accurately revealed, and the experimental phenomenon was further explained. The proposed method could be used for the qualitative investigation and visualization of the migration and distribution of Cr(VI).     

混合菌种对地下水中三氯乙烯的生物降解和吸附解吸的实验研究

由于氯代有机溶剂的大量使用和不合理的处置,致使三氯乙烯(以下简称TCE)成为地下水中常见的有机污染物.本实验以TCE为靶污染物,采用批试验方法,研究了灭菌后的混合菌种对不同浓度TCE的吸附影响.实验结果表明:当TCE浓度在10～200mg/l范围内,TCE的吸附模式符合Cs=0.17976C2.3639e等温方程;TCE的解吸模式符合C=0.02987C2.1461e等温方程;吸附在15min内平衡;解吸在1h内平衡.     

Scaling of adsorption reactions: U(VI) experiments and modeling

Iron-coated sands were prepared via two common protocols, a precipitation method, where Fe was precipitated directly onto the sand in a single step, and an adsorption method, where pure goethite was prepared in the first step and then adsorbed onto the sand in a second step. The coated sands from both the systems were characterized using scanning electron microscopy, energy-dispersive spectroscopy, X-ray diffraction, and selective Fe extraction. Although neither of the methods produced a completely crystalline Fe coating, the precipitation method produced sands with larger portions of amorphous Fe than the adsorption method, with the fraction of amorphous Fe decreasing with increasing Fe content. Uranium(VI) adsorption isotherms and pH adsorption edges were measured on three coated sands with Fe contents ranging from 0.04% to 0.3%. Experimentally, the adsorption of U(VI) onto the three sands was more comparable when normalized to surface area than when normalized to Fe content. A surface complexation model, although originally developed for U(VI) adsorption onto amorphous Fe oxide, captured the differences in adsorption when adjusted for the surface area of the coated sand. The findings indicate that surface area is a better scaling parameter than Fe content in predicting U(VI) adsorption to Fe-dominated media. These findings are significant because many common surface complexation models are parameterized on the basis of Fe content rather than specific surface area. Although the interactions of U(VI) and Fe-coated sands were used as representative adsorbate and adsorbent, the general principles may be applicable to other adsorbate–adsorbent systems as well.     

Impact of recharge water temperature on bioclogging during managed aquifer recharge: a laboratory study

To investigate the effect of recharge water temperature on bioclogging processes and mechanisms during seasonal managed aquifer recharge (MAR), two groups of laboratory percolation experiments were conducted: a winter test and a summer test. The temperatures were controlled at ~5±2 and ~15±3 °C, and the tests involved bacterial inoculums acquired from well water during March 2014 and August 2015, for the winter and summer tests, respectively. The results indicated that the sand columns clogged ~10 times faster in the summer test due to a 10-fold larger bacterial growth rate. The maximum concentrations of total extracellular polymeric substances (EPS) in the winter test were approximately twice those in the summer test, primarily caused by a ~200 μg/g sand increase of both loosely bound EPS (LB-EPS) and tightly bound EPS (TB-EPS). In the first half of the experimental period, the accumulation of bacteria cells and EPS production induced rapid bioclogging in both the winter and summer tests. Afterward, increasing bacterial growth dominated the bioclogging in the summer test, while the accumulation of LB-EPS led to further bioclogging in the winter test. The biological analysis determined that the dominant bacteria in experiments for both seasons were different and the bacterial community diversity was ~50% higher in the winter test than that for summer. The seasonal inoculums could lead to differences in the bacterial community structure and diversity, while recharge water temperature was considered to be a major factor influencing the bacterial growth rate and metabolism behavior during the seasonal bioclogging process.     

Europium sorption to sediments in the presence of natural organic matter: A laboratory and modeling study

Cellulosic materials, such as wood, paper products and cardboard that have been co-disposed with low-level nuclear waste have been shown to produce leachate with natural organic matter (NOM) concentrations of hundreds of mg/L C and, as such, have the potential to influence the fate and transport of radionuclides in the subsurface environment. The objective of this study was to examine the influence of NOM on the sorption of Eu (an analogue for trivalent radionuclides) to two coastal plain sediments from the US Department of Energy’s Savannah River Site. Particular attention was directed at quantifying Eu interactions with NOM sorbed to sediments (NOM_sed) in laboratory experiments and developing conditional stability constants for that interaction using the thermodynamic equilibrium speciation model MINTEQA2. Europium sorption to the two sediments systematically increased as pH increased from 3.9 to 6.7. With increasing additions of NOM to the aqueous phase from 0 to 222 mg/L C, Eu sorption initially increased to a maximum at 10 mg/L C NOM_aq and then decreased with increasing NOM_aq concentrations. Increases in Eu sorption at low NOM additions was attributed to the sorption of NOM to the sediment surface increasing the number of sorption sites on the low cation-exchange capacity sediments and/or increasing the association constant (log K) for the Eu-sediment surface reaction. Decreases in Eu sorption at higher NOM levels was attributed to Eu_aq complexation to NOM_aq being more favored than Eu sorption to the solid phase. A component additivity model was developed to describe the Eu–NOM-sediment system by the additive effects of the three binary system models: Eu–NOM, Eu-sediment and NOM-sediment. The model generally captured the data trends in the ternary system. Conditional stability constants developed from the experimental data for the complexation of Eu to NOM_sed were as much as four orders of magnitude greater than Eu complexation with NOM_aq, presumably due to the NOM_sed deriving additional negative (attractive) charge from the sediment surface. At high initial NOM_aq levels, >99 mg/L C, the model captured the trend of reduced Eu sorption but tended to over-estimate Eu sorption. The additivity approach of combining binary models to form a ternary model was only successful when the unique complexation properties of the NOM_sed were properly calculated.     

Influence of HCl/HF treatment on organic matter in aquifer sediments: A Rock-Eval pyrolysis study

Rock–Eval pyrolysis is increasingly used for the routine characterization of natural organic matter in soils and sediments. In this work the bulk composition of sedimentary organic matter (SOM) in sandy aquifer sediments is studied, as well as purified samples (isolation of SOM) by HCl/HF treatment. This treatment is necessary to avoid detection limit problems for samples with low SOM contents, but the results presented here indicate that this treatment influences the organic geochemistry of the aquifer sediment samples. The FID and CO₂/CO pyrograms show a shift of 10–40 °C of the major peak to a lower temperature. Organic matter alteration or removal of components containing O-bearing groups may explain this. It is also suggested that destruction of the mineral matrix may lead to the reduced retention of the material. For the change of the CO₂/CO pyrograms of the RC fraction only organic matter alteration seems to be likely. Concentrated organic matter samples may also accelerate the release of exothermic energy and influence the pyrograms. Results indicate that the organic matter concentration in the sample influences the measured total organic matter (TOM) content and the T_max of the FID pyrogram, while the sample loading (absolute organic matter amount) up to 80 mg in the Rock–Eval apparatus does not. The FID pyrograms can be deconvoluted into four subpeaks, which allows comparison of samples at various depths. Rock–Eval pyrolysis may only be routinely applied to characterize SOM in aquifer sediments when such systematic and analytical phenomena are taken into account.     

A comparative study of the effect of desferrioxamine B, oxalic acid, and Na-alginate on the desorption of U(VI) from goethite at pH 6 and 25 °C

Organic ligands affect the sorption and mobility of radionuclides in soils. Batch desorption experiments on goethite particles reveal the extent of uranyl desorption and hence bioavailability with different organic acids. The desorptive strength increases in the following order: background electrolyte < Na-alginate < desferrioxamine B (DFO-B) < oxalate. The sequence is consistent with decreasing molecular size and mass from alginate via DFO-B to oxalate. The concomitant Fe release in the desorption experiments indicates that desorption from goethite and not dissolution of goethite governs the mobility of adsorbed U(VI). A compilation of DFO-B surface excesses on goethite from our experiments together with literature values indicate that DFO-B adsorbs at a constant ∼3% to the goethite surface. It is surprising that such a small fraction suffices to account for the considerable uranyl desorption and thus remobilization of a radionuclide into solution. Oxalate displays higher surface concentrations but still lower than the determined uranyl surface excess. It follows that based on the high U(VI) stability constants, both organic ligands induce the desorption of uranyl species by increasing the chemical affinity of the aqueous phase. In the case of alginate, desorption of uranyl is weak and adsorbed alginate hampers any considerable detachment of U(VI) in the presence of the more potent ligands, DFO-B and oxalate. This inhibition is based on biosorption and in this respect polysaccharides in soils may retard and even halt the advance of actinides through the soil column. This hypothesis calls for further studies into the interaction of siderophores and polysaccharides with soil adsorbents and their role in the mobilization of contaminant metals.     

Identifying vulnerable areas of aquifer under future climate change (case study: Hamadan aquifer,West Iran)

Groundwater is the main source of water in arid and semi-arid regions, so it is very important to recognize vulnerable parts of aquifer under future climate change conditions. In this research, 16 climate models were evaluated based on weighting approach. HADCM3 and CGCM2.3.2a models were selected for temperature and precipitation prediction, respectively. LARS-WG was used for downscaling AOGCMs outputs. Results show that temperature increase by 1.4 °C and precipitation changes between +10 and ?6 % under B1 and A2 emission scenario, respectively. Runoff volumes will decrease by ?39 % under A2 emission scenario whereas runoff volume will increase by +12 % under B1 emission scenario. Simulation of groundwater head variation by MODFLOW software indicates higher groundwater depletion rate under A2 scenario compared to B1 scenario. Groundwater model outputs indicate that the most vulnerable part of the aquifer is located in the southwest region. Large number of extraction wells and low aquifer transmissivity are the reasons for high vulnerability of the region.     

Site characterization and monitoring of natural attenuation indicator parameters in a fuel contaminated coastal aquifer: Karaduvar (Mersin,SE Turkey)

This paper presents results from a site characterization and monitoring study at Karaduvar area (Mersin, SE Turkey), where high concentrations of refined petroleum products have been detected in domestic and irrigation water wells. The saturated and unsaturated zones in the deltaic aquifer are contaminated by large quantities of gasoline and diesel range fuel hydrocarbons (GRHs and DRHs) released from diverse sources that include accidental spills, storage tank fires, pipeline breaks, deliberate discharge of waste petroleum products from slop tanks and illegal tanker truck washing facilities. At the site, due to the complex nature of the pollution sources, overlapping contaminant plumes exist and cover an area of about 0.5 km². In both polluted and unpolluted parts of the aquifer, monitoring of groundwater physicochemical parameters in a total of 55 sampling points was carried out between 2006 and 2007. The results show that the terminal electron acceptors (e.g. dissolved oxygen, nitrate, Mn(IV), Fe(III), sulfate) were reduced near the source area(s) indicating presence of actively operating biodegradation processes at the site. Close to the contaminant source area(s), conditions in the plume are highly anoxic and reducing; where high amounts of transformation products (e.g. bicarbonate, dissolved iron, and manganese) are present in solution. Additionally, at the site, excessive pumping, careless land use, and deliberate wastewater discharges significantly deteriorated the quality and quantity of groundwater. Excessive groundwater pumping for industrial and agricultural uses has resulted in substantial water level declines (2–3 m) near the coastal part where seawater intrusion threatens the groundwater resources.     

Modeling complex aquifer systems: a case study in Baton Rouge,Louisiana (USA)

Hydrogeology Journal - This study targets two challenges in groundwater model development: grid generation and model calibration for aquifer systems that are fluvial in origin. Realistic...     

Methodological proposal to assess groundwater contamination danger: study case of Bajo Cauca aquifer (Colombia)

Interaction between vulnerability and contaminating charge was used in order to determine the groundwater contamination danger. The result of danger being adapted to the scale of impact on human or animal health and ecosystems is known as “risk”. Index and overlapping methodologies such as EPNNA, DRASTIC, SINTACS, GOD AVI, and Ekv were used and compared to evaluate vulnerability. Contaminating charge to the subsoil, which is generated from specific human activity, has four characteristics: kind of contaminant, means of disposal, intensity, and duration. Interaction among these characteristics obtains a Contaminating Charge Index. In the Bajo Cauca Antioqueño region, over 150,000 inhabitants require ground water for meeting their basic needs at home, for cattle breeding activities, and for irrigation. For this region, an assessment of the groundwater contamination of the free aquifer, as well as an estimation of its impact and the danger this contamination may pose to ecosystems or communities has been performed. Analysis of the interaction between vulnerability and threat allows for the creation of danger and risk maps.     

Reactions of the feldspar surface with metal ions: Sorption of Pb(II), U(VI) and Np(V), and surface analytical studies of reaction with Pb(II) and U(VI)

Feldspar minerals are thermodynamically unstable in the near-surface environment and their surfaces are well known to react readily with aqueous solutions, leading to incongruent dissolution at low pH values, but congruent dissolution at neutral and high pH values. Interactions with mineral surfaces are an important control on the environmental transport of trace elements and detrital feldspars are abundant in soils and sediments. However, the interactions of metal ions in solution with the reacting feldspar surface have not been widely explored. The interactions of Pb(II), U(VI) and Np(V) ions with the feldspar surface have therefore been studied. Lead is taken up by the microcline surface at pH 6 and 10, but no uptake could be measured at pH 2. There was measurable uptake of Pb(II) on the plagioclase surface at pH 2, 6 and 10. Uptake always increased with pH. In most conditions, Pb(II) reacts through cation exchange process although, at high pH, a discrete phase, probably hydrocerrusite, is observed by atomic force microscopy (AFM) to precipitate on the plagioclase surface. Supersaturation with hydrocerrusite in these conditions is expected from thermodynamic calculations. Uptake of uranyl ion , generally through surface complex formation, could only be measured at pH 6 and 10. At pH 6 and an initial U(VI) concentration above 21.0 μM, precipitation of becquerelite (Ca[(UO₂)₃O₂(OH)₃]₂·8H₂O), identified by AFM and characterised by grazing incidence X-ray diffraction and X-ray photoelectron spectroscopy, is observed on plagioclase. The U(VI) concentration range in which becquerelite precipitation begins (dissolved U(VI) 1-5 μM) is consistent with that predicted from thermodynamic modelling. On plagioclase feldspar, secondary ion mass spectrometry showed diffusion of uranium into the altered surface layer. Uptake of the neptunyl ion (Np(V)) was found at pH 6 and 10 for microcline and at pH 2, 6 and 10 for plagioclase, and was generally lower than uptake of U(VI). By combining batch sorption experiments with imaging and surface analysis, and thermodynamic modelling, it has been possible to gain a mechanistic insight into the reactions of the feldspar surface with metal ions in solution.     

Erratum to: Geochemical and environmental magnetic characteristics of high arsenic aquifer sediments from Datong Basin,northern China

Geochemical and environmental magnetic studies were carried out to identify the effect of iron oxyhydroxides on arsenic mobilization in high arsenic aquifer system. Using high arsenic sediment samples from two boreholes, specifically drilled for this study, chemical composition and magnetic properties including magnetic susceptibility, saturation remnant magnetization, and isothermal remnant magnetization were measured. Results of correlation analysis of element contents show that arsenic and iron are closely associated with each other (r ² = 0.40, α = 0.05, n = 21). In contrast, the correlation of phosphorus with iron (r = 0.11, α = 0.05, n = 21) and arsenic (r ² = 0.18, α = 0.05, n = 21) was poor, which might result from competitive adsorption of phosphorus and arsenic on the surface of Fe-oxyhydroxides. The high correlation coefficients between arsenic contents and magnetic parameters suggest that the ferrimagnetic minerals including maghemite and hematite are the dominant carrier of arsenic in aquifer sediments. The results of sequential extraction experiments also revealed the association of arsenic with reducible iron oxides, such as maghemite and hematite in aquifer sediments. Therefore, under reducing conditions, reductive dissolution and desorption of arsenic from Fe-oxyhydroxides into the aqueous phase should be the dominant geochemical processes for its enrichment in groundwater at Datong. An erratum to this article can be found at