铁砷复合污染下铁砷比对除砷效果的影响研究

针对铁砷复合污染型地下水,以原水铁砷比作为控制参数,通过烧杯试验研究了曝气接触氧化除铁工艺的除砷效果。结果表明,当初始砷含量分别为100,200,300和400μg/L时,原水铁砷比分别为35∶1,50∶1,52∶1和55∶1,能达到除铁效果且同时满足出水砷含量小于10μg/L的限值要求;根据氢氧化铁对砷的吸附机理,利用Freundlich吸附等温式建立了铁砷比与残余砷含量的数学模型,试验数据拟合结果与模型相吻合。此外,采用曝气氧化工艺处理铁砷复合污染地下水时,可以通过投加二价铁盐控制原水铁砷比,以实现同时去除铁砷的目的。     

Iron salts dosage for sulfide control in sewers induces chemical phosphorus removal during wastewater treatment

Chemical phosphorus (P) removal during aerobic wastewater treatment induced by iron salt addition in sewer systems for sulfide control is investigated. Aerobic batch tests with activated sludge fed with wastewater containing iron sulfide precipitates showed that iron sulfide was rapidly reoxidised in aerobic conditions, resulting in phosphate precipitation. The amount of P removed was proportional to the amount of iron salts added, and for the sludge used, ratios of 0.44 and 0.37 mgP/mgFe were obtained for ferric and ferrous dosages, respectively. The hydraulic retention time (HRT) of iron sulfide in sewers was found to have a crucial impact on the settling of iron sulfide precipitates during primary settling, with a shorter HRT resulting in a higher concentration of iron sulfide in the primary effluent and thus enabling higher P removal. A mathematical model was developed to describe iron sulfide oxidation in aerated activated sludge and the subsequent iron phosphate precipitation. The model was used to optimise FeCl₃ dosing in a real wastewater collection and treatment system. Simulation studies revealed that, by moving FeCl₃ dosing from the WWTP, which is the current practice, to a sewer location upstream of the plant, both sulfide control and phosphate removal could be achieved with the current ferric salt consumption. This work highlights the importance of integrated management of sewer networks and wastewater treatment plants.     

Kinetics and stoichiometry of sulfide oxidation by sewer biofilms

Oxidation of sulfide under aerobic conditions by biofilms grown on municipal wastewater in 6 identical pipe reactors was investigated. The biofilms were grown at pH 7.6 and temperatures of 20 and 25 degrees C under aerobic-anaerobic transient conditions with pulse dosing of sulfide in the bulk water. The pulse dosing of sulfide served to simulate conditions in a gravity sewer located downstream of a pressure main. During growth of the biofilms, sulfide was pulse dosed in concentrations of 0, 0.5, 2.0 and 5.0 g Sm(-3) with a frequency of 1h(-1). Based on a series of batch experiments, kinetics and stoichiometry of sulfide oxidation by the sewer biofilms was investigated and a rate equation and a stoichiometric constant proposed. Sulfide oxidation kinetics was significantly faster for biofilms grown at sulfide loadings of 0.5, 2.0 and 5.0 g Sm(-3)h(-1) than for biofilms grown in the absence of sulfide. However, the kinetics of sulfide oxidation was relatively constant for biofilms grown at sulfide loadings above 0.5 g Sm(-3)h(-1). Mass balance calculations of dissolved oxygen and sulfur compounds suggested the oxidation product to be elemental sulfur. Further oxidation of elemental sulfur could not be documented.     

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.     

Inhibition of sulfate-reducing and methanogenic activities of anaerobic sewer biofilms by ferric iron dosing

Ferric iron is commonly used for sulfide precipitation in sewers, thus achieving corrosion and odour control. Its impact on the activities of sulfate-reducing bacteria and methanogens in anaerobic sewer biofilms is investigated in this study. Two lab-scale rising main sewer systems fed with real sewage were operated for 8 months. One received Fe³⁺ dosage (experimental system) and the other was used as a control. In addition to precipitating sulfide from bulk water, Fe³⁺ dosage was found to significantly inhibit sulfate reduction and methane production by sewer biofilms. The experimental reactor discharged an effluent containing a higher concentration of sulfate and a lower concentration of methane in comparison with the reference reactor. Batch experiments showed that the addition of ferric ions reduced the sulfate reduction and methane production rates of the sewer biofilms by 60% and 80%, respectively. The batch experiments further showed that Fe³⁺ dosage changed the final products of sulfate reduction with sulfide accounting for only 54% of the sulfate reduced. The other products could not be confirmed, but were not dissolved inorganic sulfur species such as sulfite or thiosulfate. The results suggest the addition of Fe³⁺ at upstream locations would minimize the ferric salts required for achieving the same level of sulfide removal. Fe³⁺ dosing could also substantially reduce the formation of methane, a potent greenhouse gas, in sewers.     

Research on the danger of fires in oil tanks with sulfur

Hydrogen sulfide reacts with the corrosion product Fe₂O₃ in oil tanks to form ferrous sulfide. The reaction is highly exothermic and the heat release can cause incandescence of the ferrous sulfide. This pyrophoric oxidation can ignite flammable hydrocarbon in oil tanks. In this paper, the simulated production process of pyrophoric ferrous sulfide in oil tanks, the rate of the oxidation reaction and other influencing factors for oxidation of ferrous sulfide are studied. The possibility of the oil tank fire being caused by the pyrophoric oxidation of ferrous sulfide is then analyzed.     

Evaluation of chemicals to control the generation of malodorous hydrogen sulfide in waste water

The effect of hydrogen peroxide, sodium/calcium hypochlorite and ferrous/ferric salts on hydrogen sulfide dissolved in waste water were investigated to establish an effective odour control system for Kuwait Sewage Networks. The waste water samples were collected from the inlet structure of main pumping station with pressure pipelines and analyzed for dissolved sulfide and pH before and after addition of chemicals individually and in combination under controlled laboratory conditions. The waste water contained dissolved sulfide in the range of 18 to 25 mg/l and pH ranged between 7.2 and 7.8. Various concentrations of above mentioned chemicals were tried to determine the accurate chemical requirement for oxidation or precipitation of dissolved sulfide in waste water. The reaction temperature was maintained at 35°C (±2°C), the normal temperature of waste water in Kuwait during summer. To oxidize 1 g of sulfide 1.25, 2.0 and 1.8 g hydrogen peroxide, sodium hypochlorite and calcium hypochlorite were required respectively. To remove 1 g of sulfide by precipitation with ferrous sulfate and ferric salt solution, 8 g and 4 g ferrous and ferric salt were required respectively under laboratory investigations. A combination of sodium hydroxide and sodium hypochlorite was also studied to control malodorous hydrogen sulfide in waste water. The addition of sodium hydroxide with sodium hypochlorite in waste water reduced the demand of hypochlorite 50%. This procedure was found to be cost effective and best suited for the warm climate of Kuwait and was implemented in the field at a screw conveyor type lifting station with gravity sewer pipelines. When sodium hypochlorite was injected without shock loadings of sodium hydroxide 46% reduction of dissolved sulfides was recorded and it was increased to 57% with shock loadings of sodium hydroxide, though the quantity of sodium hypochlorite was reduced to half than the former case. Similarly, 45 and 70% reduction in the emission of gaseous hydrogen sulfide was recorded with NaOCl injection without and with NaOH shock loading respectively. The cost comparison of all the chemicals when applied in field is also presented.     

Biogeochemistry of the compost bioreactor components of a composite acid mine drainage passive remediation system

The compost bioreactor ("anaerobic cell") components of three composite passive remediation systems constructed to treat acid mine drainage (AMD) at the former Wheal Jane tin mine, Cornwall, UK were studied over a period of 16 months. While there was some amelioration of the preprocessed AMD in each of the three compost bioreactors, as evidenced by pH increase and decrease in metal concentrations, only one of the cells showed effective removal of the two dominant heavy metals (iron and zinc) present. With two of the compost bioreactors, concentrations of soluble (ferrous) iron draining the cells were significantly greater than those entering the reactors, indicating that there was net mobilisation (by reductive dissolution) of colloidal and/or solid-phase ferric iron compounds within the cells. Soluble sulfide was also detected in waters draining all three compost bioreactors which was rapidly oxidised, in contrast to ferrous iron. Oxidation and hydrolysis of iron, together with sulfide oxidation, resulted in reacidification of processed AMD downstream of the compost bioreactors in two of the passive treatment systems. The dominant cultivatable microorganism in waters draining the compost bioreactors was identified, via analysis of its 16S rRNA gene, as a Thiomonas sp. and was capable of accelerating the dissimilatory oxidation of both ferrous iron and reduced sulfur compounds. Sulfate-reducing bacteria (SRB) were also detected, although only in the bioreactor that was performing well were these present in significant numbers. This particular compost bioreactor had been shut down for 10 months prior to the monitoring period due to operational problems. This unforeseen event appears to have allowed more successful development of AMD-tolerant and other microbial populations with critical roles in AMD bioremediation, including neutrophilic SRB (nSRB), in this compost bioreactor than in the other two, where the throughput of AMD was not interrupted. This study has revealed new insights into the operation of compost bioreactors used to remediate mine waters and has shown that, when operated under appropriate conditions, they can be highly efficient at generating alkalinity and removing metals from extremely acidic, metal-rich AMD.     

Iron amendment and Fenton oxidation of MTBE-spent granular activated carbon

Fenton-driven regeneration of methyl tert-butyl ether (MTBE)-spent granular activated carbon (GAC) involves an Fe amendment step to increase the Fe content and to enhance the extent of MTBE oxidation and GAC regeneration. Four forms of iron (ferric sulfate, ferric chloride, ferric nitrate, ferrous sulfate) were amended separately to GAC. Following Fe amendment, MTBE was adsorbed to the GAC followed by multiple applications of H₂O₂. Fe retention in GAC was high (83.8-99.9%) and decreased in the following order, FeSO₄·7H₂O > Fe₂(SO₄)₃·9H₂O > Fe(NO₃)₃·9H₂O > FeCl₃. A correlation was established between the post-sorption aqueous MTBE concentrations and Fe on the GAC for all forms of Fe investigated indicating that Fe amendment interfered with MTBE adsorption. However, the mass of MTBE adsorbed to the GAC was minimally affected by Fe loading. Relative to ferric iron amendments to GAC, ferrous iron amendment resulted in lower residual iron in solution, greater Fe immobilization in the GAC, and less interference with MTBE adsorption. MTBE oxidation was Fe limited and no clear trend was established between the counter-ion (SO₄²⁻, Cl⁻, NO₃⁻) of the ferric Fe amended to GAC and H₂O₂ reaction, MTBE adsorption, or MTBE oxidation, suggesting these processes are anion independent.     

Hydrogeochemische Reaktionen im Sicker- und Grundwasserbereich von Braunkohlentagebaukippen

The changes in the chemical composition of water and solid phases in pyrite oxidation zones and in lignite mining dump aquifers are described and modelled. At pH-values below pH 4, sulfate and ferrous iron as pyrite oxidation products, are mobile. They are observed in a stoichiometric ratio of 1 to 2 in the aqueous phase. If pyrite oxidation takes place with no pH-buffering with the solid phases, pH-values below 1 are possible. This leads to more intensive silicate weathering which increases the pH-value of the solution to pH 2–3. However, equilibrium with silicates is not reached. At pH-values above pH 4, the iron concentration of water under oxidized conditions is limited by the precipitation of ferric hydroxide. This has an impact on sulfide oxidation itself, because ferric iron is involved in the oxidation reactions of pyrite. Products of sulfide oxidation stored in acidic material in overburden are leached by seepage water and ground water filling the dumps. Reaction with carbonate phases in non-acidic material mainly takes place during ground water recharge. The geogenic calcite minerals of the non-acidic sediments are dissolved. Gypsum and iron-rich carbonates precipitate as secondary minerals in the dump aquifer. The pH-value increases and the concentration of iron and trace metals (Co, Ni, Zn) in the ground water are controlled by equilibrium with iron-rich carbonates at pH-values above pH 5.     

A simplified method for estimation of jarosite and acid-forming sulfates in acid mine wastes

In acid base accounting (ABA) estimates of acid mine wastes, the acid potential (AP) estimate can be improved by using the net carbonate value (NCV) reactive sulfide S method rather than total S assay methods but this does not give recovery of potentially acid producing ferrous and ferric sulfates present in many wastes. For more accurate estimation of AP, an effective, site-specific method to quantify acid sulfate salts, such as jarosite and melanterite, in waste rocks has been developed and tested on synthetic and real wastes. The SPOCAS (acid sulfate soils) methods have been modified to an effective, rapid method to speciate sulfate forms in different synthetic waste samples. A three-step sequential extraction procedure has been established. These steps are: (1) argon-purged water extraction (3 min) to extract soluble Fe(II) salts (particularly melanterite), epsomite and gypsum (<10 wt.%), (2) roasting at 550 degrees C (1 h) to remove sulfur from pyrite and other reactive sulfides, (3) HCl extraction (4 M, 30 min) for determination of jarosites. Products (solid and aqueous) have been characterized at each step including the jarosite decomposition process in Step 2 where temperature control is critical to avoid S loss. The sequential extraction procedure was used to quantitatively determine melanterite, epsomite, gypsum, pyrite and jarosite concentrations in a synthetic waste sample containing these mineral phases at 5 wt.% in quartz, and also tested using a tailings waste sample to quantitatively determine epsomite, gypsum and jarosite contents. The method is applicable to most waste samples including those with non-pyrite sulfides but for samples containing significant amounts of sulfur (>1 wt.% S) as copper sulfides, the second step of roasting needs to be excluded from the procedure with an increased time of 4 M HCl extraction to 16 h for jarosite determination.     

Abiotic reduction of dinitroaniline herbicides

The importance of abiotic reductive transformations as a sink for four dinitroaniline herbicides (trifluralin, pendimethalin, nitralin, and isopropalin) has been evaluated. Using reductants representative of abiotic reductants found in natural systems, the results of this study indicate that nitro groups present on the dinitroaniline herbicides can be reduced by surface-bound Fe(II) species in goethite suspensions or by hydroquinone moieties such as (mercapto)juglone in a hydrogen sulfide solution. Aqueous iron species are also effective at pH values above 7.0. The reaction in aqueous Fe(II) and in Fe(II)/goethite systems is strongly pH dependent, with rates increasing with increasing pH. Montmorillonite clay, however, is not effective in mediating the reduction of dinitroaniline herbicides in the presence of Fe(II). Because the selected dinitroaniline herbicides have a mixture of electron withdrawing and electron donating groups, linear free energy relationships were developed for the H(2)S/(mercapto)juglone and Fe(II)/goethite systems. Anilines resulting from reduction of the nitro group as well as cyclization products (benzimidazoles) were observed in the degradation of trifluralin. Only one aniline product was observed for pendimethalin.     

Influence of sediment redox conditions on release/solubility of metals and nutrients in a Louisiana Mississippi River deltaic plain freshwater lake

The influence of sediment redox conditions on solubility of selected metals and nutrients in sediment from a coastal Louisiana freshwater lake (Lake Cataouatche) receiving diverted Mississippi River water was quantified. Sediment redox was cycled step wise in 50 mV increments between oxidized (-200 to +500 mV) and reduced (+500 to -200 mV) conditions. Changes in sediment oxidation/reduction status and pH influenced solubility of both metals and nutrients. When redox potential (Eh) was increased from -200 to +500 mV, sediment pH decreased from 7.1 to 5.7. When the sediment Eh decreased from +500 to -200 mV, pH increased from 5.7 to 7.1. The increase in sediment acidity upon oxidation resulted in the release of the Pb, Ca, Mg, Al, and Zn into solution. The solution concentration of these elements was inversely proportional to Eh (P相似文献   

Zero-valent iron reduction of nitrate in the presence of ultraviolet light,organic matter and hydrogen peroxide

This paper describes the use of metallic iron (Fe(0)) powder for nitrate removal in a well-mixed batch reactor. Important variables explored include Fe(0) dosage (1-3g/L), UV light intensity (64-128 W), and the presence of propanol (20 mg/L as DOC) and H(2)O(2) (100-200 mg/L). Accumulation of ferrous ions released from the Fe(0) surface can be expressed by an S-curve, which involves lag growth phase, exponential phase, rate-declining phase, and saturation phase. The removal of nitrate increases with increasing Fe(0) dosage; however, the removal makes no difference as the Fe(0) dosage is greater than 2 g/L. UV irradiation retards the dissolution of ferrous ion and the removal of nitrate. The species of propanol, which has a functional group of -OH, plays a role of organic inhibitor for Fe(0) corrosion. The presence of H(2)O(2) appears to inactivate all reactions as the Fe(0) of 10 microm was used; the final H(2)O(2) remains intact throughout the entire reaction period, and there were no removal of nitrate and no dissolution of ferrous ion. Surprisingly, with the use of a larger Fe(0) particle size of 150 microm, the H(2)O(2) was seen to decompose rapidly through Fenton reaction. Nevertheless, the rate of ferrous accumulation or nitrate removal is slow.     

Speciation and fate of ethylenediaminetetraacetate (EDTA) in municipal wastewater treatment

The speciation of EDTA in sewage effluents leaving wastewater treatment plants determines its ultimate fate in natural surface waters, since only the Fe(III)-EDTA complex (FeEDTA) is quickly degraded by direct photolysis, whereas other EDTA species are very slowly transformed, if at all, by biological or chemical processes. Field studies were undertaken to quantify the speciation of EDTA in influents and effluents of sewage treatment plants. Chemical equilibrium calculations are of only limited use for this purpose because several weeks are needed to reach thermodynamic equilibrium in wastewater due to slow metal exchange processes. In the effluents from treatment plants that precipitate phosphate, concentrations of dissolved Fe (0.05 μm- and 0.45 μm-filterable) correlated with the concentrations of EDTA. An operational scheme, using sunlight or artificial light sources for specific photoconversion of FeEDTA species, was applied to distinguish between photo-degradable (=FeEDTA) and photo-resistent EDTA species. Field studies conducted at three municipal wastewater treatment facilities showed that EDTA speciation changes from the input to the output because FeEDTA is formed from other metal-EDTA complexes after addition of iron(II)-containing solutions into the aeration tanks. With respect to total amounts of EDTA, fractions of FeEDTA in the influents and effluents varied from 10 to 55% and from 20 to 90%. Mass balances comprising sampling periods of several days showed that no significant elimination of EDTA occured by biological or chemical processes during sewage treatment, whereas the chemically related phosphate substitute nitrilotriacetic acid (NTA) was efficiently degraded (>90%). As long as the speciation of EDTA in wastewaters is dominated by FeEDTA, and aerobic conditions are maintained, the remobilization of common heavy metals out of sewage sludge is unlikely to occur.     

Addition of an aerated iron‐rich waste‐activated sludge to control the soluble sulphide concentration in sewage

Hydrogen sulphide emission in sewers is associated with toxicity, corrosion and odour and also yields considerable costs. The purpose of this study was to evaluate whether the soluble sulphide concentration in raw sewage can be controlled by dosing an iron‐rich waste‐activated sludge (WAS) or an iron‐rich aerated waste‐activated sludge (AWAS). An average soluble sulphide elimination of 99% was achieved at an iron‐rich AWAS to sewage ratio (v/v) of 16%, whereas dosage of iron‐poor AWAS at the same ratio decreased the soluble sulphide in the raw sewage by only 53%. Our lab‐scale tests suggest that dosing iron‐rich AWAS to sewage did not affect the chemical oxygen demand (COD) and total ammonia nitrogen (TAN) removal as well as the nitrification efficiency in the receiving activated sludge system. The results indicate that iron‐rich AWAS dosage is a feasible technique to remediate the sulphide problem in sewers.     

Chemical dosing for sulfide control in Australia: An industry survey

Controlling sulfide (H₂S) production and emission in sewer systems is critical due to the corrosion and malodour problems that sulfide causes. Chemical dosing is one of the most commonly used measures to mitigate these problems. Many chemicals have been reported to be effective for sulfide control, but the extent of success varies between chemicals and is also dependent on how they are applied. This industry survey aims to summarise the current practice in Australia with the view to assist the water industry to further improve their practices and to identify new research questions. Results showed that dosing is mainly undertaken in pressure mains. Magnesium hydroxide, sodium hydroxide and nitrate are the most commonly used chemicals for sewers with low flows. In comparison, iron salts are preferentially used for sulfide control in large systems. The use of oxygen injection has declined dramatically in the past few years. Chemical dosing is mainly conducted at wet wells and pumping stations, except for oxygen, which is injected into the pipe. The dosing rates are normally linked to the control mechanisms of the chemicals and the dosing locations, with constant or profiled dosing rates usually applied. Finally, key opportunities for improvement are the use of mathematical models for the selection of chemicals and dosing locations, on-line dynamic control of the dosing rates and the development of more cost-effective chemicals for sulfide control.     

Impact of nitrate addition on biofilm properties and activities in rising main sewers

Anaerobic sewer biofilm is a composite of many different microbial populations, including sulfate reducing bacteria (SRB), methanogens and heterotrophic bacteria. Nitrate addition to sewers in an attempt to control hydrogen sulfide concentrations affects the behaviour of these populations, which in turn impacts on wastewater characteristics. Experiments were carried out on a laboratory reactor system simulating a rising main to determine the impact of nitrate addition on the microbial activities of anaerobic sewer biofilm. Nitrate was added to the start of the rising main during sewage pump cycles at a concentration of 30 mg-N L⁻¹ for over 5 months. While it reduced sulfide levels at the outlet of the system by 66%, nitrate was not toxic or inhibitory to SRB activity and did not affect the dominant SRB populations in the biofilm. Long-term nitrate addition in fact stimulated additional SRB activity in downstream biofilm. Nitrate addition also stimulated the activity of nitrate reducing, sulfide oxidizing bacteria that appeared to be primarily responsible for the prevention of sulfide build up in the wastewater in the presence of nitrate. A short adaptation period of three to four nitrate exposure events (approximately 10 h) was required to stimulate biological sulfide oxidation, beyond which no sulfide accumulation was observed under anoxic conditions. Nitrate addition effectively controlled methane concentrations in the wastewater. The nitrate uptake rate of the biofilm increased with repeated exposure to nitrate, which in turn increased the consumption of biodegradable COD in the wastewater. These results provide a comprehensive understanding of the impact of nitrate addition on wastewater composition and sewer biofilm microbial activities, which will facilitate optimization of nitrate dosing for effective sulfide control in rising main sewers.     

Chemical treatment of sludge: in-depth study on toxic metal removal efficiency, dewatering ability and fertilizing property preservation

The presence of toxic metals in municipal sewage sludge restricts the application of this biomass in agricultural area. A chemical leaching process using a combination of inorganic acid and two oxidants has been developed for sludge decontamination. The present study investigated the effects of the concentrations of sulphuric acid (H2SO4), hydrogen peroxide and ferric chloride on metal solubilization from sewage sludge, as well as preservation of fertilizing properties (nutrient content) and dewatering ability of the treated sludge. The analysis of the results from batch leaching tests has allowed to define the optimal conditions for the reagent concentrations, which are 56 kg Fe3+ tonne(-1) of dry sludge solids (tds), 8 kg H2O2 tds(-1), and enough H2SO4 to reach a pH between 2.0 and 2.5 but less than 142 kg H2SO4 tds(-1). Finally, under these conditions, oxidoreduction potential values are found to be between 450 and 475 mV.