Kinetics and stoichiometry of aerobic sulfide oxidation in wastewater from sewers-effects of pH and temperature.

Kinetics and stoichiometry of aerobic chemical and biological sulfide oxidation in wastewater from sewer networks were studied. In this respect, the effects of temperature and pH were investigated in the ranges 10 to 20 degrees C and 5 to 9, respectively. The temperature dependency of sulfide oxidation kinetics was described using an Arrhenius relationship. The effect of pH on the rate of chemical sulfide oxidation is related to the dissociation of hydrogen sulfide (H2S) to hydrogen sulfide ion (HS(-)), with HS(-) being more readily oxidized than H2S. Biological sulfide oxidation exhibited the highest rates at ambient wastewater pH, and the reaction was inhibited at both low and high pH values. Chemical sulfide oxidation was found to produce thiosulfate and sulfate, while elemental sulfur was the main product of biological sulfide oxidation. Based on the investigations, general rate equations and stoichiometric constants were determined, enabling the processes to be incorporated to conceptual sewer process models.     

Effect of initial sulfide concentration on sulfide and phenol oxidation under denitrifying conditions

The objective of this work was to evaluate the effect of the initial sulfide concentration on the kinetics and metabolism of phenol and sulfide in batch bioassays using nitrate as electron acceptor. Complete oxidation of sulfide (20 mg L(-1) of S(2-)) and phenol (19.6 mg L(-1)) was linked to nitrate reduction when nitrate was supplemented at stoichiometric concentrations. At 32 mg L(-1) of sulfide, oxidation of sulfide and phenol by the organo-lithoautotrophic microbial culture was sequential; first sulfide was rapidly oxidized to elemental sulfur and afterwards to sulfate; phenol oxidation started once sulfate production reached a maximum. When the initial sulfide concentration was increased from 20 to 26 and finally to 32 mg L(-1), sulfide oxidation was inhibited. In contrast phenol consumption by the denitrifying culture was not affected. These results indicated that sulfide affected strongly the sulfide oxidation rate and nitrate reduction.     

接种物对厌氧同步脱硫反硝化特性的影响实验研究

分别以厌氧污泥、脱氮硫杆菌菌悬液和厌氧污泥并添加脱氮硫杆菌菌悬液为接种物,以硫化物和硝酸盐为进水基质,考察不同接种物条件下,各反应器的硫化物氧化特性、反硝化特性、生化反应机理及微生物特性。结果表明,在无菌条件下,硫化物不能被硝酸盐化学氧化。接种脱氮硫杆菌菌悬液的2#反应器的硫氧化速率为1.98 g S/(m3.h),停留24 h硫化物的去除率高达97%,脱硫能力最强,该接种条件下以硝酸盐氧化硫化物为主反应,优势菌为杆菌,进水的NO3--N/S应控制在0.4以下,可以实现高效生物脱硫。接种厌氧污泥的1#和3#反应器的脱氮效果比2#反应器好,停留时间为24 h时,硝酸盐的平均去除率为96%。单独接种厌氧污泥的1#反应器的硫氧化速率为1.78 g S/(m3.h),其优势菌为球菌,该接种条件下以硝酸盐氧化硫化物和硝酸盐氧化单质硫为主反应,进水的NO3--N/S应控制在0.8左右。以厌氧污泥联合脱氮硫杆菌为接种物时,硫氧化速率为1.71 g S/(m3.h),反应器以硝酸盐氧化硫化物、硝酸盐氧化单质硫以及异养反硝化为主反应,驯化后优势菌为球形、卵圆形和短杆状,应控制进水NO3--N/S为1.2,可以实现同步脱硫反硝化,该工艺既可以用于含硫废水的处理,也可以用于C/N低的硝酸盐废水的处理。     

Evaluation of long-term sulfide oxidation processes within pyrrhotite-rich tailings, Lynn Lake, Manitoba

Oxidation reactions have depleted sulfide minerals in the shallow tailings and have generated sulfate- and metal-rich pore water throughout the East Tailings Management Area (ETMA) at Lynn Lake, Manitoba, Canada. Information concerning the tailings geochemistry and mineralogy suggest the sulfide oxidation processes have reached an advanced stage in the area proximal to the point of tailings discharge. In contrast, the distal tailings, or slimes area, have a higher moisture content close to the impoundment surface, thereby impeding the ingress of oxygen and limiting sulfide oxidation. Numerical modelling of sulfide oxidation indicates the maximum rate of release for sulfate, Fe, and Ni occurred shortly after tailings deposition ceased. Although the sulfide minerals have been depleted in the very shallow tailings, the modelling suggests that sulfide oxidation will continue for hundreds and possibly thousands of years. The combination of sulfide minerals, principally pyrrhotite, that is susceptible to weathering processes and the relatively dry, coarse-grained nature of the tailings have resulted in the formation of a massive-hardpan layer in the proximal area of the ETMA. Because extensive accumulations of secondary oxyhydroxides of ferric iron are already present, remediation strategies for the ETMA should focus on mitigating the release of sulfide oxidation products rather than on preventing further oxidation.     

Nitrogen Dioxide Absorption and Sulfide Oxidation in Aqueous Sulfide

ABSTRACT

Rates of nitrogen dioxide (NO₂) absorption and sulfide oxidation were measured in a highly characterized stirred cell contactor at 55 °C, with O₂ present in the gas phase. The rate constant of the reaction between NO₂ and sul-fide at 55 °C was determined to be 26.4 x10⁵ M^-1sec^-1. A reaction mechanism was proposed that is consistent with the kinetic data. NO₂ absorption initiates sulfide oxidation in the presence of oxygen. The rate of sulfide oxidation increased with sulfide and oxygen concentration and with the rate of NO₂ absorption. Furthermore, thiosulfate was an effective inhibitor of sulfide oxidation.     

Effect of sewer headspace air-flow on hydrogen sulfide removal by corroding concrete surfaces

Hydrogen sulfide adsorption and oxidation by corroding concrete surfaces at different air-flows were quantified using a pilot-scale sewer reactor. The setup was installed in an underground sewer research station with direct access to wastewater. Hydrogen sulfide gas was injected into the headspace of the sewer reactor once per hour in peak concentrations of approximately 500 ppmv. The investigated range of sewer air-flows was representative for natural ventilated sewer systems, and covered both laminar and turbulent conditions. The experiments demonstrated a significant effect of sewer air-flow on the kinetics of hydrogen sulfide removal from the sewer headspace. From the lowest to the highest air-flow investigated, the rate of adsorption and oxidation increased more than threefold. At all air-flows, the reaction kinetics followed a simple n-th order rate equation with a reaction order of 0.8. The effect of air-flow on hydrogen sulfide adsorption and oxidation kinetics was quantified by a simple empirical equation.     

硫化氢废气治理研究进展

综合评述了硫化氢废气的各类净化方法及最新的研究进展。硫化氢废气的净化有吸收法、吸附法、氧化法、分解法和生物法。本文对超级克劳斯法和分解法研究进展进行了重点阐述。     

Sulfur speciation: Methodology and application to sulfide oxidation studies at the sediment-water interface

A single column ion chromatographic method for the determination of sulfide, sulfite, sulfate and thiosulfate was developed. It uses an anion exchange column (Waters, IC-Pak A) and a borate-gluconate buffer at pH 8.5 that contains EDTA and ascorbic acid to prevent sulfite oxidation. This eluent has relatively low background values for both conductivity and ultraviolet absorption, which allows determination of the above sulfur anions with high sensitivity. The mean percent recovery of the investigated anions in synthetic mixtures were 98.6, 100.0, 99.6 and 100.2 % for sulfide, sulfite, thiosulfate and sulfate, respectively. The method was applied to study sulfide ion oxidation at the water-sediment interface using six aquifer samples collected within the continental United States. Results indicated that sulfide ion disappearance follows a pseudo first-order profile and that the rate of disappearance correlates with the total organic carbon and clay content of the sediment.     

Online oxygen control for sulfide oxidation in anaerobic treatment of high-sulfate wastewater.

A new technique for sulfide control was investigated in an upflow-anaerobic filter (UAF) treating high-strength, sulfate-rich wastewater. The technique used periodic oxygen injection using oxidation-reduction potential (ORP) as a controlling parameter to regulate oxygen injection. The UAF was operated at a constant influent total-organic carbon of 6740 mg/L but with different influent sulfates of 1000, 3000, and 6000 mg/L. At 1000 and 3000 mg/L influent sulfates, the produced sulfide did not impose any inhibition to methane-producing bacteria (MPB). However, at 6000 mg/L influent sulfate, the produced dissolved sulfide of 804 mg S/L (free sulfide = 280 mg S/L) severely inhibited the methanogenesis, but not the sulfidogenesis. Upon oxygen injection at elevated ORP of -265 mV, sulfides were almost completely eliminated with a concomitant improvement in methane yield by 46%. If oxygenation was excessive because of an oversetting of ORP, the excess oxygen could be used rapidly by facultative heterotrophs, thereby protecting the MPB from oxygen stress. Regarding online sulfide oxidation, it was found that the biogas and injected oxygen needed to pass through an aqueous layer containing trace metals, which were found to have a significant catalytic effect on abiotic sulfide oxidation.     

Aerobic and anaerobic transformations of sulfide in a sewer system--field study and model simulations.

The formation and fate of sulfide in a force main and a downstream-located gravity sewer were investigated in an extensive field study. Sulfide formation in the force main was significant. However, during 14 minutes of transport in the gravity sewer, the sulfide concentration decreased 30%, on average. An application of a conceptual sewer process model for simulating the formation and fate of sulfide was demonstrated. Overall, the model predicted that approximately 90% of the decrease of the sulfide concentration in the gravity sewer was the result of sulfide oxidation and that only a small fraction entered the sewer atmosphere, causing odor and corrosion. Even so, the model predicted concrete corrosion rates of up to 1.2 mm/y in the gravity sewer section.     

硫酸盐在偶氮染料厌氧生物脱色中的作用

以沼泽红假单胞菌W1为研究对象,考察了厌氧条件下硫酸盐还原对活性黑5(Reactive Black 5,RB5)和直接黄11(Direct Yellow 11,DY11)生物脱色的影响。结果表明,硫酸盐本身对2种染料脱色无明显影响,而硫酸盐的还原产物———硫化物能通过氧化还原介体使2种染料化学脱色,其脱色过程能在3 min内迅速完成。在无介体加入的情况下,硫化物能够通过RB5自身产生的介体加速RB5的脱色;而对于不能产生氧化还原介体的DY11,硫化物对其脱色无明显影响。硫化物经染料氧化后形成的硫单质能够被菌株W1重新转化为硫化物,继续还原染料。     

Biological treatment process of air loaded with an ammonia and hydrogen sulfide mixture

The physico-chemical characteristics of granulated sludge lead us to develop its use as a packing material in air biofiltration. Then, the aim of this study is to investigate the potential of unit systems packed with this support in terms of ammonia and hydrogen sulfide emissions treatment. Two laboratory scale pilot biofilters were used. A volumetric load of 680 g H2S m(-3) empty bed day(-1) and 85 g NH3 m(-3) empty bed day(-1) was applied for eight weeks to a unit called BGSn (column packed with granulated sludge and mainly supplied with hydrogen sulfide); a volumetric load of 170 g H2S m(-3) empty bed day(-1) and 340 g NH3 m(-3) empty bed day(-1) was applied for eight weeks to the other called BGNs (column packed with granulated sludge and mainly supplied with ammonia). Ammonia and hydrogen sulfide elimination occur in the biofilters simultaneously. The hydrogen sulphide and ammonia removal efficiencies reached are very high: 100% and 80% for BGSn; 100% and 80% for BGNs respectively. Hydrogen sulfide is oxidized into sulphate and sulfur. The ammonia oxidation products are nitrite and nitrate. The nitrogen error mass balance is high for BGSn (60%) and BGNs (36%). This result could be explained by the denitrification process which would have occurred in anaerobic zones. High percentages of ammonia or hydrogen sulfide are oxidized on the first half of the column. The oxidation of high amounts of hydrogen sulfide would involve some environmental stress on nitrifying bacterial growth and activity.     

Removal of insoluble heavy metal sulfides from water

The necessity of heavy metal removal from wastewater has led to increasing interest in absorbents. We have developed a new approach to obtain high metal adsorption capacity by precipitating metal sulfides with sodium sulfide on the surface of bentonite and adhere them to the absorbent. This method allowed to remove approximately 90% of cadmium as CdS from 10(-4)-10(-6) M CdCl2 solutions. Additional reactions are related to the removal of excess sodium sulfide by the release of hydrogen sulfide and oxidation to sulfur using carbogen gas (5% CO2, 95% O2) followed by aeration.     

Silicic protective surface films for pyrite oxidation suppression to control acid mine drainage at the source

Environmental Science and Pollution Research - The tailings produce acid mine drainage (AMD) due to sulfide minerals, especially pyrite oxidation. AMD has caused serious pollution to the...     

Sulfate contamination in groundwater from a carbonate-hosted mine

Sulfide oxidation in a carbonate environment produces groundwater contamination with high sulfate making the water unsuitable for drinking supplies. The zinc-lead mines near Shullsburg, Wisconsin are located in the Galena-Platteville Formation, a carbonate aquifer that was dewatered during mining. Sulfate levels have reached as high as 40 nmol/l in some local wells and eleven wells were abandoned.Geochemical modeling of chemical reactions and isotope effects using the USGS computer program PHREEQE showed the importance of dolomite, calcite, CO₂, and siderite or iron hydroxide in controlling the water chemistry. The decrease in sulfate levels with time indicated that dilution by incoming recharge water was an ongoing process. The results of carbon isotope reaction modeling are consistent with dilution of contaminated water. The evidence for localization of contamination and dilution means that area farmers have seen the worst of the contamination. The mechanism of contamination was further examined by microbiological sampling and sulfur isotope determinations, which indicated that bacteria of the Thiobacillus species that thrive under neutral pH conditions may have catalyzed sulfide oxidation.Research into the chemical evolution of contamination in this environment not only explains how sulfide oxidation causes contamination despite buffering by carbonate rocks, but also suggests how oxidation is initiated in the case of acid mine drainage.     

Adsorption-oxidation of hydrogen sulfide on activated carbon fibers: effect of the composition and the relative humidity of the gas phase

The removal of hydrogen sulfide by oxidation-adsorption on two type carbon fibers, Actitex FC1201 and RS1301, was studied. Two kinetic steps where identified. During the first step, the degradation appears to be limited by the oxidation reaction. In the second kinetic step, the by-products inhibit the hydrogen sulfide degradation. This leads to a limitation in the carbon site's accessibility and to a lower kinetic. The Langmuir-Hinshelwood model was used to correlate the experimental results and to estimate the kinetic (k) and the Langmuir adsorption (K) constants. For FC1201 fibers, the kinetic constant (k) is five time higher and the adsorption constant is five time lower compared to the RS1301 fibers. The role of the humidity was found to be highly beneficial for the removal of hydrogen sulfide. Especially in the second kinetic step, where it removes the by-product formed and therefore delays the occurrence of this low kinetic step. The kinetic constant (k) is strongly influenced by humidity while the Langmuir adsorption constant (K) seems independent. The effect of the nature of the gas phase on the reaction kinetic was also studied. Under a dry atmosphere, we note that the oxidation-reaction occurs even if the gaseous oxygen is not present. This oxidation is due to the oxygen surface function of the carbon fibers. Moreover, the degradation kinetic is faster under a dry nitrogen atmosphere. The presence of water traces leads to the acidification of the carbon surface, under oxygen or carbon dioxide atmospheres, and hence limits the hydrogen sulfide dissociation. In a humid atmosphere, the oxygen or carbon dioxide leads to a faster reaction kinetic. The acidification of the carbon surface is largely counterbalanced by the dissolution of the by-products.     

Effect of high influent sulfate on anaerobic wastewater treatment.

A laboratory-scale study was conducted using a completely mixed reactor with a constant influent-total-organic carbon (TOC) of 3750 mg/L to evaluate the effect of increasing influent-sulfate levels on anaerobic-treatment performance. The sulfate levels were increased stepwise from 333 to 666, 1000, 1333 and 1666 mg S/L. The results showed that an elevation of influent sulfate actually increased the TOC removal efficiency as long as the produced sulfide level did not induce toxicity. At 1333 mg S/L influent sulfate, the produced dissolved sulfide was 613 mg S/L (free sulfide = 228 mg S/L), which started to impose toxicity to the methane-producing bacteria (MPB). It was also found that the percent electron flow to the sulfate-reducing pathway increased with the increasing influent sulfate, but the direction toward the methanogenesis was correspondingly reduced. Nevertheless, under the experimental conditions tested, the majority of the influent organics was still degraded through the methanogenic pathway. Through this study, an oxidation-reduction-potential (ORP)-based oxygenation process was developed for online oxidation of sulfide in recirculating biogas. With controlled oxygen injection to raise the reactor's ORP by 25 mV, the residual sulfide in the reactor was almost totally eliminated. In case of over oxygenation, any excess oxygen was quickly consumed by the facultative organisms in the reactor, thereby imposing no toxicity to the MPB.     

Adsorption of hydrogen sulfide on montmorillonites modified with iron

Sodium-rich montmorillonite was modified with iron in order to introduce active centers for hydrogen sulfide adsorption. In the first modification, interlayer sodium cations were exchanged with iron. In another modification, iron oxocations were introduced to the clay surface. The most elaborated modification was based on doping of iron within the interlayer space of aluminum-pillared clay. The modified clay samples were tested as hydrogen sulfide adsorbents. Iron-doped samples showed a significant improvement in the capacity for H2S removal, despite of a noticeable decrease in microporosity compared to the initial pillared clay. The smallest capacity was obtained for the clay modified with iron oxocations. Variations in adsorption capacity are likely due to differences in the chemistry of iron species, degree of their dispersion on the surface, and accessibility of small pores for H2S molecule. The results suggest that on the surface of iron-modified clay hydrogen sulfide reacts with Fe(+3) forming sulfides or it is catalytically oxidized to SO2 on iron (hydro)oxides. Subsequent oxidation may lead to sulfate formation.     

Oxidation of acid-volatile sulfide in surface sediments increases the release and toxicity of copper to the benthic amphipod Melita plumulosa

Acid-volatile sulfides (AVS) are an important metal-binding phase in sediments. For sediments that contain an excess of AVS over simultaneously extracted metal (SEM) concentrations, acute or chronic effects should not result from the metals Cd, Cu, Ni, Pb and Zn. While AVS phases may exist in surface sediments, the exposure to dissolved oxygen may oxidize the AVS and release metals to more bioavailable forms. We investigated the role of oxidation of AVS, and specifically copper sulfide phases, in surface sediments, in the toxicity to juveniles of the epibenthic amphipod, Melita plumulosa. Sediments containing known amounts of copper sulfide were prepared either in situ by reacting dissolved copper with AVS that had formed in field sediments or created in sediments within the laboratory, or by addition of synthesised CuS to sediments. Regardless of the form of the copper sulfide, considerable oxidation of AVS occurred during the 10-d tests. Sediments that had a molar excess of AVS compared to SEM at the start of the tests, did not always have an excess at the end of the tests. Consistent with the AVS-SEM model, no toxicity was observed for sediments with an excess of AVS throughout the tests. However, the study highlights the need to carefully consider the changes in AVS concentrations during tests, and that measurements of AVS and SEM concentrations should carefully target the materials to which the organisms are being exposed throughout tests, which in the case of juvenile M. plumulosa is the top few mm of the sediments.     

Feasibility study on high-temperature sorption of hydrogen sulfide by natural soils

In this study, seven natural soils were tested for the sorption of hydrogen sulfide from coal gasification gas at high temperature. Results indicate that the LP natural soil has the best performance and the highest sulfur sorption capacity. After extracting free iron oxides, most natural soils have no sorption efficiency. The free iron oxides, therefore, proved to be the major components that react with hydrogen sulfide to form iron sulfides. The sulfur sorption capacity, either determined by EA or breakthrough time, is very close to the theoretical value based on the stoichiometric calculation with the content of free iron oxides. Moreover, the presence of CO is a positive effect while H2 is a negative effect. This can be explained via the water-shift reaction. On the basis of the results of temperature-programmed sulfidation (TPS), the starting temperature for the sorption of hydrogen sulfide is between 623-673 K. From the analyses of temperature-programmed oxidation (TPO) and XPS, the iron polysulfides are the major products and approximately 90% regeneration efficiency can be theoretically achieved while the temperature is controlled higher than 813 K. In the regeneration tests, the results show that the LP natural soil can be regenerated and thus reused after the oxidation process. No significant degeneration occurs on the LP natural soil after five sorption/regeneration cycles. The sulfur sorption capacity of the tenth regenerated soil can be achieved at least 80% compared to the fresh one. The experimental analyzed SO2 concentration from the regeneration process is almost identical to the theoretical calculated equilibrium concentration of the process. Maghemite is the main product after the regeneration process.