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1.
It is known that hydrogen peroxide interferes with chemical oxygen demand analysis by consuming oxidation agents such as potassium dichromate, thus leading to overestimation of the chemical oxygen demand measurements. The objective of the study was to investigate the effects of hydrogen peroxide interference and to determine true chemical oxygen demand values on interpreting treatment performance during ozone-based advanced oxidation of livestock wastewater in which hydrogen peroxide concentration and chemical oxygen demand values are dynamically changing. According to the chemical oxygen demand monitoring data, chemical oxygen demand values were always higher than the initial chemical oxygen demand load when hydrogen peroxide was involved and the treatment performance with ozone alone or ozone/ultraviolet was better than with coupled hydrogen peroxide. The extent of overestimation was proportional to the remaining hydrogen peroxide concentration and the average overestimation ratio in livestock wastewater was in the range of 0.50～0.58 mg per 1 mg of hydrogen peroxide, depending upon the quality of the wastewater treated. True chemical oxygen demand values were estimated by correlating the extent of overestimation with the remaining hydrogen peroxide concentration during treatment. The extent of overestimation decreased to zero gradually as the amount of hydrogen peroxide also approached zero as oxidation proceeded. The corrected chemical oxygen demand values indicated underlying tendency of oxidation, which could not be seen in the original chemical oxygen demand monitoring data. Application of ozone/hydrogen peroxide was more efficient for reducing chemical oxygen demand than ozone alone, as was ozone/hydrogen peroxide/ultraviolet compared to ozone/ultraviolet. When coupled with ozone, ultraviolet irradiation was more efficient than hydrogen peroxide for decreasing chemical oxygen demand during treatment of livestock wastewater.  相似文献   

2.
A large portion of water is consumed during various textile operations thereby discharging wastewaters with pollutants of huge environmental concern. The treatment of such wastewaters has promising impact in the field of environmental engineering. In this work, Fenton oxidation treatment was engaged to treat simulated textile wastewater. Box–Behnken design and response surface methodology were employed to optimize the efficiency of Fenton process. Iron dose, peroxide dose and pH were considered as input variables while the responses were taken as chemical oxygen demand and color removal. A total of 17 experiments were conducted and analyzed using second-order quadratic model. The quadratic models generated for chemical oxygen demand and color removal efficiencies were validated using analysis of variances, and it was found that the experimental data fitted the second-order model quite effectively. Analysis of variances demonstrated high values of coefficient of determination (R 2) for chemical oxygen demand and color removal efficiencies with values of 0.9904 and 0.9963 showing high conformation of predicted values to the experimental ones. Perturbation plots suggested that the iron dosage produced the maximum effect on both chemical oxygen demand and color removal efficiencies. The optimum parameters were determined as Fe2+ dose—550 mg/L, H2O2 dose—5538 mg/L, pH—3.3 with corresponding chemical oxygen demand and color removal efficiencies of 73.86 and 81.35%. Fenton process was found efficient in treatment of simulated textile wastewater, and optimization using response surface methodology was found satisfactory as well as relevant. From the present study, it can also be concluded that if this method is used as pretreatment integrated with biological treatment, it can lead to eco-friendly solution for treatment of textile wastewaters.  相似文献   

3.
In the present study, the effectiveness of physicochemical treatment processes (coagulation and Fenton’s oxidation) was investigated for simulated dairy wastewater (pH = 7.3, chemical oxygen demand (COD) = 3600 mg/l, 5-day biochemical oxygen demand (BOD5) = 1950 mg/l, total Kjeldahl nitrogen (TKN) = 87 mg/l, and total phosphorous (TP) = 14 mg/l). Plain and ballasted coagulation runs were carried out in a jar apparatus, while Fenton’s oxidation was performed in a three-neck glass reactor. Ballasted coagulation caused an enhancement in the settling rate of sludge though no significant enhancement in the removal of organics was observed. Individually, coagulation and Fenton’s oxidation processes resulted in ~67 and 80 % COD removals, respectively, from the wastewater. The sequential treatment exploring coagulation followed by Fenton’s oxidation showed overall COD, BOD5, TKN, and TP reductions of ~93, 97, 84, and 70 %, respectively, from the wastewater. However, a biological post-treatment would be required to achieve the effluent discharge standards. The removal of proteins, fats, and amino acids from wastewater was confirmed from Fourier transform infrared analysis of the settled sludge (obtained after coagulation process). Preliminary cost analysis suggested coagulation and the sequential treatment (i.e. coagulation followed by Fenton’s oxidation) as the preferred options.  相似文献   

4.
Produced water (PW) from natural gas field, characterized with high organic contents, has brought high environmental concerns world widely. Fenton and enhanced Fenton technologies were considered as the potential methods to degrade the organic contaminates in the PW, but with very limited data or reference. Here, we examined the optimum conditions of Fenton on organics and colour removal from natural gas PW after coagulation pre-treatment. Simultaneously, the optimal Fenton process integrated with ultraviolet (UV) and ultrasonic (US) irradiation were applied to enhance pollutants removal efficiencies. The optimal Fenton conditions were found at 60 min with molar ratios of 6:1 and 25:1 for H2O2/COD and H2O2/Fe2+, respectively and the initial pH of 3. Among these the three treatment processes, chemical oxygen demand (COD), total organic carbon, 5-day biological oxygen demand (BOD5), and colour removal efficiencies were highest during UV–Fenton (82, 73, 68, and 95%,) followed by US–Fenton (79, 70, 66, and 95%) and Fenton treatment (70, 58, 51, and 92%), respectively. High biodegradability (BOD5/COD) was also observed after UV–Fenton process (0.76) than the others (both 0.73). The current study showed a satisfactory carbon and colour removal efficiencies from PW using different Fenton processes; however, there still is a need for final polishing such as biological treatment or low cost constructed wetland before discharge. This study can be a good reference for engineering application PW treatment.  相似文献   

5.
This study focuses on treatment of landfill leachate in column experiments by immobilized Trametes versicolor on polyurethane foam, collected from Nonthaburi landfill site, Thailand. In this study, glucose was used as a co-substrate. The effect of biomass growth on color removal was observed by immobilizing fungi on polyurethane foam. The same immobilized fungi were used for four cycles of 5 days each to find the reuse of fungi. Leachate was diluted to see the effect of organic loading on color removal. At optimum pH of 4 and in 20 days with 3 g/L of glucose, the fungi could decolorize 78 % and 63 % for 5-times dilution and concentrated leachate, respectively, using immobilized fungi after 4 days initial growth. Fungi could also reduce biological oxygen demand and chemical oxygen demand of 52 % and 42 % (with initial biological oxygen demand and chemical oxygen demand of 48,900 and 96,512 mg/L), respectively, with glucose 3 g/L in concentrate leachate and with 4 days initial immobilization of fungi on polyurethane foam. About 1–6% higher color removal was observed on day 20 with 15 days fungi immobilization initially as compared to 4 days immobilization. Higher removal efficiency was observed for the same leachate after dilution due to reduction in organic loading. Addition of co-substrate enhances significantly removal of color, biological oxygen demand and chemical oxygen demand. Chemical oxygen demand removal reached to 0.6 mg/mg of biomass with the co-substrate. Therefore, white rot fungi can be considered as potentially useful microorganisms in landfill leachate treatment.  相似文献   

6.
选取某农药厂旧厂区为试验场地,考察化学氧化技术异位处理地下水非水相有机污染物的运行效果。基于小试研究,确定高锰酸钾、高铁酸钾、芬顿试剂以及次氯酸钠4种氧化剂在中试试验中的适宜投加量。中试结果表明,当进水流量为1.0 m^3/h时,不同氧化剂对于常规水质指标及特征有机污染物的去除效果存在差异性。总体而言,四种氧化剂对于中长链石油烃类污染物(C10-C36)的去除率可达20%~70%,但对氯代烷烃类污染物的去除效果低于20%;高铁酸钾和次氯酸钠分别对于苯酚类和多环芳烃类污染物的去除效果较好(70%~100%);芬顿试剂对各类污染物均有显著氧化效果,其中对于短链石油烃(C6-C9,去除率20%~40%)、苯系物(去除率40%~90%)的去除效果高于其他三种氧化剂。研究不同氧化剂对于多组分有机污染地下水的处理效果,为将化学氧化技术应用于此类污染场地提供了理论和技术支持。  相似文献   

7.
Hydrogen peroxide and hydroxyl radical are readily formed during the oxidation of pyrite with molecular oxygen over a wide range of pH conditions. However, pretreatment of the pyrite surface influences how much of the intermediates are formed and their fate. Acid-washed pyrite produces significant amounts of hydrogen peroxide and hydroxyl radical when suspended in air-saturated water. However, the hydrogen peroxide concentration shows an exponential decrease with time. Suspensions made with partially oxidized pyrite yield significantly lower amounts of hydrogen peroxide product. The presence of Fe(III)-oxide or Fe(III)-hydroxide patches facilitates the conversion of hydrogen peroxide to oxygen and water. Hence, the degree to which a pyrite surface is covered with patches of Fe(III)-oxide or Fe(III)-hydroxide patches is an important control on the concentration of hydrogen peroxide in solution.Hydrogen peroxide appears to be an important intermediate in the four-electron transfer from pyrite to molecular oxygen. Addition of catalase, an enzyme that decomposes hydrogen peroxide to water and molecular oxygen, to a pyrite suspension reduces the oxidation rate by 40%. By contrast, hydroxyl radical does not appear to play a significant role in the oxidation mechanism. It is estimated on the basis of a molecular oxygen and sulfate mass balance that 5-6% of the molecular oxygen is consumed without forming sulfate.  相似文献   

8.
Cellular exposure to particulate matter with concomitant formation of reactive oxygen species (ROS) and oxidization of biomolecules may lead to negative health outcomes. Evaluating the particle-induced formation of ROS and the oxidation products from reaction of ROS with biomolecules is useful for gaining a mechanistic understanding of particle-induced oxidative stress. Aqueous suspensions of pyrite particles have been shown to form hydroxyl radicals and degrade nucleic acids. Reactions between pyrite-induced hydroxyl radicals and nucleic acid bases, however, remain to be determined. Here, we compared the oxidation of adenine by Fenton-generated (i.e., ferrous iron and hydrogen peroxide) hydroxyl radicals to adenine oxidation by hydroxyl radicals generated in pyrite aqueous suspensions. Results show that adenine oxidizes in the presence of pyrite (without the addition of hydrogen peroxide) and that the rate of oxidation is dependent on the pyrite loading. Adenine oxidation was prevented by addition of either catalase or ethanol to the pyrite/adenine suspensions, which implies that hydrogen peroxide and hydroxyl radicals are causing the adenine oxidation. The adenine oxidation products, 8-oxoadenine and 2-hydroxyadenine, were the same whether hydroxyl radicals were generated by Fenton or pyrite-initiated reactions. Although nucleic acid bases are unlikely to be directly exposed to pyrite particles, the formation of ROS in the vicinity of cells may lead to oxidative stress.  相似文献   

9.
The objective of this study was to explore the extent of 2,4,6-trinitrotoluene synthetic solution and red water mineralization by comparing conventional direct ozonation and multi-stage ozonation-biological treatment process. The alkaline hydrolysis was used for remediation 2, 4, 6-trinitrotoluene and red water at pH = 10.9. Nevertheless, the hydroxyl radicals would be generated by ozone decomposition with ozone dose of 0.177 g/L. The samples were subjected to chemical oxygen demand and total organic carbon analysis to monitor pollutants removal. The rate of 2, 4, 6-trinitrotoluene and red water pollutants degradation were quantified using high performance liquid chromatography. 2, 4, 6-trinitrotoluene synthetic solution resulted 55.5 % chemical oxygen demand removal by 3 h direct ozonation. Following direct ozonation the biological treatment twenty four hours chemical oxygen demand reached 98.9 % and 98.7 % removal using humic acid and river water 1 % ( v/v) inoculation singly and respectively. Conventional direct ozonation showed non significant change in total organic carbon degradation. While on using multi-stage ozone-biological treatment process where humic acid and/or river water were used as inoculums singly and respectively, total organic carbon fulfilled 73 % and 98.3 % removal. The process was one hour direct ozonation and followed by three days multi-stage ozone-biological treatment. In multi-stage ozone-biological treatment process, ozonation was effective to decompose total organic carbon and to produce biodegradable dissolved organic carbon easily removed by ozone oxidation up to 98.3 % in 2,4,6-trinitrotoluene synthetic solution. Pollutants removal achieved 99 % in authentic red water effluent using river inoculation 1 % (v/v) in 5 days. Nuclear Magnetic Resonance and Fourier Transformation Infra Red methods were performed to confirm types of pollutants content in red water.  相似文献   

10.
For treating oily sludge, wet peroxide oxidation (WPO) and catalytic wet oxidation (CWO) were investigated. The CWO experiment was carried out in a 0.5?L batch reactor using FeCl3 as catalyst. By using WPO, the effects of reaction parameters such as residence time, temperature, H2O2 excess, and initial COD were investigated. The results demonstrated that >80?% chemical oxygen demand (COD) was removed by CWO and >90?% COD was removed by WPO. Significantly, more of COD could be removed from the oily sludge by adding H2O2 in small doses. In conclusion, WPO was much more effective in the removal of organic compounds from oily sludge.  相似文献   

11.
We have conducted a series of laboratory studies to investigate the generation of ferrous iron and reactive oxygen species when solutions of seawater containing natural organic matter (NOM) and ferric iron are exposed to simulated sunlight. Total ferrous iron and hydrogen peroxide were measured at nanomolar concentrations with high temporal resolution using chemiluminescence-based methods. In all cases, ferrous iron concentrations rapidly peaked at several nanomoles per litre after a few minutes, and then declined over time, while hydrogen peroxide concentrations increased in a non-linear manner. Although concentrations of both species depended on the concentration of NOM, hydrogen peroxide concentrations were only minimally affected by the presence of iron. Increasing the NOM concentration while the total iron concentration was maintained constant led to an increase in the maximum ferrous iron concentration, suggesting that superoxide-mediated reduction of iron may be a major pathway for ferrous iron formation. This was supported by measurements of superoxide production from irradiation of NOM in the absence of iron and kinetic calculations, as well as an experiment in which superoxide dismutase was added. Further analysis of the data suggested that dissolved oxygen and photo-produced hydrogen peroxide were the primary oxidants of the Fe(II) formed. Thus we propose that superoxide and ferrous iron may be intricately coupled in the system, and that their generation is determined by the supply of NOM available to harvest light and donate electrons.  相似文献   

12.
现代海洋生物有机组分的动态变化过程是利用正演法评价海相优质烃源岩的重要中间环节, 可以为估算沉积过程中有机质的损耗提供参考.从化学组成来看, 生物体的脂类与原油成分最为接近, 而且与其他生化组分相比, 脂类的化学性质相对稳定, 可以长期保存在地层中, 因此脂类是最重要的生油母质.温度、盐度、CO2等环境条件以及生物的种类和生长阶段对生物脂类组成有重要影响, 不同环境条件和不同种类的生物对烃源岩有机质的贡献也不同.海水中的有机质在沉积过程中受原始生产力和氧化还原条件的影响.在特定生境中, 在一定的生产力范围内, 沉积有机质的通量与生产力有正相关关系.超过此范围, 沉积有机质通量与生产力关系不大.氧化条件下有机质降解速度快, 而还原条件则有利于沉积有机质的保存.生物膜的形成不仅使有机质更容易沉积, 而且降低了有机质被降解的机会.地质历史时期生物膜的识别对研究烃源岩有机质的保存具有重要意义.   相似文献   

13.
The effect of soil organic matter (SOM) content and composition on sorption behavior of toluene for fluvo-aquic, red and black soils in China was investigated in batch experiments. Tested SOM was fractionated into two primary sorptive domains (‘soft’ and ‘hard’) to explain the dependence of sorption behavior on SOM composition. All the tested soils exhibited similar sorption kinetics and nonlinear sorption isotherms. Soils with high SOM content possessed a high sorptive capacity. Clay minerals also contributed to the sorptive capacity, especially for fluvo-aquic and red soils with low SOM content. In comparison, after removing most ‘soft’ SOM fraction from soils through hydrogen peroxide treatment, the residual ‘hard’ SOM fraction of three soil samples exhibited a slower sorption rate and a less sorption capacity compared to the untreated soil samples. The nonlinear degree of sorption was positively correlated with the content of ‘hard’ SOM for all soil samples. This is explained by the combined effect of SOM content and the composition on toluene sorption rates, sorption capacity and nonlinear degree of sorption of three typical soils in China.  相似文献   

14.
Antibiotic contamination of aqueous environment due to pharmaceutical sewage may lead to development of antibiotic-resistant bacteria strain. In this research, elimination of antibiotics from synthetic wastewater was investigated. For this purpose, sulfamethoxazole and trimethoprim were treated by a pilot scale of net-like rotating biological contactor with three compartments, 48 plastic discs with total volume of 78.75 L. This system was continuously operated for about one year at various organic loading rates with different antibiotic dosages. The obtained results indicated that by increasing hydraulic retention time, the chemical oxygen demand (COD) removal was gradually increased. The optimal hydraulic retention time for desired rate of COD removal was 36 h. In addition, the effect of hydraulic retention time, organic load rate and sulfamethoxazole concentration in the removal of sulfamethoxazole and organic matter was assessed. Moreover, the results demonstrated that with increasing in organic load rate, sulfamethoxazole elimination was enhanced. In the next step, simultaneous removal of both antibiotics for constant inlet COD concentration of 8000 mg/L at optimum hydraulic retention time was analysed. The results showed that trimethoprim removal efficiency was approximately 100%, even at high concentration of trimethoprim (50 mg/L). For observation of dominant microorganism, samples of the developed biofilm on rotating biological contactor discs were scanned by scanning electron microscopy. In the first compartment where biomass was exposed to highest concentration of antibiotics, fungus strains were the dominant organism. In the second and third compartment antibiotic-resistant bacteria were the dominant attached living organisms.  相似文献   

15.
Removal of Congo red from textile wastewater by ozonation   总被引：7，自引：6，他引：1  
Congo red, which has a complex molecular structure with various diazo aromatic groups, is widely used in textile industry as an anionic dye. The purpose of this study was to investigate the degradation of Congo red in laboratory solution which had the chemical properties of the rinse waters of textile manufacturing dye-houses and the samples with Congo red alone wastewater by ozonation and to optimize the reaction parameters such as pH and time which influence the efficiencies of total organic carbon, total kjeldahl nitrogen and chemical oxygen demand removal. Ozonation of Congo red dye were carried out in a semi-batch reactor with constant ozone flow rate and concentration of 23 mL/sec and 13.6 mg/L, respectively. Decolorization was complete within a few minutes of ozonation possibly due to the cleavage of chromophore groups. It was observed that its structural destruction occurs predominantly at higher pHs. The reduction of chemical oxygen demand and destruction of the dye was more than 60 % and 42 %, respectively. Total kjeldahl nitrogen removal was accompanied by slight changes in nitrogen oxides. It can be deduced from the experimental results that: (a) the mineralization is very weak; (b) the reaction follows the indirect mechanism; i.e., the interaction of hydroxyl radicals with the dye and (c) the nitrification is rather predominant. Biological oxygen demand is declined in simulated alkalic and neutral samples respectively. At 13.6 mg O3/L, the biological oxygen demand levels were significantly enhanced. This might be attributable to the enhancement of its biodegradation at alkaline pHs.  相似文献   

16.
Continuous upflow anaerobic sludge blanket reactor performs more favorably at the higher organic loading rate than other anaerobic treatment. The treatment of municipal landfill leachate of Shiraz??s city investigated using continuous flow anaerobic reactor and subsequently aerated lagoon. Landfill leachate has chemical oxygen demand of 45,000?C90,000?mg/L and ammonia nitrogen at 1,000?C2,500 and heavy metals that can impact biological treatments. Capacity of anaerobic and aerobic reactors is 10 and 20?L that operated at detention time of 2 and 4?days, respectively. Organic loading rate of upflow anaerobic sludge blanket is between 0.5?C20?g chemical oxygen demand/L/day. Chemical oxygen demand removal efficiencies are between 57?C87, 35?C70 and 66?C94% in the anaerobic, aerobic and whole system, respectively. As the entry, leachate organic loading rate increased from 1 to 20?g/L/day, the chemical oxygen demand removal efficiency reached a maximum of 71% and 84% in the anaerobic reactor and whole system, respectively, at high organic loading rate. Ammonium removal efficiency was about 54% after the aerobic stage.  相似文献   

17.
Man Wu 《地球科学进展》2014,29(7):765-773
Hydrogen peroxide can oxidize or reduce a number of biological important trance metals in seawater. Therefore, it can indirectly affect the marine ecosystem by causing the changes in the speciation of these metals. The results of researches about hydrogen peroxide in seawater in the last more than thirty years were reviewed and the direction of study in the further was proposed in this paper. Hydrogen peroxide can be found rather ubiquitously in the upper water at concentration of 0~102 nmol/L. In water column the maximum of the concentrations of hydrogen peroxide presents in surface water and the concentrations decrease with the increase of depth. In general, the concentrations in costal seawater are higher than these in the oligotrophic ocean. Diel variation of hydrogen peroxide occurs in seawater: the concentrations increase since sunup until the mixmum of afternoon and decrease until the minimum at drawn. The sources of hydrogen peroxide in marine environment include photochemical production, atmospheric deposition and biological production, and the photochemical production is primary among them. The sinks of hydrogen peroxide in the ocean consist of biological and chemical and photochemical decomposition and the main one is biological decomposition. The biogeochemistry of hydrogen peroxide in the continental shelf influenced by river water and factors affecting photochemical production and detail of decomposition should be studied in the future.  相似文献   

18.
Sources of oxygen demand in the lower San Joaquin River,California   总被引：1，自引：0，他引：1  
Dissolved oxygen concentration below 5 mg 1−1 has characterized the lower tidal portion of the San Joaquin River downstream of Stockton, California, during the summer and fall for the past four decades. Intensive field research in 2000 and 2001 indicated low dissolved oxygen concentration was restricted to the first 14 km of the river, which was deepened to 12 m for shipping, downstream of Stockton. The persistent low dissolved oxygen concentration in the shipping channel was not caused by physical stratification that prevented aeration from vertical mixing or respiration associated wigh high phytoplankton biomass. The low dissolved oxygen concentration was primarily caused bynitrification that produced up to 81% of the total oxygen demand. Stepwise multiple regression analysis isolated dissolved ammonia concentration and carbonaceous oxygen demand as the water quality variables most closely associated with the variation in oxygen demand. Between these two sources, dissolved ammonia concentration accounted for 60% of the total variation in oxygen demand compared with a maximum of 30% for carbonceous oxygen demand. The Stockton wastewater treatment plant and nonpoint sources upstream were direct sources of dissolved ammonia in the channel. A large portion of the dissolved ammonia in the channel was also produced by oxidation of the organic nitrogen load from upstream. The phytoplankton biomass load from upstream primarily produced the carbonaceous oxygen demand. Mass balance models suggested the relative contribution of the wastewater and nonpoint upstream load to the ammonia concentration in the shipping channel at various residence times was dependent on the cumulative effect of ammonification, composition of the upstream load, and net downstream transport of the daily load.  相似文献   

19.
U.S. National Bureau of Standards (NBS) estuarine sediment 1646 from the Chesapeake Bay, Maryland, and surface sediment collected at two sites in the Calcasieu River estuary, Louisiana, were used to evaluate the dilute hydrochloric acid extraction of Cr, Fe and Mn from air-dried and freeze-dried samples that had been treated by one of three methods to remove organic carbon. The three methods for the oxidation and removal of organic carbon were: (1) 30% hydrogen peroxide; (2) 30% hydrogen peroxide plus 0.25 mM pyrophosphate; and (3) plasma oxidation (low-temperature ashing). There was no statistically significant difference at the 95% confidence level between air- and freeze-dried samples with respect to the percent of organic carbon removed by the three methods. Generally, there was no statistically significant difference at the 95% confidence level between air- and freeze-dried samples with respect to the concentration of Cr, Fe and Mn that was extracted, regardless of the extraction technique that was used. Hydrogen peroxide plus pyrophosphate removed the most organic carbon from sediment collected at the site in the Calcasieu River that was upstream from industrial outfalls. Plasma oxidation removed the most organic carbon from the sediment collected at a site in the Calcasieu River close to industrial outfalls and from the NBS estuarine sediment sample. Plasma oxidation merits further study as a treatment for removal of organic carbon. Operational parameters can be chosen to limit the plasma oxidation of pyrite which, unlike other Fe species, will not be dissolved by dilute hydrochloric acid. Preservation of pyrite allows the positive identification of Fe present as pyrite in sediments.  相似文献   

20.
Oxidation of pyrite by hydrogen peroxide (H2O2) at millimolar levels has been studied from 4 to 150 °C in order to evaluate isotopic effects potentially associated with radiolytic oxidation of pyrite. Gaseous, aqueous, and solid phases were collected and measured following sealed-tube experiments that lasted from 1 to 14 days. The dominant gaseous product was molecular oxygen. No volatile sulfur species were recovered from any experiment. Sulfate was the only aqueous sulfur species detected in solution, with sulfite and thiosulfate below the detection limits. X-ray diffraction patterns and images from scanning electron microscopy reveal solid residues composed primarily of hydrated ferric iron sulfates and sporadic ferric-ferrous iron sulfates. Hematite was detected only in solid residue produced during high temperature experiments. Elemental sulfur and/or polysulfides are inferred to be form on reacting pyrite surface based on extraction with organic solvents. Pyrite oxidation by H2O2 increases in rate with increasing H2O2concentration, pyrite surface area, and temperature. Rates measured in sealed-tube experiments at 25°C, for H2O2 concentration of 2 × 10−3 M are 8.8 × 10−9 M/m2/sec, which are higher than previous estimates. A combination of reactive oxygen species from H2O2 decomposition products and reactive iron species from pyrite dissolution is inferred to aggressively oxidize the receding pyrite surface. Competing oxidants with temperature-dependent oxidation efficiencies results in multiple reaction mechanisms for different temperatures and surface conditions. Sulfur isotope values of remaining pyrite were unchanged during the experiments, but showed distinct enrichment of 34S in produced sulfate and depletion in elemental sulfur. The Δsulfate-pyrite and Δelemental sulfur-pyrite was +0.5 to +1.5‰ and was −0.2 to −1‰, respectively. Isotope data from high-temperature experiments indicate an additional 34S-depleted sulfur fraction, with up to 4‰ depletion of 34S, in the hematite. Sulfur isotope trends were not influenced by H2O2 concentration, temperature, or reaction time. Results of this study indicate that radiolytically produced oxidants, such as hydrogen peroxide and hydroxyl radicals, could efficiently oxidize pyrite in an otherwise oxygen-limited environment. Although H2O2 is generally regarded as being of minor geochemical significance on Earth, the H2O2 molecule plays a pivotal role in Martian atmospheric and soil chemistry. Additional experimental and field studies are needed to characterize sulfur and oxygen isotope systematics during radiolytical oxidation of metallic sulfides and elemental sulfur.  相似文献   

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