Redox potential and uranium sorption onto sediments: kinetic and thermodynamic characteristics

ABSTRACT

The effects of the flooding and initial Eh of sediments on the sorption of uranium onto the sediments were analysed by flooding and static experiments. The changes in uranium species with Eh and kinetic and thermodynamic characteristics of the uranium sorption onto the sediments were investigated. The flooding experiment indicates that the initial Eh of the sediment gradually decreased with the increase in flooding time. Based on the redox potential in the flooding experiment, simulation results obtained using the geochemical simulation software PHREEQC show that the concentration of U (VI) decreased. In contrast, the concentrations of U (III), U (IV), and U (V) gradually increased. The pseudo-second-order kinetic model well fitted the experimental data, which shows that the sorption was mainly chemical sorption. The thermodynamic parameters suggest that the entropy and enthalpy under the used conditions were positive and that ΔG^θ was negative. A thermodynamic analysis shows that the sorption was endothermic and spontaneous. These results are useful for the understanding of the sorption mechanism and migration of uranium onto the sediment under different initial sediment redox potentials and provide a good theoretical foundation for radioactive pollution remediation.     

Geochemical index of trace metals in the surficial sediments from the western continental shelf of India, Arabian Sea

The present study focuses on the determination and abundance of trace metals (viz. Cu, Ni, Zn, Cr, Co, Cd, Mn and Fe) in the surficial sediments of west coast of Arabian Sea along the Indian subcontinent. Sediment samples were collected from three transects along the western continental shelf of Arabian Sea. The enrichment of Fe and Mn in coastal oxic-sediments indicates the precipitation of these redox sensitive elements as Fe- and Mn-hydroxides and oxides, whereas the low Fe and Mn concentrations in the oxygen deficient sediments of deeper stations reflects the dissolution of their hydroxides and oxides. Concentrations of fairly redox insensitive trace metals like Cu, Ni, Zn, Cr and Cd (with the exceptions of Cr) showed higher values at nearshore sediments, then it decreased towards seaward and again showed a slight increase at oxygen minimum stations in all the three transects. This geochemical variability in their distributional characteristics is mainly associated with the extent to which the precipitation or dissolution of Fe- and Mn-oxides/hydroxides occur since the scavenging or releasing effects of Fe- and Mn-oxides/hydroxides act as significant ‘sinks’ or ‘sources’ of heavy metals. The change in wind pattern, coastal upwelling and increased productivity are also the reported factors which influence the biogeochemical cycling of trace metals in the surface sediments of west coast of India. Enrichment factor generally showed a high gradient accumulation from nearshore to shelf.     

Correlation analysis as a tool to investigate the bioaccessibility of nickel, vanadium and zinc in Northern Ireland soils

Correlation analyses were conducted on nickel (Ni), vanadium (V) and zinc (Zn) oral bioaccessible fractions (BAFs) and selected geochemistry parameters to identify specific controls exerted over trace element bioaccessibility. BAFs were determined by previous research using the unified BARGE method. Total trace element concentrations and soil geochemical parameters were analysed as part of the Geological Survey of Northern Ireland Tellus Project. Correlation analysis included Ni, V and Zn BAFs against their total concentrations, pH, estimated soil organic carbon (SOC) and a further eight element oxides. BAF data were divided into three separate generic bedrock classifications of basalt, lithic arenite and mudstone prior to analysis, resulting in an increase in average correlation coefficients between BAFs and geochemical parameters. Sulphur trioxide and SOC, spatially correlated with upland peat soils, exhibited significant positive correlations with all BAFs in gastric and gastro-intestinal digestion phases, with such effects being strongest in the lithic arenite bedrock group. Significant negative relationships with bioaccessible Ni, V and Zn and their associated total concentrations were observed for the basalt group. Major element oxides were associated with reduced oral trace element bioaccessibility, with Al₂O₃ resulting in the highest number of significant negative correlations followed by Fe₂O₃. spatial mapping showed that metal oxides were present at reduced levels in peat soils. The findings illustrate how specific geology and soil geochemistry exert controls over trace element bioaccessibility, with soil chemical factors having a stronger influence on BAF results than relative geogenic abundance. In general, higher Ni, V and Zn bioaccessibility is expected in peat soil types.     

Effect of natural organic matter on arsenic release from soils and sediments into groundwater

Arsenic (As) contamination in groundwater has received significant attention recently. Natural and anthropogenic sources contribute to the worldwide occurrence of As contamination. As speciation is an important factor related to its toxic and mobile behavior. The release of As from soils and sediments into groundwater is governed by several geophysicochemical processes, of which, As sorption behavior is of principle significance. This review paper summarizes existing information regarding the effects of natural organic matter (NOM) on the fate and mobility of As species in the environment. NOM may enhance the release of As from soils and sediments into the soil solution, thereby facilitating As leaching into the groundwater. The main influencing mechanisms include competition for available adsorption sites, formation of aqueous complexes, and/or changes in the redox potential of site surfaces and As redox speciation. NOM may also serve as binding agents, thereby reducing As mobility. However, comparably little research has been performed on this aspect. Since most investigations have been done on purified minerals under laboratory conditions, further research involving various geological materials under natural environmental conditions is required. Development of proper geochemical conceptual models may provide means of predicting the role of NOM in arsenic leaching and/or immobilization.     

Geophysical investigations for evaluation of environmental pollution in a mine tailings area

Sulfide-containing mill wastes of the Komsomolsk ore processing plant situated in the Kemerovo region (Russia) were examined in 2013–2015. Multipurpose studies of the mine tailings determined the composition of waste, pore water, mine drainages, and affected groundwater. Electrical resistivity tomography was used to trace the geoelectric zoning of the waste samples. Layers with low resistivity indicated areas with pore spaces filled with highly mineralized solutions with Fe, Cu, Zn, Cd, As, and Sb at total concentrations of up to 50 g/L. Anomalous zones can be specified as ‘geochemical barriers’ – specific layers where the mobility of the elements is reduced due to pH conditions, redox potential, and Fe(III) hydroxide precipitation. The zones of increased conductivity in oxidized mine tailings indicated local areas with high acid production potential and coexisting acidic pore solution. In non-oxidized tailings, high conductivity of the mineral skeleton was observed. There was a migration of drainage outside the tailings, its direction monitored by geophysical data. Chemical analysis confirmed that the concentrations of As in groundwater samples were higher than the maximum permissible concentration.     

Assessment of nutrients and heavy metals enrichment in surface sediments from Taihu Lake,a eutrophic shallow lake in China

Concentrations of the nutrients (TN and TP), phosphorus fractions and heavy metals (Co, Cr, Cu, Mn, Ni, Pb, Sr, Ti, V, Zn and Hg) in 40 surface sediment samples collected from Taihu Lake, a eutrophic shallow lake in China, were determined. The results showed that the northwest region of the lake possessed higher concentrations of TN and TP, as well as the similar spatial distribution trend in the water column. This should be related to excessive anthropogenic input from industrial effluents and domestic sewage in surrounding areas. Similarly, the concentrations of P fractions exhibited significant regularity. In addition, except for Sr showing low concentration, the rest of the heavy metals in the surface sediments had two- to four-folds of magnitude of the concentrations compared with the reference values in earth's crust. In the past decade, concentrations of heavy metals had undergone different levels of variations. Principal component analysis (PCA) and enrichment factors (EFs) of the compositional data aiming at heavy metals showed that Taihu Lake was slightly exposing to heavy metal contamination except Sr. High concentrations of heavy metals were ascribed to the discharge of untreated and partially treated industrial waste water via rivers. Co, Cr, Cu, Mn, Ni, Pb, V and Zn positively correlated with each other (R = 0.78–0.92), that indicated they had analogous sources and/or kindred geochemistry characteristics. Differing from nutrients, randomness in the space indicated that heavy metals had a complex distribution.     

Source and Effect of Heavy Metal Pollution in the Coastal Taiwan Sediments

Coastal sediments and oyster farming is severely affected by the industrial effluents in the coastal region near LuGong, Taiwan. Surficial sediments and oyster samples were collected from a coastal area near a major electro-plating industry. Spatial variation in heavy metal contents in sediments was studied in relationship to the main pathway of contamination and geochemical association with natural constituents of the sediments.

Spatial trends of heavy metals in the sediment reflected inputs of pollutants from the poorly-treated electro-plating effluents in the surrounding county and transported downstream by the Yang-tse-tru River. Effluent related heavy metal (Zn, Cu, Cd) is extremely high in the study region sediments. the highest concentrations were observed near shore, especially upstream in the Yang-tse-tru River sediments. Heavy metal concentrations decreased rapidly in a seaward direction. Heavy metal concentrations in near shore sediments were as high as some highly industrialized harbour sediments in the USA (e.g. Boston and San Diego).

Significant differences and high concentrations of heavy metals were also observed in oysters from the study region. Heavy metals from the study region were two to five times higher than in oysters from other pristine areas in Taiwan.     

Geochemical distribution,bioavailability and potential toxicity of some trace metals in a complex micro-tidal estuary,Southwest India

The spatial and temporal variations of some trace metals in the surface sediments of Cochin Estuary were analyzed along with their geochemical associations to identify the possible sources, bioavailability and the health risks posed by them. The dominance of kaolinite and suggested that clay minerals distribution is influenced by sediment sorting. Total metal analysis revealed enrichment for Cd, Pb and Zn due to anthropogenic activities. The speciation analysis established that notwithstanding the large availability, carbonate as well as organic and sulfides bound fractions showed negligible associations with most of the metals. Hydrous Fe–Mn oxides appeared to play a major role in controlling the fate and transport of these metals in the sediments of Cochin Estuary. Lower contribution of the residual fractions for Cd (21%–26%), Pb (<60%) and Zn (24%–42%) indicated an obvious increase of other geochemical fractions. Risk assessment analysis revealed that regardless of total concentration, none of the analyzed metals were at safe levels in the estuary as appreciable percentages were found to be associated with mobile geochemical forms. The speciation study conspicuously established that the metals originating from non-geogenic sources are largely associated with the labile fractions and hence are more detrimental to the aquatic biota.     

Importance of background values in assessing the impact of heavy metals in river ecosystems: case study of Tisza River,Serbia

The main objective of this paper is to evaluate how a choice of different background values may affect assessing the anthropogenic heavy metal pollution in sediments from Tisza River (Serbia). The second objective of this paper is to underline significance of using geochemical background values when establishing quality criteria for sediment. Enrichment factor (EF), geoaccumulation index (I _geo), pollution load index (PLI), and potential ecological risk index (PERI) were calculated using different background values. Three geochemical (average metal concentrations in continental crust, average metal concentrations in shale, and average metal concentrations in non-contaminated core sediment samples) and two statistical methods (delineation method and principal component analyses) were used for calculating background values. It can be concluded that obtained information of pollution status can be more dependent on the use of background values than the index/factor chosen. The best option to assess the potential river sediment contamination is to compare obtained concentrations of analyzed elements with concentrations of mineralogically and texturally comparable, uncontaminated core sediment samples. Geochemical background values should be taken into account when establishing quality criteria for soils, sediments, and waters. Due to complexity of the local lithology, it is recommended that environmental monitoring and assessment include selection of an appropriate background values to gain understanding of the geochemistry and potential source of pollution in a given environment.     

Red soil geochemistry in a semiarid Mediterranean environment and its suitability for vineyards

A geochemical study of a red soil derived from plioquaternary materials was carried out. The soil was located in a region of complex geomorphology and pedologic evolution, with particular characteristics of a Mediterranean climate associated with processes of alteration, rubification, gleying (hydromorphism) and argillization. The depth distribution of 27 trace elements was studied in order to determine the amounts of these elements in the soil and its tendency. The mineralogy of the clay fraction was also studied along with other physico-chemical properties to elucidate in terms of attributes meaningful for viticulture. The geochemical composition of the horizons was studied. The effect of human activities on the soil was investigated as well as the geographical origin of Mancha wines. It was found that these activities did not give rise to significant variations of trace elements, although a discontinuity related to the accumulation of new materials was detected. Ultimately, using established productivity standards, suitability for the cultivation of vines on these soils was determined.     

Interpretation of black sea sediments analytical data by the clustering approach

Analytical data consisting of chemical concentration of 11 inorganic components in 20 sampling stations from sediments collected from south‐western part of the Black Sea are treated by cluster analysis. The clustering reflects quite satisfactorily the relations between sampling zones and between chemical elements revealing new chemical and geochemical information.     

Sediment geochemistry and arsenic mobilization in shallow aquifers of the Datong basin,northern China

Understanding the mechanism of arsenic (As) mobilization from sediments to groundwater is important for water quality management in areas of endemic arsenic poisoning, such as the Datong basin in northern China. The bulk geochemistry analysis of sediment samples from three 50-m boreholes drilled specifically for this study at As-contaminated aquifers, the groundwaters of which have an As concentration up to 1060 μg/l, revealed that the average bulk concentrations of major and trace elements of the samples are similar to those of the average upper continental crust. The average As content of the sediment samples (18.7 mg/kg) is higher than that of modern unconsolidated sediments (5–10 mg/kg). Moreover, the abundance of elements varied with grain size, with higher concentrations in finer fractions of the sediments, such as silt and clay. The concentration of NH₂OH–HCl-extracted iron (Fe) strongly correlated with that of extracted As, suggesting that Fe oxyhydroxides may be the major sink of As in the aquifer. The results of microcosm experiments showed that As mobilization from sediments to groundwater is probably mainly related to changes in the redox conditions, with moderately reducing conditions being favorable for As release from sediments into groundwater.     

Heavy metals in top core sediments from the southern Campania shelf (Italy): Hints to define large-scale geochemical backgrounds

The results of a geochemical survey carried out on the southern Campania shelf (southern Italy) are illustrated, offering a tempting opportunity to discuss the statement and definition of regional geochemical backgrounds for selected heavy metals. A total of 104 top core sediments, collected on average 1.5 km from one another and covering a shelf area of about 1300 km², were analysed for grain size, organic carbon content (OC), and heavy-metal (As, Al, Fe, Cd, V, Cr, Zn, Cu, Ni, Hg, and Pb) concentrations. The characteristics of the area, scarcely influenced by industrial activities, and the extensive data set, make this study suitable for an appropriate multivariate and spatial geostatistical methodologies used for i) a reliable definition of large-scale marine sediments' geochemical backgrounds and ii) an accurate discrimination of different geological controls on trace-element distribution patterns. Enrichment factors estimated with respect to both the average shale composition and the weighted average metal concentrations measured in inland soils rule out significant anthropogenic inputs. A spatial-geostatistics approach (kriging of spatial component based on an accurate implementation of variographic surveying) was applied, and this is proposed as an appropriate quantitative methodology to define the geochemical backgrounds for the different heavy metals. Two nested spatial structures were identified for some of the heavy metals, thus allowing clear identification of local and regional geochemical controls related to the different spatial variability of grain size.     

秦皇岛近海养殖对潮间带微生物群落多样性的影响

潮间带微生物群落在驱动海岸带生态系统物质循环和能量流动中具有重要作用,近海养殖造成的环境问题日益凸显,但其对潮间带微生物群落结构的影响还缺乏研究。采用变性梯度凝胶电泳（DGGE）和限制性片段长度多态性（RFLP）的分子生物学技术,研究秦皇岛养殖区与旅游区潮间带沉积物中微生物多样性的差异,分析养殖区微生物的16S rRNA基因文库的组成特征。结果表明：养殖区的微生物群落结构与旅游区形成较大的差异,DGGE图谱中养殖区的特有条带主要集中于γ-变形菌纲（γ-proteobacteria）,还分布于α-变形菌纲（α-proteobacteria）,拟杆菌门（Bacteroidetes）,放线菌门（Actinobacteria）和厚壁菌门（Firmicutes）。影响潮间带微生物的群落结构的主要环境因子包括温度、盐度、pH和NO3-浓度,影响率达55.2%。对差异最大的洋河大桥南养殖区（Q1站）的微生物样品建立克隆文库分析群落结构,变形菌门（Proteobacteria）为优势菌群,占总群落的60%,其中γ-变形菌纲是主要存在的微生物纲,其余菌群包括放线菌门、拟杆菌门、蓝藻菌门（Cyanobacteria）和疣微菌门（Verrucomicrobia）的微生物。养殖区海岸带微生物群落中出现了与环境污染和赤潮密切相关的菌群,如拟杆菌门、肠杆菌属（Enterobacteriaceae）和α-变形细菌红细菌目（Roseovarius）的微生物。     

Ameliorants to immobilize Cd in rice paddy soils contaminated by abandoned metal mines in Korea

The Yarlung Tsangbo (YT) is a large river running across southern Tibet and has significant effects on its lower reaches, the Ganges–Brahmaputra Basin. In order to investigate the geochemical features of the YT, 18 surface sediment samples were collected; ten trace element concentrations were measured for bulk sediments and two fine grain size fractions. Meanwhile, basic physicochemical parameters and element concentrations of river water were also analyzed. Results indicated that the river water was alkaline (pH 8.42) and that dissolved oxygen was mainly controlled by river water temperature. Some elements (e.g., Zn and Ni) showed close negative relationship to mean grain size of the sediments. Concentrations of most heavy metals, except As of the YT bulk sediments, were similar to those of Upper Crustal Concentration and its lower reaches, indicating almost no anthropogenic impact. Arsenic of the YT sediments was derived fundamentally from the parent rocks of the YT Basin and was far higher than that of its lower reaches. This indicates that relatively small amounts of As from the study area were transported down to the Brahmaputra River under present, relatively dry climatic conditions. However, more YT sediments might have been transported to its low reaches during the Holocene due to the wet climate, giving high As concentration in Holocene sediments of the Ganges–Brahmaputra Basin. Thus, As transported by the YT may produce important influence on the Ganges–Brahmaputra Basin and contribute to its high As concentration in groundwater.     

Geological and geochemical factors affecting the radon concentration in homes in Cornwall and Devon,UK

Recently collected data for radon levels in houses in Devon and Cornwall are compared with geological and geochemical information. The region is underlain by granites intruded into folded sedimentary rocks. The highest incidence of affected houses is on granites. The granites are characterised by moderate uranium concentrations, a deep weathering profile and uranium in mineral phase which is easily weathered. However, while the uranium may be removed, radium, the immediate precursor of radon, can remain in situ. Radon is emanated easily from the host rock, and high values of radon in ground and surface waters and soil gases have been detected. The granite areas are also characterised by high values of uranium in stream sediments and waters. In contrast, other zones of high uranium in stream sediment samples do not necessarily exhibit high house radon concentrations, especially when underlain by relatively impermeable rocks. Permeable ground can give rise to high incidences, of affected houses despite having uranium levels close to the crustal abundance. It is concluded that the most efficient method of identifying zones of high radon potential is the soil gas radon survey.     

Seasonal variation of heavy metals in sediment of Lake Ulansuhai,China

Sediment samples were collected from 10 sites in Lake Ulansuhai during summer and winter 2009 to reveal seasonal variations in sediment heavy metal levels. The geoaccumulation index (GI) was calculated to assess the severity of metal pollution. The GI values suggest that, in winter, the lake sediments were polluted slightly with Cu (GI=0.66–1.34), Zn (GI=0.59–1.35), Cr (GI=0.49–0.82) and Pb (GI=0.60–0.96), and moderately with Cd (GI=1.03–4.23). The degree of pollution was higher in winter than in summer. By contrast, the degree of pollution was higher in summer than in winter for Hg and As. Correlation analysis can be used to identify factors influencing seasonal variations in heavy metals. The concetrations of Cu, Zn, Pb, Cr and Cd were negatively correlated with water temperature and hydrodynamic conditions, but positively correlated with organic matter concentration in the sediments and with a sediment particle size of<63 μm (p<0.01). Meanwhile, Hg and As concentrations were affected by redox state and salinity. Among the metals tested, Hg and Cd posed a more serious pollution risk.     

Distribution and speciation of heavy metals in Apulian coastal sediments

In the framework of the Interreg II Project Italy–Greece, distribution and speciation of trace metals in surface coastal sediments of Apulian regions were studied. A sequential extraction technique was used to determine the chemical association of heavy metals (Zn, Pb, Ni, Fe, Cr, Mn, Cu and Cd) with major sedimentary phases (acid soluble phases, easily reducible fraction and oxidizable matter). The relationship between the metals' content and the grain-size composition of the sediments was also considered: generally the elements resulted associated with the fine fraction, even if in some cases (Cu in the oxidizable phase) the opposite behaviour was observed. The studied area is not particularly polluted, except for some defined zones, as for example Brindisi's harbour. Speciation analysis revealed that the major part of the heavy metals are not easily mobilizable and bioavailable. Even in this case, there are some exceptions to the general behaviour: Cu and Pb in several samples are largely present in the oxidizable phase, which even if not immediately available can become a source of associated elements when redox conditions change.     

Geochemical fingerprints of “Prosecco” wine based on major and trace elements

The terroir can be defined as interactive ecosystem that includes climate, geology, soil and grapevine, and it is used to explain the hierarchy of high quality of wine. In order to understand the terroir functions, it is necessary to analyse the interactions among the geology, soil and wine. To define a geochemical fingerprint, the relationship between geochemistry of vineyard soil and chemical composition of wine from Veneto Italian Region was studied. The vineyards tested belonged to four distinct wineries located in the Veneto alluvial plain, included in the Controlled Designation of Origin (DOC) area of Prosecco. We investigated the relationship between major and trace elements in soil and their concentrations in Prosecco wine according to geographical origin. The detection of chemical composition in soil and wine were analysed by inductively coupled plasma mass spectrometry, and data were elaborated by nonparametric test and multivariate statistics Linear Discrimination Analysis. The geochemical and statistical analyses allowed to discriminate the vineyard soils according to geo-lithological characteristics of each area and to identify the geochemical “Prosecco” fingerprints, useful against fraudulent use of DOC wine labels.