Adsorption of zinc onto bed sediments of the River Ganga: adsorption models and kinetics

Abstract

A laboratory study was performed to study the effects of various operating factors, viz. initial metal ion concentration, solution pH, amount of sediment, contact time, particle size and temperature on the adsorption of zinc ions onto the bed sediments of the River Ganga (India). The equilibrium time was found to be of the order of 60 min. The adsorption curves are smooth and continuous leading to saturation, suggesting the possible monolayer coverage of zinc ions on the surface of the adsorbent. The extent of adsorption increases with an increase of pH. Furthermore the adsorption of zinc increases with increasing amount of adsorbent and decreases with adsorbent particle size. The important geochemical phases, iron and manganese oxide act as the active support material for the adsorption of zinc ions. The adsorption data have been analysed with the help of Langmuir and Freundlich adsorption models to determine the mechanistic parameters associated with the adsorption process. An attempt has also been made to determine thermodynamic parameters of the process, viz. free energy change, enthalpy change and entropy change. The negative values of free energy change (ΔG°) indicated the spontaneous nature of the adsorption of zinc onto the bed sediments and positive values of enthalpy change (ΔH°) suggest the endothermic nature of the adsorption process. The intraparticle diffusion of zinc in the adsorbent was found to be the main rate-limiting step.     

Adsorption of cadmium on riverine sediments: quantitative treatment of the large particles

The effects of solution pH, sediment dose, contact time, and particle size on the adsorption of cadmium ions on bed sediments have been studied for a highly polluted river in western Uttar Pradesh, India. The role of the coarser sediment and the clay and silt fractions has been examined. The optimum contact time needed to reach equilibrium is of the order of 30 and 60 min for 0–75 μm and 210–250 μm sediment size, respectively. The extent of cadmium adsorption increases with increasing pH and adsorbent doses and decreases with adsorbent particle size. The important geochemical phases, iron and manganese oxide, provide the active support material for the adsorption of cadmium. The competitive experiments conducted in the presence of lead and zinc ions indicate that both the ions suppress the ability of cadmium to adsorb on to sediments. The Langmuir and Freundlich adsorption models were used to determine the mechanistic parameters associated with the adsorption process. Copyright © 2000 John Wiley & Sons, Ltd.     

Adsorption of metal ions on bed sediments

Abstract

The adsorption of lead and zinc ions on bed sediments of the River Kali in western Uttar Pradesh, India, has been studied. The role of the coarser sediment fraction (210–250 μm) in controlling metal pollution has been elucidated and compared to those of the clay and silt fractions. The parameters controlling metal uptake, viz., solution pH, sediment dose, contact time, and particle size have been evaluated. The optimum contact time needed to reach equilibrium is of the order of 45 min for both the metal ions. The extent of adsorption increases with an increase of pH. Furthermore, the adsorption of the metal ions increases with increasing adsorbent doses and decreases with adsorbent particle size. The two geochemical phases of iron and manganese oxide act as the active support material for the adsorption of the metal ions.     

澜沧江中下游泥沙微表面电荷特性与磷吸附关系研究

河流泥沙是水生态系统生源要素的重要附着载体,其微形貌及电荷特性直接关系着泥沙对溶解态营养盐或污染物的吸附能力。本研究选取澜沧江中下游干流及主要支流为考察对象,采集28个河流水库断面的悬移质泥沙,采用原子力显微镜测定泥沙微表面电荷量,探究澜沧江泥沙的微表面电荷性质,研究纳米尺度下泥沙的微表面特性。研究结果表明:(1)微观界面,形貌对表面电荷分布影响明显,在纳米尺度下电势图与相位差图均展现出明显非均匀分布特征;(2)在流域分布上,不同区域表面电荷存在较大差异,流域沿程变化对泥沙表面电荷产生重要影响,总体变化呈现先减小后增大的趋势,表面电势值变化范围为-201.47～35.34 mV,表面电荷密度范围为0.07～3.65 mC/m²,不同区域电荷特性差别明显;(3)在梯级水电筑坝影响下,坝上坝下泥沙颗粒电势差与水库库容存在较好的线性相关关系,相关系数为0.8214,且坝下电势普遍高于坝上区域;(4)泥沙表面电势与磷吸附之间具有较强相关性,其相关系数为0.6657,同时表现出较好的线性拟合关系。研究结论对深入理解水电大坝建设对流域内污染物的迁移转化及解释泥沙的表面电性特征...     

Modelling transport dynamics of contaminated sediments in the headwater of a hydropower plant at the Upper Rhine River

Sediments are an essential habitat compartment in rivers, which is a subject to dynamic transport processes. In many rivers, the fine deposited sediments are contaminated with heavy metals and organic compounds. Contaminated deposits are considered as potential hot spots because of the risk of the mobilization under erosive hydraulic conditions. Numerical models for particulate contaminant transport are then necessary and can be applied to estimate and predict the potential impact of mobilized contaminants as an important contribution to sediment management. This paper focuses on the quantification of the amount of contaminated sediments resuspended during the extreme flood event in 1999 and the prediction of deposition one year after the flood event. To assess such erosive flood event, a 2D numerical transport model was developed to analyse the dynamics of erosion and sedimentation processes in the headwater of a cross dam at the Upper Rhine River. The dam consists of a weir, a hydropower plant, and a navigation lock. As the weir is operating only for flood management, a huge amount of sediment highly contaminated with the hexachlorobenzene (HCB) was deposited in the weir zone. Therefore, numerical simulations were performed to determine the spatial and temporal distribution of deposited contaminated sediments as depending on the river discharge and its distribution to the hydraulic structures. The numerical investigation presented here is taken as a retrospective analysis of the contaminated sediment dynamics in the headwater to improve future sediment management.     

Spatiotemporal variations of internal P-loading and the related mechanisms in the large shallow Lake Chaohu

Spatiotemporal variations of P species and adsorption behavior in water column, interstitial water, and sediments were investigated in the large shallow eutrophic Lake Chaohu. Ortho-phosphate (Ortho-P) and total phosphorus (TP) concentrations were significantly higher in the western part than in the eastern part of the lake, due to different nutrient inputs from the surrounding rivers. Moreover, paniculate phosphorus (PP) concentration was in a similar spatial pattern to Ortho-P and TP concentrations, and also showed significantly positive correlation with the biomass of Microcystis, indicating more uptake and store of phosphorus by Microcystis than by other algae. Increase of pH and intensive utilization of P by phytoplankton were the main factors promoting P (especially Fe-P) release from the sediment to interstitial water during the cyanobacterial blooms in Lake Chaohu. Spatial dynamics in TP concentration, P species and adsorption behavior of the sediment, coupled with the statistical analyses, suggested that the spatial heterogeneity of P contents in the sediment was influenced by various factors, e.g. human activities, soil geochemistry and mineral composition. In spite of similar TP contents in the sediments, increase in proportion of Fe-P concentration in the sediment may result in a high risk of P release.     

滇池表层沉积物铵态氮吸附特征

为研究滇池内源污染特征,2013年利用GIS软件针对滇池全湖布设36个采样点,采集表层沉积物,研究滇池表层沉积物铵态氮(NH_4+-N)吸附特征,同时分析沉积物的理化性质对NH_4+-N吸附特性的影响.结果表明:滇池表层沉积物对NH_4+-N的吸附量在前2 h之内呈增长趋势,吸附速率较大,之后沉积物对NH_4+-N的吸附量不随时间变化而变化,基本达到平衡,最大吸附速率均发生在0~5 min内;不同区域表层沉积物NH_4+-N最大吸附速率平均值表现为:外海南部湖心区外海北部草海,最大吸附量平均值表现为:湖心区外海南部外海北部草海,吸附效率平均值表现为:外海北部草海湖心区外海南部;沉积物对NH4+-N的吸附量与NH_4+-N的初始浓度大致呈线性关系,并且低浓度下表现出很好的吸附/解吸特征;滇池表层沉积物NH_4+-N的吸附解吸平衡浓度(ENC0)高于上覆水中NH_4+-N浓度,表明沉积物中NH_4+-N有向上覆水中释放的风险,沉积物在很长一段时间内起到水体污染"源"的作用;ENC0与沉积物中总氮、NH_4+-N含量呈显著正相关,本底吸附量和有机质总量呈显著负相关,沉积物吸附NH_4+-N主要受有机质的影响.     

Dating of sediments from Lake Zurich (Switzerland) with210Pb and137Cs

²¹⁰Pb- and¹³⁷Cs-measurements, and varve counting have been used to date sediment cores from Lake Zurich (Switzerland). Two cores from different water depths were dated with²¹⁰Pb/²¹⁰Po and revealed sediment accumulation rates of (0.055±0.015) g·cm^?2·y^?1 and (0.09±0.03) g·cm^?2·y^?1, respectively. A comparable rate of (0.07±0.01) g·cm^?2·y^?1 has been obtained from¹³⁷Cs measurements. These rates were confirmed by annual layer (varve)-counts which lead to rates of 0.07 g·cm^?2·y^?1. Constant²¹⁰Pb activities were observed in the top 6 cm of the sediment cores. This constancy is generally explained in the literature by mixing processes caused by bioturbation and by distortion during coring operations of the uppermost water-rich fluffy sediments. However the distinct¹³⁷Cs-maxima and the regular and undisturbed varve lamination of the top sediment observed in the cores of Lake Zurich contradict this assumption. In addition, measurements of⁷Be at the water/sediment interaces proved complete sediment core recovery and mechanically undisturbed sediments. Remobilization processes are assumed to cause the observed constant²¹⁰Pb activities. Remobilization may also be the reason for an incomplete²¹⁰Pb inventory in the sediments which contain only about 50% of the fallout from atmosphere. The results of the²¹⁰Pb dating should therefore be considered with some care. If existent, varve counting represents the easiest and most reliable means for dating lake sediments.     

Spatiotemporal variations of internal P-loading and the related mechanisms in the large shallow Lake Chaohu

Spatiotemporal variations of P species and adsorption behavior in water column, interstitial water, and sediments were investigated in the large shallow eutrophic Lake Chaohu. Orthophosphate (Ortho-P) and total phosphorus (TP) concentrations were significantly higher in the western part than in the eastern part of the lake, due to different nutrient inputs from the surrounding rivers. Moreover, particulate phosphorus (PP) concentration was in a similar spatial pattern to Ortho-P and TP concentrations, and also showed significantly positive correlation with the biomass of Microcystis, indicating more uptake and store of phosphorus by Microcystis than by other algae. Increase of pH and intensive utilization of P by phytoplankton were the main factors promoting P (especially Fe-P) release from the sediment to interstitial water during the cyanobacterial blooms in Lake Chaohu. Spatial dynamics in TP concentration, P species and adsorption behavior of the sediment, coupled with the statistical analyses, suggested that the spatial heterogeneity of P contents in the sediment was influenced by various factors, e.g. human activities, soil geochemistry and mineral composition. In spite of similar TP contents in the sediments, increase in proportion of Fe-P concentration in the sediment may result in a high risk of P release.     

Seasonality of low flows and dominant processes in the Rhine River

Low flow forecasting is crucial for sustainable cooling water supply and planning of river navigation in the Rhine River. The first step in reliable low flow forecasting is to understand the characteristics of low flow. In this study, several methods are applied to understand the low flow characteristics of Rhine River basin. In 108 catchments of the Rhine River, winter and summer low flow regions are determined with the seasonality ratio (SR) index. To understand whether different numbers of processes are acting in generating different low flow regimes in seven major sub-basins (namely, East Alpine, West Alpine, Middle Rhine, Neckar, Main, Mosel and Lower Rhine) aggregated from the 108 catchments, the dominant variable concept is adopted from chaos theory. The number of dominant processes within the seven major sub-basins is determined with the correlation dimension analysis. Results of the correlation dimension analysis show that the minimum and maximum required number of variables to represent the low flow dynamics of the seven major sub-basins, except the Middle Rhine and Mosel, is 4 and 9, respectively. For the Mosel and Middle Rhine, the required minimum number of variables is 2 and 6, and the maximum number of variables is 5 and 13, respectively. These results show that the low flow processes of the major sub-basins of the Rhine could be considered as non-stochastic or chaotic processes. To confirm this conclusion, the rescaled range analysis is applied to verify persistency (i.e. non-randomness) in the processes. The estimated rescaled range statistics (i.e. Hurst exponents) are all above 0.5, indicating that persistent long-term memory characteristics exist in the runoff processes. Finally, the mean values of SR indices are compared with the nonlinear analyses results to find significant relationships. The results show that the minimum and maximum numbers of required variables (i.e. processes) to model the dynamic characteristics for five out of the seven major sub-basins are the same, but the observed low flow regimes are different (winter low flow regime and summer low flow regime). These results support the conclusion that a few interrelated nonlinear variables could yield completely different behaviour (i.e. dominant low flow regime).     

Modelling floodplain sedimentation using particle tracking

Both climate change and river rehabilitation projects induce changes in floodplain sedimentation. Notably along the lower River Rhine, the sediment deposition patterns and rates are subject to change. To assess the magnitude of these changes, we developed the MoCSED model, a floodplain sedimentation model within a geographical information system for the lower Rhine River. We based MoCSED on the ‘method of characteristics’ (MoC), a particle tracking method that minimizes numerical dispersion. We implemented the MoCSED model in the PCRaster dynamic modelling language. The model input comprises initial suspended sediment concentrations, water levels, flow velocities, and longitudinal and transverse dispersivities. We used a combination of the Krone and Chen concepts to calculate the subsequent sedimentation (SED routine). We compared the model results with sediment trap data for the Bemmel floodplain along the Dutch Waal River during the 2003 inundation. This comparison showed that MoCSED was able to simulate the pattern of sediment deposition. In addition, the model proved to be an improvement in comparison with a conventional raster‐based floodplain sedimentation model for the lower River Rhine. In future, MoCSED may serve well to study the impact of a changing discharge regime due to climate change and floodplain rehabilitation plans on deposition of sediments. Copyright © 2006 John Wiley & Sons, Ltd.     

Adsorption behaviour of dibutyl phthalate on marine sediments

Laboratory experiments were carried out to investigate the adsorption behaviour of dibutyl phthalate (DBP) on marine sediments collected from five different sites in Victoria Harbour, Hong Kong. DBP adsorption can be well described by the Langmuir isotherm. The maximum DBP adsorption capacity (Q(max)) of the marine sediments ranges from 53 to 79 mg g(-1), which has a positive correlation with their organic content. Around 90% of the organic can be removed from the sediments with treatment by H(2)O(2) oxidation, and the Q(max) then decreases to a range between 13 and 22 mg g(-1). The black carbon content of the sediments has a much greater DBP adsorption capacity than does the natural organic matter of the sediments. The amount of DBP adsorbed on the sediments increases as the salinity of the marine water increases.     

Effect of extracellular polymeric substances on the phosphorus adsorption characteristics of sediment particles

Extracellular polymeric substances (EPS) have a great impact on the characteristics of sediment particles and their environmental effects in hydro-environmental systems, yet little effort has been made to study the considerable variability in the element adsorption process of sediment particles caused by EPS. Understanding the variability of the adsorption characteristics of sediment particles associated with EPS and quantifying the scale of the adsorption isotherm parameters are important for understanding how EPS mediate sediment properties and environmental factors. In this paper, isothermal equilibrium adsorption experiments are done on phosphorus to study the influence of EPS on the adsorption characteristics of sediment particles, and the Langmuir adsorption isotherm is applied to analyze the adsorption rule of sediment particles under the impact of EPS. The current research demonstrates that significant differences will take place in the adsorption characteristics of sediments coated with EPS at different development phases and the phosphorus adsorption capacity of sediment particles increases with the growth of EPS. The difference in the adsorption percentage between sediment particles coated with EPS of 0 and 6 weeks growth time is about 42%–60% for different initial aqueous phosphorus concentration. A formula describing the adsorption isotherm parameter of the maximum material (element) adsorption capacity of sediment particles change over time is further proposed based on the experimental data. The current study provides some evidence for the interaction of sediment particles, EPS, and adsorbed elements in the water environment.     

The effect of the new Massachusetts Bay sewage outfall on the concentrations of metals and bacterial spores in nearby bottom and suspended sediments

Since the new outfall for Boston's treated sewage effluent began operation on September 6, 2000, no change has been observed in concentrations of silver or Clostridium perfringens spores (an ecologically benign tracer of sewage), in bottom sediments at a site 2.5 km west of the outfall. In suspended sediment samples collected with a time-series sediment trap located 1.3 km south of the outfall, silver and C. perfringens spores increased by 38% and 103%, respectively, in post-outfall samples while chromium, copper, and zinc showed no change. All metal concentrations in sediments are <50% of warning levels established by the Massachusetts Water Resources Authority. An 11-year data set of bottom sediment characteristics collected three times per year prior to outfall startup provides perspective for the interpretation of post-outfall data. A greater than twofold increase in concentrations of sewage tracers (silver and C. perfringens) was observed in muddy sediments following the exceptional storm of December 11-16, 1992 that presumably moved contaminated inshore sediment offshore.     

Improving age-depth models of fluvio-lacustrine deposits using sedimentary proxies for accumulation rates

Lacustrine fills, including those of oxbow lakes in river floodplains, often hold valuable sedimentary and biological proxy records of palaeo-environmental change. Precise dating of accumulated sediments at levels throughout these records is crucial for interpretation and correlation of (proxy) data existing within the fills. Typically, dates are gathered from multiple sampled levels and their results are combined in age-depth models to estimate the ages of events identified between the datings. In this paper, a method of age-depth modelling is presented that varies the vertical accumulation rate of the lake fill based on continuous sedimentary data. In between Bayesian calibrated radiocarbon dates, this produces a modified non-linear age-depth relation based on sedimentology rather than linear or spline interpolation.The method is showcased on a core of an infilled palaeomeander at the floodplain edge of the river Rhine near Rheinberg (Germany). The sequence spans from ∼4.7 to 2.9 ka cal BP and consists of 5.5 m of laminated lacustrine, organo-clastic mud, covered by ∼1 m of peaty clay. Four radiocarbon dates provide direct dating control, mapping and dating in the wider surroundings provide additional control. The laminated, organo-clastic facies of the oxbow fill contains a record of nearby fluvial-geomorphological activity, including meander reconfiguration events and passage of rare large floods, recognized as fluctuations in coarseness and amount of allochthonous clastic sediment input. Continuous along-core sampling and measurement of loss-on-ignition (LOI) provided a fast way of expressing the variation in clastic sedimentation influx from the nearby river versus autochthonous organic deposition derived from biogenic production in the lake itself. This low-cost sedimentary proxy data feeds into the age-depth modelling. The sedimentology-modelled age-depth relation (re)produces the distinct lithological boundaries in the fill as marked changes in sedimentation rate. Especially the organo-clastic muddy facies subdivides in centennial intervals of relative faster and slower accumulation. For such intervals, sedimentation rates are produced that deviate 10–20% from that in simpler stepped linear age-models. For irregularly laminated muddy intervals of the oxbow fill – from which meaningful sampling for radiocarbon dating is more difficult than from peaty or slowly accumulating organic lake sediments – supplementing spotty radiocarbon sampling with continuous sedimentary proxy data creates more realistic age-depth modelling results.     

The effects of mariculture activities on the adsorption/desorption and chemical fractionations of mercury on sediments

The aims of the present study were to investigate the effects of mariculture activities on inorganic mercury (Hg(2+)) adsorption/desorption on sediments and the distributions of newly adsorbed Hg(2+) on different chemical fractionations. The adsorption amount and binding energy of Hg(2+) on mariculture sediment (MS) were significantly higher (p<0.05) than reference sediment (RS). This may be explained by the strong complexation role that exists between Hg(2+) and organic matter (OM), which derived from unconsumed fish feed and fish metabolites. The reducible Hg(2+) in MS was significantly lower (p<0.01) than RS, which may have been caused by the decreasing amount of iron and manganese hydroxide in MS, lead to the decrease of Hg(2+) bound to them. On the contrary, the residual Hg(2+) was significantly higher (p<0.01) in MS than RS, which suggests that newly adsorbed Hg(2+) was more stable in MS than RS.     

The role of vegetation in the retention of fine sediment and associated metal contaminants in London's rivers

Many urban rivers receive significant inputs of metal‐contaminated sediments from their catchments. Restoration of urban rivers often creates increased slack water areas and in‐channel vegetation growth where these metal‐contaminated sediments may accumulate. Quantifying the accumulation and retention of these sediments by in‐channel vegetation in urban rivers is of importance in terms of the planning and management of urban river restoration schemes and compliance with the Water Framework Directive. This paper investigates sediment properties at four sites across three rivers within Greater London to assess the degree to which contaminated sediments are being retained. Within paired restored and unrestored reaches at each site, four different bed sediment patch types (exposed unvegetated gravel, sand, and silt/clay (termed ‘fine’) sediments, and in‐channel vegetated sediments) were sampled and analysed for a range of metals and sediment characteristics. Many samples were found to exceed Environment Agency guidelines for copper (Cu), lead (Pb) and zinc (Zn) and Dutch Intervention Values for Cu and Zn. At all sites, sediments accumulating around in‐channel vegetation were similar in calibre and composition to exposed unvegetated fine sediments. Both bed sediment types contained high concentrations of pseudo‐total and acetic acid extractable metal concentrations, potentially due to elevated organic matter and silt/clay content, as these are important sorbtion phases for metals. This implies that the changed sediment supply and hydraulic conditions associated with river restoration may lead to enhanced retention of contaminated fine sediments, particularly around emergent plants, frequently leading to the development of submerged and emergent landforms and potential river channel adjustments. High pseudo‐total metal concentrations were also found in gravel bed sediments, probably associated with iron (Fe) and manganese (Mn) oxyhydroxides and discrete anthropogenic metal‐rich particles. These results highlight the importance of understanding the potential effects of urban river restoration upon sediment availability and channel hydraulics and consequent impacts upon sediment contaminant dynamics and storage. Copyright © 2014 John Wiley & Sons, Ltd.     

Chemical contamination of a coral reef by the grounding of a cruise ship in Bermuda

Bulk metal analyses of surficial sediments collected around the Norwegian Crown cruise ship grounding site in Bermuda indicated significant but localized contamination of reef sediments by copper and zinc, caused by the stripping of the tri-butyltin (TBT)-free antifouling (AF) paint (Intersmooth 460) from the underside of the hull. Highest copper and zinc values were found in heavily compacted and red-pigmented sediments inside the impact scar and were comparable to levels found close to slip ways of local boat yards where AF paints from hull stripping and cleaning processes are washed into the sea. The re-distribution of AF contaminated sediments by storms and deposition on nearby reefs constitutes a significant ecological risk that could delay recovery processes and reduce the effectiveness of remediation efforts. Whilst the ecotoxicological effects of AF paint particles interspersed with sediment is unknown, and in need of further study, it is argued that the significance of AF paint contamination of grounding sites has been overlooked.     

The mobility, partitioning and degradation of atrazine and simazine in the salt marsh environment

The transfer of the s-triazine herbicides onto a salt marsh and their subsequent behaviour and fate has been investigated in a series of laboratory-based experiments. The results indicate that atrazine and simazine enter the marsh system and undergo negligible adsorption onto suspended solids. Herbicide accumulation within the sediment compartment was thought to be due to other mechanisms such as partitioning into the surface microlayer, or association with sediment flocs. s-Triazine mobility within the sediment was dictated by compound and sediment type, reflecting greater mobility in the mud flat than the vegetated marsh sediment. The majority of the herbicides were, however, retained in the uppermost layers of the sediment profile indicating that salt marsh sediments act as a sink for these compounds. Although degradation rates in the sediment were relatively rapid, detectable levels of the parent compounds were still evident after 71 days, which implies that these compounds may persist in salt marsh sediments. The absence of degradation in the aqueous phase implies that adsorption to particulate matter is a prerequisite for the degradation of the s-triazine herbicides.