Kinetics and mechanisms of pH-dependent selenite removal by zero valent iron

The kinetics of Se(IV) removal by zero valent iron (ZVI) open to the air as a function of pH and the involved mechanisms were investigated in this study. The specific rate constants of Se(IV) removal by ZVI decreased from 92.87 to 6.87 L h⁻¹ m⁻² as pH increased from 4.0 to 7.0. The positive correlation between the removal rate of Se(IV) and the generation rate of Fe(II) and the depression of Se(IV) removal in the presence of 1,10-phenanthroline indicated that both ZVI and adsorbed Fe(II) on ZVI surface contributed to the reductive removal of Se(IV). The soft X-ray STXM measurement confirmed the adsorption of Fe(II) on the surface of ZVI and freshly formed ferric (hydr)oxides. Se(IV) was removed by adsorption followed by reduction to Se(0) on ZVI surface at pH 4.0–7.0, as revealed by XANES spectra. A core-shell structure was observed when ZVI reacted with Se(IV)-containing solution for 3 h at pH 6.0. Se(IV) was reduced to Se(0) and co-precipitated with the freshly formed Fe(III), forming the shell surrounding the iron core. After reaction for 24 h, the generated Se(0) was surrounded by multiple layers of Fe(III) oxides/hydroxides. SEM images and XRD patterns revealed that the corrosion products of ZVI at pH 6.0 transformed from amorphous iron hydroxides to lepidocrocite (γ-FeOOH) as reaction proceeded. The final corrosion products of ZVI contained both lepidocrocite and goethite at pH 5.0 while they were X-ray amorphous at pH 4.0 and 7.0.     

Partitioning of trace metals before and after biological removal of metals from sediments

Metal removal by biological solubilization in three strongly contaminated sediments was carried out in a two-liter stirred bioreactor. Biological treatment yielded metal removal efficiencies in the range of 11-30%, 43-57%, 60-79%, 61-90%, 18-21%, 0-10% for Pb, Cu, Zn, Cd, Ni and Cr, respectively. The treated sediments were then rinsed with a NaCl solution (0.5 M), resulting in an increase by nearly 47% in Pb removal for the three sediments, while for other metals (Cu, Zn, Cd, Ni, Cr), the NaCl rinse did not seem to allow any significant increase in metal solubilization. A standard procedure of sequential selective extraction (SSE) was applied to the sediments before and after each treatment. With regard to Pb, Zn and Cd, the carbonate bound fractions (2/3 sediments) represented 18-42% of metals prior to treatment, while the iron and manganese oxides bound fraction constituted 39-60% of metals for the three sediments. Between 90 and 100% of Pb, Zn and Cd removed by the process came from the fractions bound to carbonates and from those bound to Fe and Mn oxides. The organic matter and sulfide bound fractions contained 65-72% of total Cu present before treatment and the process removed, on average, 63% Cu present in this fraction. In contrast, Ni and Cr were found mainly in the residual fractions (50-80%). Finally, this biological treatment did not solubilize Cr appreciably, while removal of Ni mostly originated from the carbonate and Fe/Mn oxides fractions (70-80%).     

Potential kinetic availability of metals in sulphidic freshwater sediments

The insolubility of metal sulphides is believed to limit the bioavailability of trace metals in sulphidic sediments. However, if non-equilibrium conditions are important, metals may be more available than simple thermodynamic calculations suggest. To investigate the possible dynamic supply of Cu, Ni and Zn in a sulphidic freshwater sediment, they were measured, along with iron, manganese and sulphide, by the technique of diffusive gradients in thin-films (DGT). DGT measures the supply of solute from sediment to solution in response to a local solute sink. Release of Mn, Cu, Zn and Ni was observed at the sediment surface and attributed to the supply from reductive dissolution of manganese oxides. The depth profile of simultaneously extractable metals (SEM) for Cu and Ni followed the shape of the Mn profile more closely than the profiles of either acid volatile sulphur (AVS) or Fe, again consistent with supply from Mn oxides. Solubility calculations for a mesocosm of homogenised sediment indicated supersaturation with respect to the sulphides of Fe, Cu, Ni and Zn, yet DGT measurements demonstrated a substantial supply of both trace metals and sulphide from the solid phase to the pore waters. Ratios of metals measured in pore waters by DGT were consistent with their release from iron and manganese oxides, indicating that supply, as much as removal processes, determines the pseudo-steady state concentrations in the pore waters. The observations suggest that trace metals are not immediately bound in an insoluble, inert form when they are in contact with sulphide. This has consequences for modelling metal processes in sediment, as well as for uptake by some biota.     

Removal of sulfate and heavy metals by sulfate reducing bacteria in short-term bench scale upflow anaerobic packed bed reactor runs

Mildly acidic metal (Cu, Zn, Ni, Fe, Al and Mg), arsenic and sulfate contaminated waters were treated, over a 14 day period at 25 degrees C, in a bench-scale upflow anaerobic packed bed reactor filled with silica sand and employing a mixed population of sulfate-reducing bacteria (SRB). The activity of SRB increased the water pH from approximately 4.5 to 7.0, and enhanced the removal of sulfate and metals in comparison to controls not inoculated with SRB. Addition of organic substrate and sulfate at loading rates of 7.43 and 3.71 kg d(-1) m(-3), respectively, resulted in >82% reduction in sulfate concentration. The reactor removed more than 97.5% of the initial concentrations of Cu, Zn and Ni, while only >77.5% and >82% of As and Fe were removed, respectively. In contrast, Mg and Al levels remained unchanged during the whole treatment process. The removal patterns for Cu, Zn, Ni and Fe reflected the trend in their solubility for their respective metal sulfides, while As removal appeared to coincide with decreasing Cu, Zn, Ni and Fe concentrations, which suggests adsorption or concomitant precipitation with the other metal sulfides.     

The adsorption of Cu, Mn and Zn by iron oxyhydroxide in model estuarine solutions

Chemical models have been used to examine the adsorption behaviour of Cu, Mn and Zn onto freshly precipitated iron oxyhydroxide as a function of pH and salinity. Solutions of varying salinity (S = 0, 5, 10, 15‰) containing 0.05 mM Fe and 1.5 μM of each metal were allowed to attain equilibrium under carefully controlled conditions. The solutions were analysed for the dissolved metals (passing a 0.45 μm filter) over the pH range 3.5–10. The pH of the onset of adsorption followed the order Cu < Zn < Mn and it occurred at pHs well below the hydrolysis of the cations in the bulk solution. Hypotheses on the metal uptake involving coulombic interactions between the precipitate and the metal species in solution did not fit the observations and it was concluded that a detailed knowledge of surface complexation reactions was required, as was shown for Cu. The adsorption isotherms for Cu were independent of salinity, on the other hand, those for Zn and Mn showed an increase in the pH of the adsorption edge with increases in salinity. It was suggested that the major cations, Ca²⁺ and Mg²⁺, were probably co-adsorbed and competition from these species for adsorption sites increased with increasing salinity. The results reported here are useful for the development of predictive models for the fate of trace metals injected into estuarine systems where iron compounds may be freshly precipitated.     

Equilibrium and kinetics of metal ion adsorption onto a commercial H-type granular activated carbon: experimental and modeling studies

Systematic studies on metal ion adsorption equilibrium and kinetics by a commercial H-type granular activated carbon were carried out. Titration of the carbon showed that the surface charge density decreased with an increasing pH. Higher copper adsorption was obtained with increasing solution pH and ionic strength. Metal removal was in the descending order: Cu2+ > Zn2+ approximately Co2+. Copper removal was not affected by addition of zinc or cobalt, while copper can reduce both zinc and cobalt removal. Kinetic experiments demonstrated that the copper adsorption rapidly occurred in the first 30-60 min and reached the complete removal in 3-5 h. Removal of zinc and cobalt was slightly slower than that of copper. It was found that the mass transfer is important in the metal adsorption rate. The surface complex formation model was used successfully to describe the surface change density, as well as the single- and multi-species metal adsorption equilibrium. The copper removal was due to adsorption of Cu2+, CuOH+, and CuCl+, while the zinc and cobalt uptake was due to the formation of surface metal complexes of SOM2+ and SOMOH+ (M = Zn and Co). It was found that the diffusion-control model well described the adsorption kinetics with various metal ions and pH values. Finally sensitivity analysis on the kinetic model's parameters was carried out.     

Simultaneous removal of As, Cd, Cr, Cu, Ni and Zn from stormwater: experimental comparison of 11 different sorbents

The potential of using alumina, activated bauxsol-coated sand (ABCS), bark, bauxsol-coated sand (BCS), fly ash (FA), granulated activated carbon (GAC), granulated ferric hydroxide (GFH), iron oxide-coated sand (IOCS), natural zeolite (NZ), sand, and spinel (MgAl(2)O(4)) as sorbents for removing heavy metals from stormwater are investigated in the present study. The ability of the sorbents to remove a mixture of As, Cd, Cr, Cu, Ni and Zn from synthetic stormwater samples were evaluated in batch tests at a starting pH of 6.5. The metal speciation and saturation data is obtained using the PHREEQ-C geochemical model and used to elucidate the sorption data. It is found that BCS, FA, and spinel have significantly higher affinity towards heavy metals mainly present as cationic or non-charged species (i.e. Cd, Cu, Ni and Zn) compared to those present as anionic species (i.e. As and Cr). However, IOCS, NZ and sand have higher affinity towards As and Cr, while alumina has equally high affinity to all tested heavy metals. The Freundlich isotherm model is found to fit the data in many cases, but ill fitted results are also observed, especially for FA, BCS and GAC, possibly due to leaching of some metals from the sorbents (i.e. for FA) and oversaturated conditions making precipitation the dominant removal mechanism over sorption in batches with high heavy metal concentrations and pH. Calculated sorption constants (i.e. K(d)) are used to compare the overall heavy metal removal efficiency of the sorbents, which in a decreasing order are found to be: alumina, BCS, GFH, FA, GAC, spinel, ABCS, IOCS, NZ, bark, and sand. These findings are significant for future development of secondary filters for removal of dissolved heavy metals from stormwater runoff under realistic competitive conditions in terms of initial heavy metal concentrations, pH and ionic strength.     

Simultaneous removal of Cu, Mn and Zn from drinking water with the use of clinoptilolite and its Fe-modified form

Zeolites have been widely used in water treatment and especially clinoptilolite, due to its low cost and high abundance. It has large cation-exchange capacity and is capable of removing large quantities of heavy metals from contaminated water samples. By loading the surface of clinoptilolite with amorphous Fe-oxide species, a total improvement in adsorption capacity could be achieved. Thus, the Clin–Fe oxide system is capable of adsorbing significantly higher heavy metal concentrations than untreated clinoptilolite with simultaneous noticeable decrease in water hardness. Batch adsorption experiments have shown that Clin–Fe system has very large Cu, Zn and Mn adsorption capacity and for most of the cases the treated water samples were suitable for human consumption or agricultural use. New experiments were conducted to study the effectiveness of clinoptilolite and of the Clin–Fe system in removal of Cu, Mn, Zn, present simultaneously in water samples, so that the study of metal–sorbent chemical behavior and of the adsorption selectivity would be feasible. Desorption of metals was also examined and an integrated approach of the effectiveness of such materials in drinking water treatment is presented.     

Hexavalent chromium removal from near natural water by copper-iron bimetallic particles

The reduction of hexavalent chromium (Cr(VI)) by zero-valent iron (ZVI) is self-inhibiting in near natural groundwater because insulating Fe(III)-Cr(III) (oxy)hydroxide film forms on the ZVI surface during the reaction. This study tries to overcome this deficiency by coating the surface of ZVI with copper to form copper-iron bimetallic particles. The Cr(VI) removal rate by ZVI rose significantly after the copper coating was applied. The copper loading needed for enhancing Cr(VI) removal was much higher than that needed for enhancing removal of chlorinated organic compounds or other oxidative contaminants, because of the higher oxidation potential of Cr(VI). The results of X-ray photoelectron spectroscopy (XPS) indicate that coating copper onto the surface of ZVI can not only increase the deepness of the oxidation film but also increase the oxidation state of iron in the film. This phenomenon means higher Cr(VI) removal capacity per unit weight of ZVI.     

Size dependent elemental composition of road-associated particles

Stormwater particles often provide transport for metals and other contaminants, however only larger particles are effectively removed by typical best management practices. Fine particles and their associated constituents are more likely to reach receiving waters; this merits further investigation regarding the metal contribution of fine (d(p)<10 microm) and very fine (d(p)<1.5 microm) particles. Road associated particles were collected by vacuuming a road surface and by collecting highway stormwater runoff. A cell sorter was employed to sort road associated particles into four size ranges: 0.1-0.3, 0.3-0.5, 0.5-1.0, and 1.0-1.5 microm. These very fine particles, along with six particle size ranges (total range <2-63 microm) separated using a settling column, were analyzed for Al, Mn, Fe, Cr, Ni, Cu, Zn, and Pb using Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Enrichment factors (EFs), calculated using Al as a basis to represent crustal contributions, were similar for the vacuumed road dust and the stormwater runoff. Fe and Mn were minimally depleted (0.1x) or near unity for all size ranges (Fe EF range 0.01-3.7; Mn EF range 0.02-10.6). Cr, Ni, Cu, Zn, and Pb were moderately (10x) to considerably (>100x) enriched for most size ranges; these metals were most enriched in the very fine fractions (max EF ~ 4900 in Zn, 0.1-0.3 microm). Based on this preliminary study, a cell sorter is an acceptable means of fractionating aqueous particles of diameter 0.1-1.5 microm. In spite of their minimal relative mass contribution, the very fine particles are environmentally relevant due to their mobility and enrichment in potentially toxic metals.     

Bifunctional resin-ZVI composites for effective removal of arsenite through simultaneous adsorption and oxidation

Bifunctional resin-supported nanosized zero-valent iron (N–S-ZVI) composite was developed by combining the oxidation properties of nZVI/O₂ with adsorption features of iron oxides and anion-exchange resin N–S. In batch culture experiments, N–S and the N–S-ZVI composite were examined for As(III) and As(V). The results reveal that ZVI in the composite played a key role in enhancing As(III) removal. The N–S-ZVI composites could oxidize more toxic As(III) to less toxic As(V) with high efficiency under ambient conditions without the need of noble metals. At the same time, the oxidized As(V) could be effectively removed by adsorption onto the surface of composites. The mechanisms for the oxidation of As(III) to As(V) and the simultaneous removal of As(V) are proposed. In order to investigate the potential performance of N–S-ZVI in practical use, the effects of solution pH and coexisting anions on arsenite removal and on fixed-bed column treatment of simulated waters were studied. All the results indicated that the bifunctional composites have a great potential for As(III) removal from contaminated waters.     

Removal of copper ions from aqueous solutions by a steel-making by-product

A study is made of the use of a steel-making by-product (rolling mill scale) as a material for removing Cu(2+) ions from aqueous solutions. The influence of contact time, initial copper ion concentration and temperature on removal capability is considered. The removal of Cu(2+) ions from an aqueous solution involves two processes: on the one hand, the adsorption of Cu(2+) ions on the surface of mill scale due to the iron oxides present in the latter; and on the other hand, the cementation of Cu(2+) onto metallic iron contained in the mill scale. Rolling mill scale is seen to be an effective material for the removal of copper ions from aqueous solutions.     

Prediction of heavy metal concentrations in urban stormwater

Heavy metals in urban stormwater runoff can adversely impact aquatic ecosystems. Successful management of such systems requires the accurate prediction of contaminant concentrations. This has created the need for simplistic statistical models. In this study, models were constructed to predict three of the most prevalent heavy metal constituents in urban stormwater: copper (Cu), lead (Pb) and zinc (Zn). Data from the United States, obtained during the Nationwide Urban Runoff Program (NURP), were used to calibrate and verify the models. A comparison of the models revealed that regression models were more accurate than the landuse‐based or metropolitan area averages of event mean concentration (EMC). The regression models also provided insight into important stormwater processes. It was found that pollutant accumulation on the catchment surface was essentially supply limited, and that significant portions of heavy metals originate from highly impervious areas.     

Urban Water Journal: Special Issue on Transients

Retention/detention basins are commonly used to remediate runoff from road surfaces in an attempt to remove contaminants before these materials enter adjacent waterways. However, the efficiency of such devices in removing contaminants is not well known, especially for Australian conditions. The efficiency of a retention/detention device adjacent to a major motorway in Sydney (Australia) was assessed for total suspended solids (TSS), a suite of trace metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb, Zn), nutrients (TP, TKN, NO_x, TN) and faecal coliforms. The mean removal efficiency of Cu, Pb, Mn and Zn was 23, 41, 43 and 41%, respectively, whereas the mean reduction in Cr, Fe and Ni concentrations was only 0, 3 and 1%, respectively. TSS in stormwater entering the retention/detention basin was highly variable resulting in large variations in removal efficiencies (range: ?12 to 93%; mean: 40%). The mean removal efficiency of Kjeldahl nitrogen (TKN) and total nitrogen (TN) was high (56 and 28%, respectively) in contrast to total NO_x and total phosphorus (TP) (?42 and ?5%, respectively). Faecal coliform was low to very low (<5000 cfu/100 ml) and removal efficiency was 16 to 68%. Possible leaching of fine terrigenous particles from the gravel bed of the retention/detention basin may have contributed to the increase in Cr, Fe and Ni concentrations in effluent stormwater.     

黄河口表层沉积物中的可提取铜和锌

通过偏相关分析和逐步回归分析发现黄河口及其附近海域表层沉积物中可提取铜主要结合在水含氧化物和粘土矿的外表面上．而可提取锌主要结合在水合氧化铁上，其次结合在水含氧化锰上．用１ｍｏｌ盐酸提取沉积物中的铜、锌、铁和锰，同时测定了沉积物的外比表面积．     

Size fractionation of metals in runoff from residential and highway storm sewers

Stormwater sampling for particulate, colloidal, and dissolved metals was conducted for several storms at six outfalls in Monmouth County, NJ. Samples were initially sequentially filtered through 5 microm, 0.45 microm, and 10 kDa filters. Of the heavy metals, Cu and Zn were mostly either dissolved (<10 kDa) (20-100%) or in the particulate size fractions >5 microm (0->70%). Pb and Cr were associated exclusively with particles >5 microm in size. Fe, Al, and Si were found mostly in larger size fractions (>70%), with smaller amounts 0.45-5 microm in size. Preliminary data from a small set of samples passed through coarser filters suggested that metals may actually be largely associated with particles larger than 20 microm. Variable and sometimes large dissolved fractions of Cu and Zn can contribute to erratic metals removal by structural best management practices (e.g., wet ponds, detention basins). The size fractionation of stormwater constituents has implications for the design and performance of stormwater control structures and the aquatic toxicity risks posed by the metals. The results demonstrate the importance of obtaining particle size data when planning stormwater treatment.     

Decomposition of belowground litter and metal dynamics in salt marshes (Tagus Estuary, Portugal)

The concentrations of C, Fe, Mn, Zn, Cu, Pb and Cd were determined monthly in decomposing roots of Halimione portulacoides, using litterbag experiments, in two salt marshes of the Tagus estuary with different levels of contamination. Although carbon concentrations varied within a narrow interval during the experiment, litter decomposed rapidly in the first month (weight loss between 0.051 and 0.065 g d(-1)). The time variation of metals was examined in terms of Me/C ratios and metal stocks. Ratios of Fe/C and Mn/C and their metal stocks increased in spring, presumably due to the precipitation of oxides in the surface of decomposing roots. Subsequent decrease of Fe/C and Mn/C ratios suggests the use of Fe and Mn oxides, as electron acceptors, in the organic matter oxidation. Zinc, Cu, Pb and Cd ratios to C were, in general, higher than at initial conditions implying that metal that leached out was slower than carbon. However, metal stocks decreased during the experiment indicating that incorporation or sorption of metals in Fe and Mn oxides did not counterbalance the amount of Zn, Pb and Cd released from decomposing litter. An exception was observed for Cu, since stock in the less contaminated marsh (Pancas) increased during the decomposition, indicating that litter was efficient on Cu binding under more oxidising conditions. These results emphasize the importance of litter decomposition and sediment characteristics on metal cycling in salt marshes.     

Adsorption of Zn(II) in Oxisols as affected by selective removal of soil fractions

The relative contribution of organic matter, amorphous and crystalline Fe oxides and Al oxides to soil Zn adsorption was evaluated in contaminated and uncontaminated Brazilian soils. Soil samples were equilibrated with Zn solutions and Zn adsorption was determined using the Langmuir adsorption isotherm. The Fe and Al oxides (non‐silicated clays) and the organic matter contents of the soils were the main contributors to the variation in Zn adsorption. The Zn maximum adsorption capacity in the soil with the greatest sand and organic carbon contents was higher than in the higher clay content soil, which was second in organic carbon content. Related to the whole soil samples, as the soil organic matter was removed, the Zn maximum adsorption capacity decreased in most of the observations. The removal of Fe and Al oxides decreased the soil Zn maximum adsorption capacity in some cases and increased it in others, with no clear variation in the pathway. For both whole soil and soil fractions, the isotherms for Zn adsorption to soil, fitted to the Langmuir equation, showed two linear portions or pathways (Part I and Part II). The bonding energy coefficient was higher in Part I (related to specific chemical adsorption) than in Part II (related to electrostatic interactions), which suggests a higher affinity between Zn and soil particles in Part I as compared with Part II.     

Effects of PVC,cast iron and concrete conduit on concentrations of copper in stormwater

Architectural applications of copper on roofs, gutters and facades exposes it to weathering forces, such as wind and all forms of precipitation. This leads to the dissolution of copper from these surfaces and its introduction into local watersheds. The potential for exposure in local watersheds is a function of the amount of copper entering the watershed and the assimilation capacity of a wide variety of natural and manmade substrates that transform and sequester copper, thus reducing exposure of sensitive organisms to bioavailable copper. This study investigates one type of manmade substrate, stormwater conduit, commonly used to transport stormwater away from buildings. Conduits made of PVC and cast iron did not significantly remove copper from a synthetic stormwater spiked with copper averaging 2391 μg Cu/L. Concrete conduit significantly removed copper from the synthetic water and at high rates (12 – 18%) over a short distance (610 cm). A high percentage (81 – 100%) of the copper removed from the water was from the dissolved copper fraction. Once adsorbed to the concrete, copper did not readily leach back into copper-free water subsequently pumped into the conduit. These characteristics have significant implications for watershed management and best management practices for reducing concentrations of copper in stormwater runoff.     

Efficiency of a continuous deflective separation (CDS) unit in removing contaminants from urban stormwater

The weighted average concentration (WAC) of total suspended solids (TSS) in stormwater effluent from a continuous deflective separation (CDS) unit in Port Jackson (Australia) catchment was reduced by an average 28% during six high-flow events, but some TSS was released during turbulent, high-flow events. The average removal efficiency of metals Cr, Cu, Pb Mn, Ni, Zn and Fe varied considerably (?49% for Pb and +10% for Mn), whereas Ni and Zn were inefficiently removed by the device. Average concentrations of TKN, NO_x and TP were similar at both in- and out-flow points and faecal coliforms counts were slightly reduced.