Adsorptive removal of phosphate from aqueous solutions using iron oxide tailings

This study explored the feasibility of utilizing industrial waste iron oxide tailings for phosphate removal in laboratory experiments. The experimental work emphasized on the evaluation of phosphate adsorption and desorption characteristics of the tailing material. The adsorption isotherm, kinetics, pH effect and desorption were examined in batch experiments. Five isotherm models were used for data fitting. The three-parameter equations (Redlich-Peterson and Langmuir-Freundlich) showed more applicability than the two-parameter equations (Freundlich, Langmuir and Temkin). A modified equation for calculation of the separation factor using the Langmuir-Freundlich equation constants was developed. The initial phosphate adsorption on the tailings was rapid. The adsorption kinetics can be best described by either the simple Elovich or power function equation. The phosphate adsorption on the tailings tended to decrease with an increase of pH. A phosphate desorbability of approximately 13-14% was observed, and this low desorbability likely resulted from a strong bonding between the adsorbed PO(4)(3-)and iron oxides in the tailings. Column flow-through tests using both synthetic phosphate solution and liquid hog manure confirmed the phosphate removal ability of the tailings. Due to their low cost and high capability, this type of iron oxide tailings has the potential to be utilized for cost-effective removal of phosphate from wastewater.     

Metal speciation in sulphidic sediments: a new method based on oxidation kinetics modelling in the presence of EDTA

The solid phase partitioning of metals (Zn, Cu and Pb) was determined in four anoxic, metal polluted sediments by investigating at pH 8 the 1 day oxidation kinetics of the metal sulphide phases present in the sediments in a background solution containing excess EDTA. A mathematical model consisting of a combination of two pseudo-first order reactions was used to fit the metal release data as a function of oxidation time. The model permitted to fractionate the trace metals in a 'quickly-oxidizable' and a 'slowly-oxidizable' fraction, which could be assigned to two different trace metal pools, respectively (1) FeS minerals (e.g. amorphous FeS, mackinawite) and (2) discrete trace metal sulphide phases. The sum of the fractions associated with these sulphide pools was taken as an approximation for the sulphide-associated fraction of the trace metals and coincided (for the case of Zn and Pb) with the sulphide-associated fraction derived from the analysis of acid volatile sulphide (AVS) and simultaneously extracted metals (SEM). Oxidation kinetics modelling allowed also determining the sulphide-associated fraction of a broad range of trace metals (as demonstrated for Cu) more accurately than the AVS/SEM method, which suffers from non-efficient extraction of a number of trace metal sulphides. A correction was made for the determination of the sulphide-associated fraction by subtracting the trace metal fraction dissolved after 1 day under anoxic conditions in the background EDTA solution. The combination of (1) one day oxidation kinetics modelling and (2) correction for the 1 day anoxic EDTA-soluble fraction is a suitable method to determine accurately the true sulphide speciation of trace metals in anoxic sediments.     

FeS-coated sand for removal of arsenic(III) under anaerobic conditions in permeable reactive barriers

Iron sulfide (as mackinawite, FeS) has shown considerable promise as a material for the removal of As(III) under anoxic conditions. However, as a nanoparticulate material, synthetic FeS is not suitable for use in conventional permeable reactive barriers (PRBs). This study developed a methodology for coating a natural silica sand to produce a material of an appropriate diameter for a PRB. Aging time, pH, rinse time, and volume ratios were varied, with a maximum coating of 4.0 mg FeS/g sand achieved using a pH 5.5 solution at a 1:4 volume ratio (sand: 2 g/L FeS suspension), three days of aging and no rinsing. Comparing the mass deposited on the sand, which had a natural iron-oxide coating, with and without chemical washing showed that the iron-oxide coating was essential to the formation of a stable FeS coating. Scanning electron microscopy images of the FeS-coated sand showed a patchwise FeS surface coating. X-ray photoelectron spectroscopy showed a partial oxidation of the Fe(II) to Fe(III) during the coating process, and some oxidation of S to polysulfides. Removal of As(III) by FeS-coated sand was 30% of that by nanoparticulate FeS at pH 5 and 7. At pH 9, the relative removal was 400%, perhaps due to the natural oxide coating of the sand or a secondary mineral phase from mackinawite oxidation. Although many studies have investigated the coating of sands with iron oxides, little prior work reports coating with iron sulfides. The results suggest that a suitable PRB material for the removal of As(III) under anoxic conditions can be produced through the deposition of a coating of FeS onto natural silica sand with an iron-oxide coating.     

Effects of water chemistry and flow rate on arsenate removal by adsorption to an iron oxide-based sorbent

Arsenate removal from water using an iron oxide-based sorbent was investigated to determine the optimal operating conditions and the influence of water composition on treatment efficiency. The novel sorbent with a high surface area was studied in flow-through column experiments conducted at different flow rates to quantify the effect of empty bed contact time (EBCT) on treatment performance. Arsenic removal efficiency declined with decreasing EBCT. Arsenic breakthrough curves at different EBCT values were successfully simulated with a pore and surface diffusion model (PSDM). Surface diffusion was the dominant intraparticle mass transfer process. The effect of water composition on arsenic removal efficiency was evaluated by conducting experiments with ultrapure water, ultrapure water with either phosphate or silica, and a synthetic groundwater that contained both phosphate and silica. Silica was more inhibitory than phosphate, and the silica in synthetic groundwater controlled the arsenic removal efficiency.     

Removal of dissolved metals by zero-valent iron (ZVI): kinetics, equilibria, processes and implications for stormwater runoff treatment

Infiltration of stormwater runoff contaminated with metals is often questionable in several cases due to its long-term potential to cause deterioration of groundwater quality. To ensure the quality of filtrate, a pre-treatment of contaminated runoff is required. This study investigates the processes of copper and zinc ion removal from stormwater runoff using zero-valent iron (ZVI, Fe0). Kinetic and equilibrium tests were performed with laboratory-prepared and in situ stormwater runoff samples collected from roof, street and highway catchments. Based on the results, a substantial portion of Cu2+ is reduced and transformed to insoluble forms of Cu0 and Cu2O. Unlike copper, the adsorption and co-precipitation associated with freshly precipitated iron oxides play important roles for the removal of Zn2+. Investigations under various water quality conditions demonstrated a relatively minor impact on Cu2+ uptake rates. However, the different conditions apparently altered the removal stoichiometry and phases of the copper deposits. The removal rates of Zn2+ increase with higher dissolved oxygen (DO), ionic strength (IS), temperature (T) and pH. Dissolved organic carbon (DOC) in runoff samples forms complexes with metals and Fe2+, thereby kinetically decreasing the metal uptake rates. Furthermore, depending on its composition, a larger molecular weight organic fraction was found to preferentially compete for the adsorption sites. The study demonstrates that ZVI is a promising medium for achieving comparable capacity to a commercial adsorbent like granular ferric hydroxide (GFH). Long-term performance of ZVI, however, may be limited and governed by the formation of non-conductive layers of iron and cuprous oxides.     

Oxidation and removal of arsenic (III) from aerated groundwater by filtration through sand and zero-valent iron

Removing arsenic from contaminated groundwater in Bangladesh is challenging due to high concentrations of As(III), phosphate and silicate. Application of zero-valent iron as a promising removal method was investigated in detail with synthetic groundwater containing 500 microg/L As(III), 2-3mg/L P, 20mg/L Si, 8.2mM HCO3-, 2.5mM Ca2+, 1.6mM Mg2+ and pH 7.0. In a series of experiments, 1L was repeatedly passed through a mixture of 1.5 g iron filings and 3-4 g quartz sand in a vertical glass column (10mm diameter), allowing the water to re-aerate between each filtration. At a flow rate of 1L/h, up to 8 mg/L dissolved Fe(II) was released. During the subsequent oxidation of Fe(II) by dissolved oxygen, As(III) was partially oxidized and As(V) sorbed on the forming hydrous ferric oxides (HFO). HFO was retained in the next filtration step and was removed by shaking of the sand-iron mixture with water. Rapid phosphate removal provided optimal conditions for the sorption of As(V). Four filtrations lead to almost complete As(III) oxidation and removal of As(tot) to below 50 microg/L. In a prototype treatment with a succession of four filters, each containing 1.5 g iron and 60 g sand, 36 L could be treated to below 50 microg/L in one continuous filtration, without an added oxidant.     

基于径流污染控制的生物滞留设施填料优化研究

为实现对径流污染的有效控制,对生物滞留设施种植土层之下的人工填料层组成优化进行了系统性研究,在静态条件下考察了9组填料对氮磷营养物的吸附性能。结果显示,蛭石和沸石对氨氮的吸附性能较好,对氨氮的吸附量分别为3.7和3.2 mg/g,并且粒径越小,吸附性能越好;蛭石和麦饭石对磷酸盐的去除效果较好,磷酸盐去除量分别为0.13和0.1 mg/g。由此筛选出对污染物净化效果较好的1~3 mm沸石和蛭石、2~3 mm麦饭石作为去除污染物的功能性填料。动态水力循环试验显示,相同体积的蛭石和沸石对氨氮的吸附效果接近,水力停留时间(HRT)为60 min时,对氨氮的去除率均接近100%,此时麦饭石对氨氮的去除率为93%。对磷酸盐吸附效果的优劣排序为蛭石>麦饭石>沸石,当HRT为60 min时,对磷酸盐的去除率分别为78.8%、53%和19.7%。填料掺混体积比为沸石∶蛭石∶麦饭石∶砂=3∶7∶1∶6的组合系统对氨氮、磷酸盐和COD的去除效果最好,且下覆5 cm砂层有利于降低出水颗粒物导致的浊度。在此填料配比条件下,当填料层厚度在30~50 cm之间时,对氮、磷和COD的综合去除效果最好。     

Arsenic removal from geothermal waters with zero-valent iron--effect of temperature, phosphate and nitrate

Field column studies and laboratory batch experiments were conducted in order to assess the performance of zero-valent iron in removing arsenic from geothermal waters in agricultural regions where phosphates and nitrates were present. A field pilot study demonstrated that iron filings could remove arsenic, phosphate and nitrate from water. In addition, batch studies were performed to evaluate the effect of temperature, phosphate and nitrate on As(III) and As(V) removal rates. All batch experiments were conducted at three temperatures (20, 30 and 40 degrees C). Pseudo-first-order reaction rate constants were calculated for As(III), As(V), phosphate, nitrate and ammonia for all temperatures. As(V) exhibited greater removal rates than As(III). The presence of phosphate and nitrate decreased the rates of arsenic removal. The temperature of the water played a dominant role on the kinetics of arsenic, phosphate and nitrate removal. Nitrate reduction resulted in the formation of nitrite and ammonia. In addition, the activation energy, Eact, and the constant temperature coefficient, theta were determined for each removal process.     

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.     

高效脱硫脱氨氮菌株的分离、鉴定及特性研究

从具有脱臭功能的曝气生物滤池中分离出一株能同时脱硫和氨氮的菌株TS-1.根据形态学、生理生化特征及16S rDNA基因序列分析结果,初步鉴定该菌株为巨大芽孢杆菌(Bacil-lus megaterium).对菌株TS-1的生长性能和脱硫、脱氨氮性能进行了测试,结果表明,在(30±2)℃、转速为150 r/min的条件下,该菌株的最佳生长pH值为7.0,对数生长期为12～32 h;当S~(2-)和NH_4~+-N分别为80、88 mg/L时,对硫化物和氨氮的去除率分别可达91.8%、96.6%,且去除率随底物初始浓度的增加而逐渐降低.     

Effects of water chemistry on arsenic removal from drinking water by electrocoagulation

Exposure to arsenic through drinking water poses a threat to human health. Electrocoagulation is a water treatment technology that involves electrolytic oxidation of anode materials and in-situ generation of coagulant. The electrochemical generation of coagulant is an alternative to using chemical coagulants, and the process can also oxidize As(III) to As(V). Batch electrocoagulation experiments were performed in the laboratory using iron electrodes. The experiments quantified the effects of pH, initial arsenic concentration and oxidation state, and concentrations of dissolved phosphate, silica and sulfate on the rate and extent of arsenic removal. The iron generated during electrocoagulation precipitated as lepidocrocite (γ-FeOOH), except when dissolved silica was present, and arsenic was removed by adsorption to the lepidocrocite. Arsenic removal was slower at higher pH. When solutions initially contained As(III), a portion of the As(III) was oxidized to As(V) during electrocoagulation. As(V) removal was faster than As(III) removal. The presence of 1 and 4 mg/L phosphate inhibited arsenic removal, while the presence of 5 and 20 mg/L silica or 10 and 50 mg/L sulfate had no significant effect on arsenic removal. For most conditions examined in this study, over 99.9% arsenic removal efficiency was achieved. Electrocoagulation was also highly effective at removing arsenic from drinking water in field trials conducted in a village in Eastern India. By using operation times long enough to produce sufficient iron oxide for removal of both phosphate and arsenate, the performance of the systems in field trials was not inhibited by high phosphate concentrations.     

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.     

Biological conversion of hydrogen sulphide to elemental sulphur in a fixed-film continuous flow photo-reactor

The green sulphur bacterium Chlorobium thiosulfutophilum was used to remove hydrogen sulphide from synthetic industrial wastewater and convert it to elemental sulphur in a fixed-film continuous-flow photosynthetic bioreactor. Twenty 150 mm x 3 mm ID Tygon tubes formed the active part of the reactor resulting in a total volume of 21.2 mL. Seven steady states were achieved under different experimental conditions using this tubular photo-reactor. Sulphide loading rates ranged from 111 to 328 mg/hL under influent flowrates of 9.0-42.4 mL/h and hydraulic retention times of 0.50-2.35 h. The irradiance at the reactor surface averaged 25.4 W/m2. The sulphide removal rates were found to be 82-100% and elemental sulphur recovery rates were found to be 75-95%. The maximum sustainable sulphide loading rate was found to be 286 mg/h L, which is 2.5 times higher than the previous reported highest value. Sulphide loading rate was found to be the function of radiant flux per unit reactor volume and the bacteriochlorophyll concentration as expressed by the van Niel curve.     

Peat Biofiltration as an Odour Control Technology for Sulphur-Based Odours

Due to their low odour thresholds and common occurrence in sewage-treatment operations, volatile sulphur compounds are generally considered to be the most significant malodorants at sewage-treatment works. Biofiltration is an odour-control technology which has proven success in industrial and agricultural applications, and in more recent years has been applied in the water industry.
Experiments were carried out using a test rig to measure the removal efficiencies of hydrogen sulphide and methyl mercaptan, when passed through peat-based materials, under a range of environmental conditions. Temperature, gas loading rate and inoculation with sulphur oxidizing bacteria were all found to significantly affect performance. Removal rates of over 99% of hydrogen sulphide, and 95% methyl mercaptan were achieved. Investigations of full-scale installations at sewage-treatment works supported the experimental results.     

The kinetics of hexavalent chromium reduction by metallic iron

The rate reduction of hexavalent chromium (Cr(VI)) by metallic iron under a range of conditions was studied in batch systems. The chemical variables studied were the Cr(VI) concentration, hydrogen ion concentration and surface area of iron. The influence of ionic strength and mixing rate was also examined. The reaction kinetics were found to be dependent on hydrogen ion concentration, hexavalent chromium concentration and iron surface area and to adhere to the following kinetic expression.

Full-size image (1K)

.The rate constant was evaluated and found to have a value of 5.45 × 10⁻⁵ 1 cm⁻² min⁻¹ over a wide range of conditions.The rate constant was found to increase as mixing rate increased up to a maximum value beyond which the rate was essentially independent of mixing. Increases in ionic strength were found to result in a rapid decrease in the rate constant at ionic strengths below 0.1 M. Further increases in ionic strength had no detectable impact on the rate constant. All rate determination studies were run in the mixing and ionic strength independent regions of these systems.Reaction stoichiometry was found to be, with one exception, independent of environmental conditions. In general, 1.33 mol of iron dissolved for each mol of Cr(VI) reduced. This highly efficient utilization of iron in the reduction suggests that hydrogen generated during iron dissolution may be acting as a reductant for the Cr(VI). The single parameter which influenced the reaction stoichiometry was the initial Cr(VI) concentration. The ratio of Cr(VI) reduced to iron dissolved increased rapidly as the Cr(VI) concentration increased. This observation was taken as being consistant with a surface interaction between the hexavalent chromium and some metastable hydrogen species at the iron surface.     

Sulfide-iron interactions in domestic wastewater from a gravity sewer

Interactions between iron and sulfide in domestic wastewater from a gravity sewer were investigated with particular emphasis on redox cycling of iron and iron sulfide formation. The concentration ranges of iron and total sulfide in the experiments were 0.4-5.4mgFeL(-1) and 0-5.1mgSL(-1), respectively. During anaerobic conditions, iron reduction kinetics were investigated and reduction rates amounted on average to 1.32mgFeL(-1)d(-1). Despite the very low solubility of iron sulfide, the reduced iron reacted only partly with sulfide to produce iron sulfide, even when dissolved sulfide was in excess. When a ferric chloride solution was added to sulfide containing anaerobic wastewater, the ferric iron was quickly reduced to ferrous forms by oxidation of dissolved sulfide and the ferrous iron precipitated almost completely as iron sulfide. During aerobic conditions, iron sulfide was oxidized with a half-life period of 11.7h. The oxidation rate of iron sulfide was significantly lower than that reported for the oxidation of dissolved sulfide.     

Effect of redox potential on heavy metal binding forms in polluted canal sediments in Delft (The Netherlands)

Heavy metal binding forms for Cu, Zn and Pb were determined at four representative sediment sites in the canals of Delft (The Netherlands), using selective chemical extraction methods. Small differences (on average <5%) were found between duplicate extraction experiments. The dominant Cu binding form was always related to sulphide and organics in the sediment. Zn was mainly bound to iron+manganese (hydr)oxides, whereas Pb was rather evenly distributed over the different labile and non-labile binding fractions. A gradual (over about 1 month) increase in redox potentials of the anaerobic sediments led to a 7-37% sediment release of the above heavy metals; this could mainly be ascribed to oxidation of the heavy metal-sulphide bindings. Part of the released heavy metals was re-adsorbed by the labile binding phases ("exchangeable" and "carbonate bound"). Contrary to expectations, we found a decrease rather than an increase in the Fe+Mn (hydr)oxide binding forms. This can probably be ascribed to non-equilibrium reactions in the time span of the experiments, as well as side reactions such as complexation with humic acids and hindered precipitation reactions due to organic matter coatings.     

Biological treatment of Mn(II) and Fe(II) containing groundwater: kinetic considerations and product characterization

In the present article, the treatment of groundwater containing Mn(II) and Fe(II) has been investigated. The biological oxidation of Mn(II) and Fe(II) in upflow filtration units comprised the applied experimental technique. The oxidation processes were mediated by specific bacteria, namely the Leptothrix ochracea and Gallionella ferruginea, which belong to the general category of manganese and iron oxidizing bacteria. This work was focused on the characterization of the products of biological oxidation and to the examination of the kinetics of Mn(II) removal as compared with Fe(II) removal from groundwaters. The products of biological oxidation were characterized using the spectroscopic techniques XRD, XPS and SEM-EDS and comprised a mixture of biogenic hydrous manganese and iron oxides. The oxidation state of manganese in the precipitates was found to be between 3 and 4. Iron oxides were mainly in the form of amorphous ferrihydrite. The kinetic results indicated that the rates of manganese and iron oxidation were several orders of magnitude greater than the respective for abiotic oxidation. The bacterially mediated oxidation of iron was faster than manganese oxidation, presenting half-lives of reaction 0.9 and 3.98 min, respectively.     

A study of the cycling of manganese and other elements in a seasonally anoxic lake, Rostherne Mere, U.K.

The vertical distribution of sulphate, dissolved sulphide, alkalinity, pH, total iron and manganese, Fe(II) and Mn(II) and humic substances was monitored for a year in a seasonally anoxic lake, Rostherne Mere, U.K. During summer stratification Mn(II), probably of sediment origin, accumulated in the hypolimnetic bottom waters to a concentration of 50μm. Release occurred in two stages and appeared to be related to the supply of organic material to the sediment. No ferrous iron or dissolved sulphide were detected in the water column, although they were measured in the interstitial waters of the sediment. Ferrous sulphide formation in the sediment controls the iron(II) and dissolved sulphide concentrations and so minimises the concentration gradients at the sediment-water interface. Electron acceptors other than oxygen are capable of oxidising ferrous and sulphide ions in the water column. pH and alkalinity were the only other chemical components to show appreciable variation with depth, reflecting the biological processes of photosynthesis, respiration and decomposition. Iron and humic substances simultaneously increased in the surface waters after a major flood indicating that they are both present in the solution in contact with the soils of the catchment.     

Soil aquifer treatment of artificial wastewater under saturated conditions

A 2000 mm long saturated laboratory soil column was used to simulate soil aquifer treatment under saturated conditions to assess the removal of chemical and biochemical oxygen demand (COD and BOD), dissolved organic carbon (DOC), nitrogen and phosphate, using high strength artificial wastewater. The removal rates were determined under a combination of constant hydraulic loading rates (HLR) and variable COD concentrations as well as variable HLR under a constant COD. Within the range of COD concentrations considered (42 mg L⁻¹-135 mg L⁻¹) it was found that at fixed hydraulic loading rate, a decrease in the influent concentrations of dissolved organic carbon (DOC), biochemical oxygen demand (BOD), total nitrogen and phosphate improved their removal efficiencies. At the high COD concentrations applied residence times influenced the redox conditions in the soil column. Long residence times were detrimental to the removal process for COD, BOD and DOC as anoxic processes and sulphate reduction played an important role as electron acceptors. It was found that total COD mass loading within the range of 911 mg d⁻¹-1780 mg d⁻¹ applied as low COD wastewater infiltrated coupled with short residence times would provide better effluent quality than the same mass applied as a COD with higher concentration at long residence times. The opposite was true for organic nitrogen where relatively high concentrations coupled with long residence time gave better removal efficiency.