Degradation of carbon tetrachloride by iron metal: Complexation effects on the oxide surface

Dehalogenation of chlorinated aliphatic contaminants at the surface of zero-valent iron metal (Fe⁰) is mediated by the thin film of iron (hydr)oxides found on Fe⁰ under environmental conditions. To evaluate the role this oxide film plays in the reduction of chlorinated methanes, carbon tetrachloride (CCl₄) degradation by Fe⁰ was studied under the influence of various anions, ligands, and initial CCl₄ concentrations ([P]_o). Over the range of conditions examined in these batch experiments, the reaction kinetics could be characterized by surface-area-normalized rate constants that were pseudo-first order for CCl₄ disappearance (k_CCl4), and zero order for the appearance of dissolved Fe²⁺ (k_Fe²⁺). The rate of dechlorination exhibits saturation kinetics with respect to [P]_o, suggesting that CCl₄ is transformed at a limited number of reactive surface sites. Because oxidation of Fe⁰ by CCl₄ is the major corrosion reaction in these systems, k_Fe²⁺ also approaches a limiting value at high CCl₄ concentrations. The adsorption of borate strongly inhibited reduction of CCl₄, but a concomitant addition of chloride partially offset this effect by destabilizing the film. Redox active ligands (catechol and ascorbate), and those that are not redox active (EDTA and acetate), all decreased k_CCl4 (and k_Fe²⁺). Thus, it appears that the relatively strong complexation of these ligands at the oxide–electrolyte interface blocks the sites where weak interactions with the metal oxide lead to dehalogenation of chlorinated aliphatic compounds.     

纳米级铁粉脱氯降解四氯化碳

四氯化碳的生产和使用,给人类带来了较大危害.为此,采用纳米铁粉这一新方法对其进行脱氯处理.试验以纳米级铁粉对四氯化碳的脱氯率为考察指标,选用L25(56)正交试验方案,考察了降解介质的初始pH值、纳米铁粉的质量、降解温度、摇床转速和脱氯时间5个影响因素.结果表明,pH值这一因素有极显著影响;在得出的纳米铁粉对四氯化碳脱氯的最佳工艺条件下,获得了99.5%的脱氯率,为有机氯化物脱氯开辟了一条新途径.     

纳米级铁粉脱氯降解四氯化碳

四氯化碳的生产和使用，给人类带来了较大危害。为此，采用纳米铁粉这一新方法对其进行脱氯处理。试验以纳米级铁粉对四氯化碳的脱氯率为考察指标，选用L25（5^6）正交试验方案，考察了降解介质的初始pH值、纳米铁粉的质量、降解温度、摇床转速和脱氯时间5个影响因素。结果表明，pH值这一因素有极显著影响；在得出的纳米铁粉对四氯化碳脱氯的最佳工艺条件下，获得了99．5％的脱氯率，为有机氯化物脱氯开辟了一条新途径。     

Soil- and surfactant-enhanced reductive dechlorination of carbon tetrachloride in the presence of Shewanella putrefaciens 200

Sorption of organic contaminants to soils has been shown to limit bioavailability and biodegradation in some systems. Use of surfactants has been proposed to reverse this effect. In this study, the effects of a high organic carbon content soil and a nonionic surfactant (Triton X-100) on the reductive dechlorination of carbon tetrachloride (CCl₄) were examined in anaerobic systems containing Shewanella putrefaciens. Although more than 70% of the added CCl₄ was sorbed to the soil phase in these systems, the reductive dechlorination of CCl₄ was not diminished. Rather, rates of CCl₄ dechlorination in systems containing soil were enhanced relative to systems containing non-sorptive sand slurries. This enhancement was also observed in sterile soil slurries to which a chemical reductant, dithiothreitol was added. It appears that the organic soil used in these experiments contains some catalytic factor capable of transforming CCl₄ in the presence of an appropriate chemical or microbial reductant. The addition of Triton X-100 to sand and soil slurries containing S. putrefaciens resulted in increased CCl₄ degradation in both systems. The effect of Triton could not be explained by: (i) surfactant induced changes in the distribution of CCl₄, (i.e. decreased sorption) or the rate of CCl₄ desorption; (ii) a direct reaction between Triton and CCl₄; or (iii) increased cell numbers resulting from use of the surfactant as a substrate. Rather, it appears that Triton X-100 addition resulted in lysis of bacterial cells, a release of biochemical reductant, and enhanced reductive transformation of CCl₄. These results provide insights to guide the development of more effective direct or indirect bioremediation strategies.     

Degradation of aqueous carbon tetrachloride by nanoscale zerovalent copper on a cation resin

Nanoscale zerovalent copper supported on a cation resin was successfully synthesized to enhance the removal of carbon tetrachloride (CCl(4)) from contaminated water. The use of the cation resin as a support prevents the reduction of surface area due to agglomeration of nanoscale zerovalent copper particles. Moreover, the cation resin recycles the copper ions resulting from the reaction between CCl(4) and Cu(0) by simultaneous ion exchange. The decline in the amount of CCl(4) in aqueous solution results from the combined effects of degradation by nanoscale zerovalent copper and sorption by the cation resin; thus the amount of CCl(4) both in aqueous solution and sorbed onto the resin were measured. The pseudo-first-order rate constant normalized by the surface-area and the mass concentration of nanoscale zerovalent copper (k(SA)) was 2.1+/-0.1 x 10(-2)lh(-1)m(-2), approximately twenty times that of commercial powdered zerovalent copper (0.04 mm). Due to the exchange between Cu(2+) and the strongly acidic ions (H(+) or Na(+)), the pH was between 3 and 4 in unbuffered solution and Cu(2+) at the concentration of less than 0.1 mg l(-1) was measured after the dechlorination reaction. In the above-ground application, resin as a support would facilitate the development of a process that could be designed for convenient emplacement and regeneration of porous reductive medium.     

Degradation of nitrogen containing organic compounds by combined photocatalysis and ozonation

The combination of TiO2-assisted photocatalysis and ozonation in the degradation of nitrogen-containing substrates such as alkylamines, alkanolamines, heterocyclic and aromatic N-compounds has been investigated. A laboratory set-up was designed and the influence of the structure of the N-compound, the TiO2 and ozone concentration on the formation of breakdown products were examined. The experimental results showed that a considerable increase in the degradation efficiency of the N-compounds is obtained by a combination of photocatalysis and ozonation as compared to either ozonation or photocatalysis only. The mineralization of the model substances was monitored by measurements of the TOC and ion-chromatographic determinations of the formed NO2- and NO3-. The temporal changes of concentrations of breakdown products, such as NH4+, short chain alkyl- and alkanolamines were determined by single column ion chromatography (SCIC) and as well as by electrospray mass spectrometry (EI-MS).     

Chlorination of p-cymene by chlorine in carbon tetrachloride: Model compounds for environmental analyses

p-Cymene was chlorinated by chlorine in CCl₄. The products of the chlorination were separated by distillation and purified by preparative gas chromatography. The structures of chlorocompounds were confirmed by means of their NMR and mass spectra. The distillation gave as the main compounds: (2) 2-chloro-, (4) 2,3-dichloro-, (5) 2,5-dichloro-, (6) 2,3,6-trichloro-, (7) 2,3,5,6-tetrachloro-p-cymenes and as by-products: (8) 2,5,7-trichloro-p-cymene, (9) 2,6-dichloro-1-methyl-4-(1-methylethenyl)benzene (cymenene), and (10) 2,3,6-trichloro-1-methyl-4-(1-methylethenyl)benzene (cymenene).     

Water-soluble sulphur compounds in aerosols

Sampling of particles and analysis of their water-soluble part for H⁺, NH₄⁺, SO₄²⁻ and NO₃⁻ were carried out in a remote and an urban area on the Swedish west coast. For the determination of H⁺ a special procedure based on Gran's plot was used. High concentrations of sulphate were found in two types of particles of apparently different genetic origin. In fine particles the following solid sulphate phases were identified: (NH₄)₂SO₄, (NH₄)₃H(SO₄)₂ and NH₄HSO₄. Conditions for the formation and range of existence of these phases are discussed. The observed sulphate maxima are divided according to genetic and to some extent geographic origin of the particles into black and white episodes. Black episodes are associated with Continental air. They are accompanied by increased concentrations of nitrate, dark components and metals e.g. Mn. Particles characteristic of white episodes seem to occur in air masses of varying origin. The sulphate maxima in this category are usually accompanied by hydrogen ion maxima, and minima for nitrate, dark components and metals. The formation of particle-borne ions in an urban area (Gothenburg, population 500,000) was also studied. For sulphate, this local contribution was found to be 16% of the mean concentration. Processes which might lead to black and white episodes are discussed.     

Recent history of atmospheric trace gas concentrations deduced from measurements in the deep sea: Application to sulphur hexafluoride and carbon tetrachloride

On a time scale of several decades, an increase in the atmospheric burden of certain stable trace gases results in a characteristic oceanic depth profile for the concentration of the dissolved gas. If the atmosphere is the only source of the gas to the sea, the time delay inherent in its downward penetration from the surface results in a profile which decreases with depth. By referencing to compounds such as Freon 11 or Freon 12, the atmospheric histories of which are relatively well known, limits can be placed on the increase of a trace gas whose history is unknown. The method may be particularly valuable in distinguishing the contributions of natural and anthropogenic sources of gases such as CCl₄ and CF₄, which may have both. The method is here applied to estimate the concentration of atmospheric SF₆ since 1970. Both exponential and linear fits are investigated, but the best fit is a linear increase, C = 0.34 + 0.084 (Yr-1970), where Yr is the calendar year and C is the concentration in pptv. A preliminary look at two CCl₄ profiles suggests that at least 50% of the atmospheric burden is of recent anthropogenic origin.     

Homogeneous oxidation of sulphur compounds in the atmosphere

Work carried out under the European COST 61a Project on the homogeneous oxidation of sulphur compounds in the atmosphere is briefly reviewed. Mechanisms for sulphur dioxide can be divided into three classes;

• 1.(a) oxidation by free radicals generated photochemically,
• 2.(b) oxidation by intermediates produced in thermal reactions, and
• 3.(c) direct photo-oxidation.

Only (a) makes a substantial contribution to SO₂ oxidation with calculated maximum rates of between 2 and 6% h⁻¹ in sunlight irradiated urban air during summer months and 1–2% h⁻¹ in unpolluted air. Most of the oxidation is brought about by the attack of the OH radical on SO₂ but the contribution of RO₂ radical attack is not well determined due to uncertainties in RO₂ rate constants. H₂S, CH₃SH and (CH₃)₂S react with OH radicals giving atmospheric life-times about 1 day.     

Effect of biogenic iron species and copper ions on the reduction of carbon tetrachloride under iron-reducing conditions

In this study, the cell-mediated and abiotic reduction of carbon tetrachloride (CCl(4)) by biogenic iron species produced from the reductive dissolution of ferrihydrite in the presence of Geobacter sulfurreducens and copper ions (Cu(II)) were investigated. 9,10-Anthraquinone-2,6-disulfonate (AQDS), serving as a surrogate of natural organic matters and an electron shuttling compound, was added to enhance the efficiency of biological reduction of the solid Fe(III) minerals. G. sulfurreducens drove the reduction of CCl(4), primarily through the formation of biogenic surface-bound iron species produced from the reductive dissolution of ferrihydrite, in the presence of 10microM AQDS. The pseudo-first-order rate constant (k(obsCT)) for CCl(4) transformation in the presence of ferrihydrite was 3.0 times higher than that resulting from the use of G. sulfurreducens alone. Addition of 0.5mM Cu(II) slightly inhibited both the growth of G. sulfurreducens and the production of biogenic Fe(II). However, the k(obsCT) values for CCl(4) transformation in ferrihydrite suspensions containing G. sulfurreducens and 0.3-0.5mM Cu(II) were 2.1-4.2 times higher than that observed in the absence of Cu(II). X-Ray powder diffraction analysis indicated that the added Cu(II) reacted with the biogenic Fe(II) ions to produce catalytic cuprous ions (Cu(I)) and secondary iron oxide minerals such as magnetite and goethite, resulting in accelerating the chemical transformation efficiency and rate of CCl(4) under iron-reducing conditions.     

The influence of iron and sulfur mineral fractions on carbon tetrachloride transformation in model anaerobic soils and sediments

The objective of this research was to identify the dissolved species or solid phase mineral fraction(s) best correlated with rates of carbon tetrachloride (CT) reductive transformation in systems modeling sulfate-reducing and iron oxide-rich soils and sediments. We used sulfide (S(-II))-treated goethite as our model system, but also studied Fe(II) and S(-II)-treated goethite, Fe(II)-treated goethite, pure FeS, and Fe(II)-treated FeS in order to isolate and evaluate the influence of different mineral fractions on reaction rates. Initial rates of CT transformation were measured for different pH values and concentrations of added Fe(II), as well as different aging times and conditions. The following dissolved species and iron and sulfur mineral fractions were quantified and compared with CT transformation rates: aqueous Fe(2+) and S(-II), surface associated Fe(II) (including weakly and strongly bound Fe(II)), FeS(s), and Cr(II) reducible solid phase S. Over the pH range of 6-10, CT transformation rates were correlated with surface associated Fe(II), while at pH 8, rates were correlated with weakly bound Fe(II). Aging of S(-II)-treated goethite led to oxidation of surface sulfur and a change in the concentration of weakly bound Fe(II), but did not change the relationship between initial rates and weakly bound Fe(II). The results of this research suggest that surface associated Fe(II) and weakly bound Fe(II) could serve as indicators of the potential for abiotic CT dechlorination in natural soils under sulfate-reducing conditions.     

Degradation and photodegradation of tetraacetylethylenediamine (TAED) in the presence of iron (III) in aqueous solution

The dark degradation of tetraacetylethylenediamine (TAED) was investigated. It is a slow process which is favored in acidic medium. There is a hydrolysis of an imide group with the scission of the C---N bond giving rise to the triacetyl derivative (TAED'). When allowed to stand for longer times a second acetyl group is eliminated with the formation of the symetric diacetyl derivative (DAED). The degradation of TAED photoinduced by iron (III) was also investigated. It appears a faster degradation which does not lead to the same products. The process only involves ^•OH radicals formed upon photolysis of aquocomplex of iron (III). They preferentially abstract a hydrogen from the methylene group. The degradation is then assisted by oxygen and leads to the formation of carbonylated oxidation products.     

含有机物铁泥的超临界水氧化法资源化

氨基染料生产过程中产生大量含有机物的铁泥,对环境造成严重污染并造成资源的极大浪费.利用超临界水氧化法对含有机物铁泥进行资源化处理研究,并对产物进行了X射线衍射分析（XRD）、色差实验与电子探针分析.研究结果显示,用超临界水氧化法处理铁泥可以将铁泥中所含的有机物完全氧化,真正实现环境友好;超临界水首先将铁泥氧化成α-Fe2O3与γ-Fe2O3,再经过800℃煅烧后可以作为氧化铁红颜料使用;超临界反应压力对样品的晶型与颜色影响不大.     

含有机物铁泥的超临界水氧化法资源化

氨基染料生产过程中产生大量含有机物的铁泥,对环境造成严重污染并造成资源的极大浪费.利用超临界水氧化法对含有机物铁泥进行资源化处理研究,并对产物进行了X射线衍射分析(XRD)、色差实验与电子探针分析.研究结果显示,用超临界水氧化法处理铁泥可以将铁泥中所含的有机物完全氧化,真正实现环境友好;超临界水首先将铁泥氧化成α-Fe2O3与γ-Fe2O3,再经过800℃煅烧后可以作为氧化铁红颜料使用;超临界反应压力对样品的晶型与颜色影响不大.     

Past and future trends in concentrations of sulphur and nitrogen compounds in the Arctic

Recent trends in nitrogen and sulphur compounds in air and precipitation from a range of Arctic monitoring stations are presented, with seasonal data from the late 70s to 2004 or 2005. Earlier findings of declining sulphur concentrations are confirmed for most stations, while the pattern is less clear for reduced and oxidized nitrogen. In fact there are positive trends for nitrogen compounds in air at several stations. Acidity is generally reduced at many stations while the precipitation amount is either increasing or stable. Variability of sulphate concentrations in air for the period 1991–2000 is reasonably well reproduced at most stations using an Eulerian, hemispherical model. Results for nitrogen compounds are weaker. Scenario studies show that even if large sulphur emission reductions take place in important source regions in South-East Asia in the coming decades, only small changes in Arctic deposition can be expected. This is because South-East Asian emissions have small influence north of the Arctic circle.     

Scrubbing intensification for sulphur and ammonia compounds removal

Operating conditions were optimised in a new compact scrubber in order to remove odorous sulphur (H(2)S and CH(3)SH) and ammonia compounds. The influence of the superficial gas and liquid velocities, pH, contactor length, inlet concentrations (sulphur compounds, ammonia, chlorine), and the mixing effects was characterised. Whereas abatement increased with velocities, pH and the chlorine concentration, an increase of inlet CH(3)SH concentration drove to a worse efficiency of process. Moreover, the contactor length and the presence of another pollutant in the gas phase only played a role on the methylmercaptan removal. Finally, the reactive consumptions were estimated at the outlet of the reactor. The chlorination by-product quantification permitted to understand the under-stoichiometry.     

Degradation of atrazine by catalytic ozonation in the presence of iron scraps: performance,transformation pathway,and acute toxicity

Degradation of atrazine by catalytic ozonation in the presence of iron scraps (ZVI/O₃) was carried out. The key operational parameters (i.e., initial pH, ZVI dosage, and ozone dosage) were optimized by the batch experiments, respectively. This ZVI/O₃ system exhibited much higher degradation efficiency of atrazine than the single ozonation, ZVI, and traditional ZVI/O₂ systems. The result shows that the pseudo-first-order constant (0.0927?min^?1) and TOC removal rate (86.6%) obtained by the ZVI/O₃ process were much higher than those of the three control experiments. In addition, X-ray diffraction (XRD) analysis indicates that slight of γ-FeOOH and Fe₂O₃ were formed on the surface of iron scrap after ZVI/O₃ treatment. These corrosion products exhibit high catalytic ability for ozone decomposition, which could generate more hydroxyl radical (HO^?) to degrade atrazine. Six transformation intermediates were identified by liquid chromatography-mass spectrometry (LC-MS) analysis in ZVI/O₃ system, and the degradation pathway of atrazine was proposed. Toxicity tests based on the inhibition of the luminescence emitted by Photobacterium phosphoreum and Vibrio fischeri indicate the detoxification of atrazine by ZVI/O₃ system. Finally, reused experiments indicate the approving recyclability of iron scraps. Consequently, the ZVI/O₃ system could be as an effective and promising technology for pesticide wastewater treatment.     

Modeling of gas-phase photodegradation of chloroform and carbon tetrachloride

The relationship between the irradiance in a photoreactor and the rate of photodegradation of organics is essential in the scaling-up of photoreactors to treat large volumes of air contaminated with organic pollutants. In this study, the analysis is adopted to compare results obtained from two different photoreactors. Initially, the applicability of two light models in calculating the irradiance in two photoreactors was evaluated. Thereafter, kinetic models of ultraviolet (UV) photooxidation of chloroform (CHCl3) and carbon tetrachloride (CCl4) from the archived literature were tested using experimental data under various operating conditions and different irradiances. Sensitivity analyses were conducted using different values of model parameters to determine the significance of each parameter on the photodegradation of the two chlorinated organics. For compounds that undergo photolysis as a primary mode of degradation, the rate of photodegradation at low initial concentrations can be predicted easily by the following equation: d[C]/dt = -2.303Iave, lambdaepsilonlambdaphilambda[C]. Although the photodegradation of chlorinated organic compounds in dry and humid air can be predicted well, it is difficult to predict the Cl* sensitized oxidation occurring at high initial concentrations. A good agreement between the simulated and experimental data provides a sound basis for the design of large-scale reactors.     

Degradation and toxicity of phenyltin compounds in soil

Although the fate of organotins has been widely studied in the marine environment, fewer studies have considered their impact in terrestrial systems. The degradation and toxicity of triphenyltin in autoclaved, autoclaved-reinoculated and non-sterilised soil was studied in a 231 day incubation experiment following a single application. Degradation and toxicity of phenyltin compounds in soil was monitored using both chemical and microbial (lux-based bacterial biosensors) methods. Degradation was significantly slower in the sterile soil when compared to non-sterilised soils. In the non-sterilised treatment, the half-life of triphenyltin was 27 and 33 days at amendments of 10 and 20 mg Sn kg(-1), respectively. As initial triphenyltin degradation occurred, there was a commensurate increase in toxicity, reflecting the fact that metabolites produced may be both more bioavailable and toxic to the target receptor. Over time, the toxicity reduced as degradation proceeded. The toxicity impact on non-target receptors for these compounds may be significant.