Ferrate(VI) oxidation of zinc-cyanide complex

Zinc-cyanide complexes are found in gold mining effluents and in metal finishing rinse water. The effect of Zn(II) on the oxidation of cyanide by ferrate(VI) (Fe(VI)O(4)(2-), Fe(VI)) was thus investigated by studying the kinetics of the reaction of Fe(VI) with cyanide present in a potassium salt of a zinc cyanide complex (K(2)Zn(CN)(4)) and in a mixture of Zn(II) and cyanide solutions as a function of pH (9.0-11.0). The rate-law for the oxidation of Zn(CN)(4)(2-) by Fe(VI) was found to be -d[Fe(VI)]/dt=k[Fe(VI)][Zn(CN)(4)(2-)](0.5). The rate constant, k, decreased with an increase in pH. The effect of temperature (15-45 degrees C) on the oxidation was studied at pH 9.0, which gave an activation energy of 45.7+/-1.5kJmol(-1). The cyanide oxidation rate decreased in the presence of the Zn(II) ions. However, Zn(II) ions had no effect on the cyanide removal efficiency by Fe(VI) and the stoichiometry of Fe(VI) to cyanide was approximately 1:1; similar to the stoichiometry in absence of Zn(II) ions. The destruction of cyanide by Fe(VI) resulted in cyanate. The experiments on removal of cyanide from rinse water using Fe(VI) demonstrated complete conversion of cyanide to cyanate.     

Modeling the reaction kinetics of Fenton's process on the removal of atrazine

The degradation of pesticide, atrazine (ATZ), 2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine, by Fenton's reagent (FR) was investigated as a function of reagents' concentrations and ratios in a batch reactor. The degradation of ATZ was effectively achieved by hydroxyl radicals, which were generated in the FR process. The decay rates of ATZ and the oxidation capacities of FR were found to depend on the concentrations of hydrogen peroxide and ferrous ion. The removal kinetics of ATZ are initiated by a rapid decay and then followed by a much slower one. After an extended reaction time (5-10 min), the reactions ceased because the Fe(II) and H(2)O(2) were consumed and would be deactivated in the process. A mathematical model was successfully developed to describe the two-stage reaction kinetics by using two simple but critical parameters: the initial ATZ decay rate and the final oxidation capacity of Fenton's process. In general, higher [Fe(II)] or H(2)O(2) concentrations result in faster initial decay rate and higher oxidation capacity. However, the oxidation capacity is more sensitive to the initial [Fe(II)] due to the presence of side reactions as discussed in the paper.     

Enhancement by anthraquinone-2-sulphonate of the photonitration of phenol by nitrite: implication for the photoproduction of nitrogen dioxide by coloured dissolved organic matter in surface waters

Anthraquinone-2-sulphonate (AQ2S) under UVA irradiation is able to oxidise nitrite to (·)NO(2) and to induce the nitration of phenol. The process involves the very fast reactions of the excited triplet state (3)AQ2S(*) and its 520-nm absorbing exciplex with water, at different time scales (ns and μs, respectively). Quinones are ubiquitous components of coloured dissolved organic matter (CDOM) in surface waters and AQ2S was adopted here as a proxy of CDOM. Using a recently developed model of surface-water photochemistry, we found that the oxidation of nitrite to (·)NO(2) by (3)CDOM(*) could be an important (·)NO(2) source in water bodies with high [NO(2)(-)] to [NO(3)(-)] ratio, for elevated values of column depth and NPOC.     

In situ iron activated persulfate oxidative fluid sparging treatment of TCE contamination--a proof of concept study

In situ chemical oxidation (ISCO) is considered a reliable technology to treat groundwater contaminated with high concentrations of organic contaminants. An ISCO oxidant, persulfate anion (S(2)O(8)(2-)) can be activated by ferrous ion (Fe(2+)) to generate sulfate radicals (E(o)=2.6 V), which are capable of destroying trichloroethylene (TCE). The property of polarity inhibits S(2)O(8)(2-) or sulfate radical (SO(4)(-)) from effectively oxidizing separate phase TCE, a dense non-aqueous phase liquid (DNAPL). Thus the oxidation primarily takes place in the aqueous phase where TCE is dissolved. A bench column study was conducted to demonstrate a conceptual remediation method by flushing either S(2)O(8)(2-) or Fe(2+) through a soil column, where the TCE DNAPL was present, and passing the dissolved mixture through either a Fe(2+) or S(2)O(8)(2-) fluid sparging curtain. Also, the effect of a solubility enhancing chemical, hydroxypropyl-beta-cyclodextrin (HPCD), was tested to evaluate its ability to increase the aqueous TCE concentration. Both flushing arrangements may result in similar TCE degradation efficiencies of 35% to 42% estimated by the ratio of TCE degraded/(TCE degraded+TCE remained in effluent) and degradation byproduct chloride generation rates of 4.9 to 7.6 mg Cl(-) per soil column pore volume. The addition of HPCD did greatly increase the aqueous TCE concentration. However, the TCE degradation efficiency decreased because the TCE degradation was a lower percentage of the relatively greater amount of dissolved TCE by HPCD. This conceptual treatment may serve as a reference for potential on-site application.     

Photocatalytic mineralization of glyphosate in a small-scale plug flow simulation reactor by UV/TiO2

The present work involves the photocatalytic mineralization of glyphosate on a plug flow reactor by UV/TiO(2). The effect of catalyst loading shows an optimal value (0.4 g L(-1)) which is necessary to mineralize glyphosate. The kinetic rate of glyphosate mineralization decreases with the increasing initial concentration of glyphosate, and the data can be described using the first-order model. An alkaline environment is conducive to glyphosate mineralization. The mineralization efficiency increases with elevated flow rate to 114 mL min(-1), which is followed by a decrease with a further increase in flow rate due to the reduction of the residence time. The presence of external oxidants (K(2)S(2)O(8), H(2)O(2) and KBrO(3)) and photosencitizer (humic acid) can significantly enhance glyphosate mineralization. Photocatalysis oxidation ability of the three studied oxidants decrease in the order of: S(2)O(8)(2-) > BrO(3)(-) > H(2)O(2). Finally, the Langmuir-Hinshelwood (L-H) model was used to rationalize the mechanisms of reactions occurring on TiO(2) surfaces and L-H model constants were also determined.     

A comparative study of the effects of chloride, sulfate and nitrate ions on the rates of decomposition of H2O2 and organic compounds by Fe(II)/H2O2 and Fe(III)/H2O2

The effects of chloride, nitrate, perchlorate and sulfate ions on the rates of the decomposition of hydrogen peroxide and the oxidation of organic compounds by the Fenton's process have been investigated. Experiments were conducted in a batch reactor, in the dark at pH < or = 3.0 and at 25 degrees C. Data obtained from Fe(II)/H2O2 experiments with [Fe(II)]0/[H2O2]0 > or = 2 mol mol(-1), showed that the rates of reaction between Fe(II) and H2O2 followed the order SO4(2-) > ClO4(-) = NO3- = Cl-. For the Fe(III)/H2O2 process, identical rates were obtained in the presence of nitrate and perchlorate, whereas the presence of sulfate or chloride markedly decreased the rates of decomposition of H2O2 by Fe(III) and the rates of oxidation of atrazine ([atrazine]0 = 0.83 microM), 4-nitrophenol ([4-NP]0 = 1 mM) and acetic acid ([acetic acid]0 = 2 mM). These inhibitory effects have been attributed to a decrease of the rate of generation of hydroxyl radicals resulting from the formation of Fe(III) complexes and the formation of less reactive (SO4(*-)) or much less reactive (Cl2(*-)) inorganic radicals.     

Reduction of ferrate(VI) and oxidation of cyanate in a Fe(VI)-TiO2-UV-NCO- system

The aqueous photocatalytic degradation of cyanate (NCO(-)), which is a long-lived neurotoxin formed during the remediation of cyanide in industrial waste streams, was studied in the ferrate(VI)-UV-TiO2-NCO(-) system. Kinetics measurements of the photocatalytic reduction of ferrate(VI) were carried out as a function of [NCO(-)], [ferrate(VI)], [O(2)], light intensity (I(o)), and amount of TiO2 in suspensions at pH 9.0. The photocatalytic reduction rate of ferrate(VI) in the studied system can be expressed as -d[Fe(VI)]/dt=kI(o)(0.5) [NCO(-)] [TiO2]. The rate of photocatalytic oxidation of cyanate with ferrate(VI) was greater than the rate in the analogous system without ferrate(VI). The possibility of involvement of reactive ferrate(V) species for this enhancement was determined by studying the reactivity of ferrate(V) with NCO(-) in a homogeneous solution using a premix pulse radiolysis technique. The rate constant for the reaction of ferrate(V) and NCO(-) in alkaline medium was estimated to be (9.60+/-0.07) x 10(2) M(-1) s(-1), which is much slower than the ferrate(VI) self-decomposition reaction (k approximately 10(7) M(-1) s(-1)). An analysis of the kinetic data in the Fe(VI)-UV-TiO2-NCO(-) system suggests that ferrate(V) is not directly participating in the oxidation of cyanate. Possible reactions in the system are presented to explain results of ferrate(VI) reduction and oxidation of cyanate.     

Reduction of Ag(I), Au(III), Cu(II), and Hg(II) by Fe(II)/Fe(III) hydroxysulfate green rust

Green rusts are mixed Fe(II)/Fe(III) hydroxides that are found in many suboxic environments where they are believed to play a central role in the biogeochemical cycling of iron. X-ray absorption fine structure analysis of hydroxysulfate green rust suspensions spiked with aqueous solutions of AgCH(3)COO, AuCl(n)(OH)(4-n), CuCl(2), or HgCl(2) showed that Ag(I), Au(III), Cu(II), and Hg(II) were readily reduced to Ag(0), Au(0), Cu(0), and Hg(0). Imaging of the resulting solids from the Ag(I)-, Au(III)-, and Cu(II)-amended green rust suspensions by transmission electron microscopy indicated the formation of submicron-sized particles of Ag(0), Au(0), and Cu(0). The facile reduction of Ag(I), Au(III), Cu(II), and Hg(II) to Ag(0), Au(0), Cu(0), and Hg(0), respectively, by green rust suggests that the presence of green rusts in suboxic soils and sediments can have a significant impact on the biogeochemistry of silver, gold, copper, and mercury, particularly with respect to their mobility.     

Ferrate(VI): green chemistry oxidant for degradation of cationic surfactant

Iron in its familiar form exists in the +2 and +3 oxidation states, however, higher oxidation state of iron +6, ferrate(VI) (Fe(VI)O(4)(2-)) can be obtained. The high oxidation power of ferrate(VI) can be utilized in developing cleaner ("greener") technology for remediation processes. This paper demonstrates the unique property of ferrate(VI) to degrade almost completely the cationic surfactant, cetylpyridinium chloride (C(5)H(5)N(+)(CH(2))(15)CH(3).H(2)O Cl(-), CPC). The Rate law for the oxidation of CPC by ferrate(VI) at pH 9.2 was found to be: -d[Fe(VI)]/dt = k[Fe(VI)][CPC](2). Ferrate(VI) oxidizes CPC within minutes and molar consumption of ferrate(VI) was nearly equal to the oxidized CPC. The decrease in total organic carbon (TOC) from CPC was more than 95%; suggesting mineralization of CPC to carbon dioxide. Ammonium ion was the other product of the oxidation. This is the first report in which Fe(VI)O(4)(2-) ion opens the pyridine ring and mineralizes the aliphatic chain of the organic molecule giving inorganic ions.     

An unconventional approach to studying the reaction kinetics of the Fenton's oxidation of 2,4-dichlorophenoxyacetic acid

The Fenton's oxidation kinetics of herbicide 2,4-D at various [Fe(II)] and [H(2)O(2)] combinations was investigated and modelled through an unconventional approach. The reaction kinetics of 2,4-D degradation demonstrated a two-stage pattern of decay, where a very fast reactive stage was followed by a retardation stage due to the depletion of oxidants and to the competitive side-reactions of the intermediates (including 2,4-dichlorophenol, chlorohydroquinone and 2,6-dichlororesorcinol). A model characterized by two newly established constants, the initial decay rate and the maximum oxidative capacity, was proposed and proven capable of describing the two-stage process, which cannot easily be described by conventional first- or second-order kinetics approaches.     

Studies on electrochemical recovery of silver from simulated waste water from Ag(II)/Ag(I) based mediated electrochemical oxidation process

In the Ag(II)/Ag(I) based mediated electrochemical oxidation (MEO) process, the spent waste from the electrochemical cell, which is integrated with the scrubber columns, contains high concentrations of precious silver as dissolved ions in both the anolyte and the catholyte. This work presents an electrochemical developmental study for the recovery of silver from simulated waste water from Ag(II)/Ag(I) based MEO process. Galvanostatic method of silver deposition on Ti cathode in an undivided cell was used, and the silver recovery rate kinetics of silver deposition was followed. Various experimental parameters, which have a direct bearing on the metal recovery efficiency, were optimized. These included studies with the nitric acid concentration (0.75-6M), the solution stirring rate (0-1400 rpm), the inter-electrode distance between the anode and the cathode (2-8 cm), the applied current density (29.4-88.2 mA cm(-2)), and the initial Ag(I) ion concentration (0.01-0.2M). The silver recovered by the present electrodeposition method was re-dissolved in 6M nitric acid and subjected to electrooxidation of Ag(I) to Ag(II) to ascertain its activity towards Ag(II) electrogeneration from Ag(I), which is a key factor for the efficient working of MEO process. Our studies showed that the silver metal recovered by the present electrochemical deposition method could be reused repeatedly for MEO process with no loss in its electrochemical activity. Some work on silver deposition from sulfuric acid solution of different concentrations was also done because of its promising features as the catholyte in the Ag(II) generating electrochemical cell used in MEO process, which include: (i) complete elimination of poisonous NO(x) gas liberation in the cathode compartment, (ii) reduced Ag(+) ion migration across Nafion membrane from anolyte to catholyte thereby diminished catholyte contamination, and (iii) lower cell voltage and hence lesser power consumption.     

Recharge processes drive sulfate reduction in an alluvial aquifer contaminated with landfill leachate

Natural attenuation of contaminants in groundwater depends on an adequate supply of electron acceptors to stimulate biodegradation. In an alluvial aquifer contaminated with leachate from an unlined municipal landfill, the mechanism of recharge infiltration was investigated as a source of electron acceptors. Water samples were collected monthly at closely spaced intervals in the top 2 m of the saturated zone from a leachate-contaminated well and an uncontaminated well, and analyzed for delta(18)O, delta(2)H, non-volatile dissolved organic carbon (NVDOC), SO(4)(2-), NO(3)(-) and Cl(-). Monthly recharge amounts were quantified using the offset of the delta(18)O or delta(2)H from the local meteoric water line as a parameter to distinguish water types, as evaporation and methanogenesis caused isotopic enrichment in waters from different sources. Presence of dissolved SO(4)(2-) in the top 1 to 2 m of the saturated zone was associated with recharge; SO(4)(2-) averaged 2.2 mM, with maximum concentrations of 15 mM. Nitrate was observed near the water table at the contaminated site at concentrations up to 4.6 mM. Temporal monitoring of delta(2)H and SO(4)(2-) showed that vertical transport of recharge carried SO(4)(2-) to depths up to 1.75 m below the water table, supplying an additional electron acceptor to the predominantly methanogenic leachate plume. Measurements of delta(34)S in SO(4)(2-) indicated both SO(4)(2-) reduction and sulfide oxidation were occurring in the aquifer. Depth-integrated net SO(4)(2-) reduction rates, calculated using the natural Cl(-) gradient as a conservative tracer, ranged from 7.5x10(-3) to 0.61 mM.d(-1) (over various depth intervals from 0.45 to 1.75 m). Sulfate reduction occurred at both the contaminated and uncontaminated sites; however, median SO(4)(2-) reduction rates were higher at the contaminated site. Although estimated SO(4)(2-) reduction rates are relatively high, significant decreases in NVDOC were not observed at the contaminated site. Organic compounds more labile than the leachate NVDOC may be present in the root zone, and SO(4)(2-) reduction may be coupled to methane oxidation. The results show that sulfur (and possibly nitrogen) redox processes within the top 2 m of the aquifer are directly related to recharge timing and seasonal water level changes in the aquifer. The results suggest that SO(4)(2-) reduction associated with the infiltration of recharge may be a significant factor affecting natural attenuation of contaminants in alluvial aquifers.     

Microbial perchlorate reduction with elemental sulfur and other inorganic electron donors

ClO(4)(-) has recently been recognized as a widespread contaminant of surface and ground water. This research investigated chemolithotrophic perchlorate reduction by bacteria in soils and sludges utilizing inorganic electron-donating substrates such as hydrogen, elemental iron, and elemental sulfur. The bioassays were performed in anaerobic serum bottles with various inocula from anaerobic or aerobic environments. All the tested sludge inocula were capable of reducing perchlorate with H2 as electron donor. Aerobic activated sludge was evaluated further and it supported perchlorate reduction with Fe(0) and S(0) additions under anaerobic conditions. Heat-killed sludge did not convert ClO(4)(-), confirming the reactions were biologically catalyzed. ClO(4)(-) (3mM) was almost completely removed by the first sampling time on d 8 with H2 (> or = 0.37mMd(-1)), after 22d with S(0) (0.18mM d(-1)) and 84% removed after 37d with Fe(0) additions (0.085mMd(-1)). Perchlorate-reduction occurred at a much faster rate (1.12mMd(-1)), when using an enrichment culture developed from the activated sludge with S(0) as an electron donor. The enrichment culture also utilized S(2-) and S(2)O(3)(2-) as electron-donating substrates to support ClO(4)(-) reduction. The mixed cultures also catalyzed the disproportionation of S(0) to S(2-) and SO(4)(2-). Evidence is presented demonstrating that S(0) was directly utilized by microorganisms to support perchlorate-reduction. In all the experiments, ClO(4)(-) was stoichiometrically converted to chloride. The study demonstrates that microorganisms present in wastewater sludges can readily use a variety of inorganic compounds to support perchlorate reduction.     

Photooxidation of naphthalenesulfonic acids: comparison between processes based on O(3), O(3)/activated carbon and UV/H(2)O(2)

The aim of the present study was to analyze and compare the efficacy of UV photodegradation with that of different advanced oxidation processes (O(3), UV/H(2)O(2), O(3)/activated carbon) in the degradation of naphthalenesulfonic acids from aqueous solution and to investigate the kinetics and the mechanism involved in these processes. Results obtained showed that photodegradation with UV radiation (254 nm) of 1-naphthalenesulfonic, 1,5-naphthalendisulfonic and 1,3,6-naphthalentrisulfonic acids is not effective. Presence of duroquinone and 4-carboxybenzophenone during UV irradiation (308-410 nm) of the naphthalenesulfonic acids increased the photodegradation rate. Addition of H(2)O(2) during irradiation of naphthalenesulfonic acids accelerated their elimination, due to the generation of ()OH radicals in the medium. Comparison between UV photodegradation 254 m and the advanced oxidation processes (O(3), O(3)/activated carbon and UV/H(2)O(2)) showed the low-efficacy of the former in the degradation of these compounds from aqueous medium. Thus, among the systems studied, those based on the use of UV/H(2)O(2) and O(3)/activated carbon were the most effective in the oxidation of these contaminants from the medium. This is because of the high-reactivity of naphthalenesulfonic acids with the *OH radicals generated by these two systems. This was confirmed by the values of the reaction rate constant of *OH radicals with these compounds k(OH), obtained by competitive kinetics (5.7 x 10(9) M(-1) s(-1), 5.2 x 10(9) M(-1) s(-1) and 3.7 x 10(9) M(-1) s(-1) for NS, NDS and NTS, respectively).     

Kinetics and mechanism of nitrite oxidation by hypochlorous acid in the aqueous phase

The rate coefficient for the reaction of nitrite with hypochlorite and hypochlorous acid has been studied using spectrophotometric measurements. The reaction rate has been determined in a wide range of H(+) concentration (5< or =-log[H(+)]< or =11). The kinetics were carried out as a function of NO(2)(-), H(+) and total hypochlorite ([HOCl](total)=[HOCl]+[ClO(-)]+[ClNO(2)]) concentrations. The observed overall rate law is described by: -d[HClO](T)dt=[a[NO(2)(-)](2)+b[NO(2)(-)]][H(+)](2)c+d[H(+)]+e[NO(2)(-)][H(+)](2)[HOCl](total)At T=298 K and in Na(2)SO(4) at an ionic strength (I=1.00 M), we obtained using a nonlinear fitting procedure: a=(1.83+/-0.36)x10(7) s(-1), b=(1.14+/-0.23)x10(5) Ms(-1), c=(1.12+/-0.17)x10(-13) M, d=(1.43+/-0.29)x10(-6) M(2) and e=(1.41+/-0.28)x10(3) M where the errors represent 2sigma. According to the overall rate law, a/b=k(1)/k(3), b/e=k(3), c=K(w), d/c=K(a), d=K(a)K(w) and e=K(1)K(a). In Na(2)SO(4) at an ionic strength (I=1.00 M), the values of K(1) and K(a) are (1.1+/-0.1)x10(-4) and 1.28x10(7) M(-1), respectively. A mechanism is proposed for the NO(2)(-) oxidation which involves the reversible initial step: NO(2)(-)+HOCl left harpoon over right harpoon ClNO(2)+OH(-) (K(1)), while ClNO(2) undergoes the two parallel reactions: attack by NO(2)(-) (k(1)) and hydrolysis (k(3)). ClNO(2) and N(2)O(4) are proposed as important intermediates as they control the mechanism. The rate coefficients k(1) and k(3) have been determined at different ionic strengths in NaCl and Na(2)SO(4). The influence of the ionic strength and ionic environment has been studied in this work.     

Effect of oxygen limitation on solid-bed bioleaching of heavy metals from contaminated sediments

The effects of oxygen limitation on solid-bed bioleaching of heavy metals (Me) were studied in a laboratory percolator system using contaminated sediment supplemented with 2% elemental sulfur (So). Oxygen limitation was realized by controlling the gas flow and oxygen concentration in the aeration gas. The oxygen supply varied between 150 and 0.5 mol So (-1) over 28 d of leaching. Moderate oxygen limitation led to temporarily suppression of acidification, rate of sulfate generation and Me solubilization. Lowering the oxygen supply to 0.5 mol O2 mol So (-1) resulted in retarding acidification over a period of three weeks and in poor Me solubilization. Oxidation of So occurred even under strong oxygen limitation at a low rate. High surplus of oxygen was necessary for almost complete oxidation of the added So. The maximum Me solubilization was reached at an oxygen supply of 7.5 mol O2 mol So (-1). Thus, the oxygen input during solid-bed bioleaching can be reduced considerably by controlling the gas flow without loss of metal removal efficiency. Oxygen consumption rates, ranging from 0.4 x 10(-8) to 0.8 x 10(-8) Kg O2 Kg dm (-1) S(-1), are primarily attributed to high reactivity of the sulfur flower and high tolerance of indigenous autotrophic bacteria to low oxygen concentrations. The So related oxygen consumption was calculated assuming a molar yield coefficient Y O2/S of 1.21. The oxygen conversion degree, defined as part of oxygen feed consumed by So oxidation, increased from 0.7% to 68% when the oxygen supply was reduced from 150 to 0.5 mol O2 mol So (-1).     

Light-induced disappearance of nitrite in the presence of iron (III)

Understanding of rapid disappearance of nitrite in natural waters and its impact on nitrogen natural cycling has remained limited. We found that NO2- disappeared rapidly in pH 3.2 aqueous Fe(III) solutions both in sunlight and in 356 nm light. Quantum yields of the NO2- loss at 356 nm were 0.049-0.14 for initial levels of 10-80 microns NO2- and 200 microns Fe(III). The NO2- loss (at 356 nm) followed apparent first-order kinetics. The rate constants were 1.3 x 10(-3) (40 microns NO2-) and 4.1 x 10(-4) s-1 (80 microns NO2-) for 100 microns Fe(III), and 2.3 x 10(-3) (40 microns NO2-) and 7.5 x 10(-4) s-1 (80 microns NO2(-1)) for 200 microns Fe(III) (t1/2 = 8.7, 27.9, 5.1, and 15.3 min, respectively). The rate constants were directly proportional to [Fe(III)]0 and inversely proportional to [NO2-]0. Agreement between the rate constants obtained experimentally and those calculated mechanistically supports the hypothesis that NO2- was oxidized to NO2 by .OH radicals from photolysis of FeOH2+ complexes, and at high [NO2-]0 (e.g., 80 microns) relative to [Fe(III)]0, hydrolysis of NO2 or N2O4 to form NO3- and NO2- could be significant. This study showed that light and Fe(III)-induced oxidation of NO2- (rate = approximately 10(-1)-10(-2) microns s-1) was more rapid than its direct photolysis (rate = approximately 10(-4) microns s-1), and the photolysis could be a significant source of .OH radicals only in cases where the Fe(III) level is much lower than the NO2- level ([Fe(III)]/[NO2-] < 1/80). This study suggests that the light and Fe(III)-induced oxidation of NO2- would be one potential important pathway responsible for the rapid transformation of NO2- in acidic surface waters, especially those affected by acid-mine drainage or volcanic activities. This study also may be of interest for modeling certain acidic atmospheric water environments.     

Reduction of silver solubility by humic acid and thiol ligands during acanthite (beta-Ag2S) dissolution

Precipitation of highly insoluble metal sulfide minerals like acanthite (beta-Ag2S) or red cinnabar (HgS) is in principle an effective means to reduce metal availability and toxicity in contaminated soils. Unfortunately, experiments have shown that red cinnabar may be solubilized in the presence of dissolved organic matter or thiol ligands. To determine whether the same applies to acanthite, a laboratory synthesized beta-Ag2S mineral was incubated for up to 3 weeks in the presence of KNO3, dissolved humic acids, cysteine, methionine and thiosulfate. XPS analysis identified Ag2O (52%), Ag2SO4 (8%) and Ag2S (40%) on the particle surfaces. Ag was released into solution in the presence of KNO3 and methionine, presumably from mixed-oxidation surface layers. Contrary to earlier results with cinnabar, however, humic acids reduced Ag concentrations in solution by about 75%, and cysteine and thiosulfate, each containing a free -SH functional group, almost completely suppressed Ag release into solution.     

Comparison of oxygen-transfer measurement methods under process conditions.

The objective of this paper is to compare the following four methods of measuring oxygen transfer in wastewater treatment plants under process conditions: the offgas, hydrogen peroxide (H2O2), reaeration, and in situ oxygen uptake rate (OUR) methods. Comparative tests were performed under controlled conditions in a pilot column and in six full-scale oxidation ditches equipped with fine-bubble diffusers and slow-speed mixers. The offgas and H2O2 methods give similar results (differences between the oxygen-transfer coefficients under field conditions [k(L)a(f)] from each method lower than 10%). The reaeration procedure gives more random results (differences from -5 to -43% compared with values obtained using the offgas method). The in situ OUR method, in the presence of a horizontal flow of mixed liquor, leads to an estimate of k(L)a(f) to within 15% of the offgas value.