Biodegradation of chlorinated phenols in subsurface soils

Microcosm studies were employed to determine the subsurface biodegradation rates of phenol, 2-chlorophenol (2-CP), 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP), and pentachlorophenol (PCP). Soil samples were taken from sites in Pennsylvania and Virginia from depths up to 31 m, and all samples contained significant microbial populations. Soil from both sites readily biodegraded all five compounds. Biodegradation rates increased as initial concentrations increased, and all biodegradation rates appeared to follow first-order kinetics with regard to the initial compound concentrations. Biodegradation rates for the five compounds followed the order: phenol = 2-CP > 2,4,6-TCP > 2,4-DCP. PCP was degraded more slowly than phenol or 2-CP, but similarly to 2,4,6-TCP and 2,4-DCP. Different soils exhibited different degradation rates, and the soil characteristics that may influence the rates are discussed. The data suggest that biological degradation is a significant attenuation mechanism for phenol and its chlorinated derivatives in subsurfaces saturated and unsaturated zones.     

Degradation of phenolic and non-phenolic aromatic pollutants by four Pleurotus species: the role of laccase and versatile peroxidase

The ability of Pleurotus eryngii, Pleurotus ostreatus, Pleurotus pulmonarius and Pleurotus sajor-caju to degrade the aromatic pollutants 2,4-dichorophenol (2,4-DCP) and benzo(a)pyrene [B(a)P] in liquid culture and microcosm (using wheat straw as growth substrate and sea sand as a xenobiotic carrier) was investigated by HPLC and ¹⁴CO₂ release from labeled pollutants. We found that 100 μM 2,4-DCP was very quickly transformed by the four fungi, disappearing 24 h after its addition to the liquid cultures. However, a 2-week incubation period was required to transform 100 μM B(a)P up to 75% by P. eryngii and P. pulmonarius. Whereas the fungi were able to begin degradation of the two pollutants with high transformation rates, their complete degradation (mineralization) rates were very low. Mineralization of B(a)P in liquid cultures was only observed with P. eryngii and P. pulmonarius, although the four Pleurotus species studied were able to mineralize this compound in solid state fermentation (SSF). The ligninolytic enzymes laccase and versatile peroxidase (VP), together with aryl-alcohol oxidase (AAO) providing extracellular H₂O₂, were found in liquid cultures. Except AAO, these enzymes were also detected in SSF experiments. In order to investigate the role of ligninolytic enzymes in the process, their action on both pollutants (50 μM) was studied in vitro in the absence and presence of redox mediators. As observed with the fungal cultures, 2,4-DCP was oxidized faster than B(a)P by both laccase (60% transformation after 6 h) and VP (100% transformation after 1 h). Moreover, laccase oxidation was strongly increased (up to 90% transformation after 3 h), by the presence of the mediators 2,2′-azino-bis-(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) or 1-hydroxybenzotriazole (HBT). In the case of B(a)P, the presence of ABTS or HBT was strictly required for oxidation by laccase (25% transformation after 8 h). Degradation of B(a)P was also observed in reactions with VP (40% transformation after 6 h). The results obtained suggest that Pleurotus species can be used in applications focused to the degradation of aromatic pollutants using wheat straw as a growth substrate, and provide the first evidence on the direct transformation of recalcitrant aromatic pollutants by VP.     

Improved Photodegradation Efficiency of 2,4-DCP Through a Combined Q<Subscript>3</Subscript>Fe(III)-Decorated Porous g-C<Subscript>3</Subscript>N<Subscript>4</Subscript>/H<Subscript>2</Subscript>O<Subscript>2</Subscript> System

Graphitic carbon nitride (g-C₃N₄) is a photocatalyst with wide application in removal of organic pollutants. In this study, we designed a porous g-C₃N₄ (p-g-C₃N₄)/8-quinolinolato iron(III) (Q₃Fe)/H₂O₂ system to enhance the organic pollutant removal efficiency by combining photocatalysis and Fenton interaction under neutral condition. The p-g-C₃N₄ was prepared through a two-step thermal oxidation reaction. Afterwards, Q₃Fe-coupled p-g-C₃N₄ was prepared by an impregnating method. The 2,4-dichlorophenol (2,4-DCP) photodegradation ratio and decomposition rate of the p-g-C₃N₄/Q₃Fe/H₂O₂ system are approximately 5 and 18 times as high as those of individual p-g-C₃N₄ system, respectively. Besides, its degradation rate is 4.3 times as high as that in the p-g-C₃N₄/H₂O₂ system. Meanwhile, Q₃Fe/g-C₃N₄ also exhibits higher activity than individual p-g-C₃N₄ in 2,4-DCP photo-decomposing. On the basis of the results of the radical trapping experiments and the Fe(II) concentration in different systems, the synergistic effect between photocatalysis and Fenton reaction is vital for the efficient pollutant degradation. The coupled system combining p-g-C₃N₄ with Q₃Fe and H₂O₂ shows potential for efficient treatment of recalcitrant organic pollutants. The combined system in this work indicated a new idea for the decomposition of organic pollutants.     

Sonochemical Degradation of Chlorinated Phenolic Compounds in Water: Effects of Physicochemical Properties of the Compounds on Degradation

This study examined a comparative degradation of various chlorinated phenolic compounds including phenol, 4-chlorophenol (4-CP), 2,6-dichlorophenol (2,6-DCP), 2,4,6-trichlorophenol (2,4,6-TCP), 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP), and pentachlorophenol (PCP) using 28, 580, and 1,000 kHz ultrasonic reactors. The concentration of hydrogen peroxide was also determined in order to investigate the efficacy of different sonochemical reactors for hydroxyl radical production. Clearly, it was observed that the 580 kHz sonochemical reactor had maximum efficacy for hydroxyl radical production. The degradation of all the compounds followed the order; 580 kHz (91?C93%) > 1,000 kHz (84?C86%) > 28 kHz (17?C34%) with an initial concentration of 2.5 mg L^?1 at a reaction time of 40 min with ultrasonic power of 200 ± 3 W and aqueous temperature of 20 ± 1°C in each experiment. Overall, the degradation of those phenolic compounds followed the order, PCP > 2,3,4,6-TeCP > 2,4,6-TCP > 2,6-DCP > 4-CP > phenol at various frequencies in the presence/absence of a radical scavenger (tert-butyl alcohol). It was revealed that the correlations between the compound degradation rates and the physicochemical parameters, R ² = 0.99 for octanol?Cwater partition coefficient, R ² = 0.95 for water solubility, R ² = 0.94 for vapor pressure, and R ² = 0.88 for Henry??s law constant, excluding PCP, were very good in the entire range of each parameter.     

Multi-Step Competitive Sorption and Desorption of Chlorophenols in Surfactant Modified Montmorillonite

Single- and bi-solute sorption and desorption of 2,4-dichlorophenol (2,4-DCP) and 2,4,5-trichlorophenol (2,4,5-TCP) in montmorillonite modified with hexadecyltrimethylammonium (HDTMA) were investigated using multi-step sorption and desorption procedure. Effect of pH on the multi-step sorption and desorption was investigated. As expected by the magnitude of octanol-water partition coefficient, K _ow , both sorption and desorption affinity of 2,4,5-TCP was higher than that of 2,4-DCP at pH 4.85 and 9.15. For both chlorophenols, the protonated speciation (at pH 4.85) exhibited a higher affinity in both sorption and desorption than the predominant deprotonated speciation (about 95% and 99% of 2,4-dichlorophenolate and 2,4,5-trichlophenolate anions at pH 9.15, respectively). Desorption of chlorinated phenols was strongly dependent on the current pH regardless of their speciation in the previous sorption stage. Freundlich model was used to analyze the single-solute sorption and desorption data. No appreciable desorption-resistant (or non-desorbing) fraction was observed in organoclays after several multi-step desorptions. This indicates that sorption of phenols in organoclay mainly occurs via partitioning into the core of the pseudo-organic medium, thereby causing desorption nearly reversible. In bisolute competitive systems, sorption (or desorption) affinity of both chlorophenols was reduced compared to that in its single-solute system due to the competition between the solutes. The ideal adsorbed solution theory (IAST) coupled to the single-solute Freundlich model successfully predicted bisolute multi-step competitive sorption and desorption equilibria.     

Fate of 14C-ring-labeled 2,4-D, 2,4-dichlorophenol and 4-chlorophenol during straw composting

Experiments were carried out to study the transformation of ¹⁴C-ring-labeled 2,4-D and the two related chlorophenols 4-chlorophenol (4-CP) and 2,4-dichlorophenol (4-DCP) during straw composting under controlled laboratory conditions. Incubation under sterile and nonsterile conditions was done to evaluate the relative importance of the biotic and abiotic processes. Pre-composted straw was treated with the three chemicals. The availability of the different chemicals was monitored during incubations as well as their degradation. Under nonsterile conditions, the mineralization of both chlorophenols reached 20% of the applied compounds, whereas it was 52% for 2,4-D. Transitory water-soluble metabolites of 2,4-D and chlorophenols were formed but they disappeared rapidly. After 21 days, 21% of the 2,4-D and 38% of the 2,4-DCP was stabilized as nonextractable (bound) residues under nonsterile conditions. Bound residues of both chemicals were negligible under sterile conditions. Availability of chemicals as estimated by water extraction decreased during incubation proportionally to mineralization and to the formation of bound residues. The increase in immobilization of the chemical residues was stronger under nonsterile conditions than under sterile conditions. Under nonsterile conditions 71% of the 4-CP was recovered as bound residues, whereas under sterile conditions 30% of the applied 4-CP formed bound residues after formaldehyde addition and only 8% with autoclaved straw. Global microbial activity decreased in the presence of the chlorophenols probably due to their toxic effect. These data indicate that the biological activity associated with straw transformation during composting stimulates the depletion of 2,4-D and chlorophenols by mineralization and by formation of bound residues. Received: 6 September 1996     

Photodegradation of Bisphenol A with ZnO and TiO<Subscript>2</Subscript>: Influence of Metal Ions and Fenton Process

In this study, photocatalytic degradation of bisphenol A (BPA) was investigated using two types of catalysts (TiO₂ and ZnO) with various metal ion concentrations and amounts of added H₂O_2. A kinetic test was performed to observe the changes of BPA over time under UV irradiation in a photocatalytic reactor. Experimental results demonstrated that degradation efficiency of ZnO was higher than that of TiO₂. The degradation rate increased as catalyst dosage increased until reaching optimum dosage, after which degradation rate decreased. The addition of H₂O₂ improved the degradation efficiency of BPA, with the degradation efficiency increasing with the amount of H₂O₂. All metal ions, including Fe²⁺, Ni²⁺, and Cu²⁺, inhibited the degradation of BPA by ZnO at natural pH, whereas Fe²⁺ and Ni²⁺ enhanced degradation efficiency of BPA at acidic pH. Comparison of BPA degradation with H₂O₂ only, ZnO/H₂O₂, Fe²⁺/H₂O₂, and ZnO/Fe²⁺/H₂O₂ revealed that Fe²⁺/H₂O₂ was more efficient than other processes at lower pH (pH?=?3.44), whereas ZnO/H₂O₂ the most efficient at higher pH (pH?=?6.44). These results indicate that ZnO/H₂O₂ process was observed to be the most efficient of all processes. Degradation efficiency of BPA by ZnO was also influenced by additional parameters, including H₂O₂ concentration, metal ions, and solution pH.     

Photodegradation of Sulfamethoxazole Applying UV- and VUV-Based Processes

The efficiency of UV- and VUV-based processes (UV, VUV, UV/H₂O₂, and VUV/H₂O₂) for removal of sulfamethoxazole (SMX) in Milli-Q water and sewage treatment plant (STP) effluent was investigated at 20??C. The investigated factors included initial pH, variety of inorganic anions (NO ₃ ^? and HCO ₃ ^? ), and humic acid (HA). The results showed that the degradation of SMX in Milli-Q water at both two pH (5.5 and 7.0) followed the order of VUV/H₂O₂ > VUV > UV/H₂O₂ > UV. All the experimental data well fitted the pseudo-first order kinetic model and the rate constant (k) and half-life time (t _1/2) were determined accordingly. Indirect oxidation of SMX by generated ^?OH was the main degradation mechanism in UV/H₂O₂ and VUV/H₂O₂, while direct photolysis predominated in UV processes. The quenching tests showed that some other reactive species along with ^?OH radicals were responsible to the SMX degradation under VUV process. The addition of 20?mg?L^?1 HA significantly inhibited SMX degradation, whereas, the inhibitive effects of NO ₃ ^? and HCO ₃ ^? (0.1?mol?L^?1) were observed as well in all processes except in UV irradiation for NO ₃ ^? . The removal rate decreased 1.7?C3.6 times when applying these processes to STP effluent due to the complex constituents, suggesting that from the application point of view the constituents of these complexes in real STP effluent should be considered carefully prior to the use of UV-based processes for SMX degradation.     

Oxidation of Chlorophenols in Aqueous Solution by Excess Potassium Permanganate

A simple spectrophotometric method was developed to quantify chlorophenol (CP) concentrations after reaction with potassium permanganate and quenching with sodium sulfite. Other quenching agents (peroxide, sodium thiosulfate and hydroxylamine hydrochloride) were found to create absorbance in the spectral range required for CP quantification. Analysis at pH 12 gave greater absorption and sensitivity for the method compared with pH 5.6. The calibration curves of the proposed methods were linear in the concentration ranges 0.0061–0.61 and 0.0078–0.78 mM with detection limit of 0.0006 and 0.0008 mM for dichlorophenols and monochlorophenols, respectively. The oxidation kinetics of five chlorophenols in aqueous solution with excess potassium permanganate were evaluated using the analytical method. The pseudo-first-order reaction rates were found to be relatively rapid 1.42 × 10⁻³ to 0.024 s⁻¹ and followed the sequence 2-chlorophenol (2-CP) > 2,6-dichlorophenol (2,6-DCP) > 4-chlorophenol (4-CP) > 2,4-dichlorophenol (2, 4-DCP) > 3-chlorophenol (3-CP). The apparent second-order rate constant was calculated from the measured pseudo-first-order rate constant with respect to CP with initial KMnO₄ concentration (1.5 mM) and follows the same sequence of pseudo-first-order rate constant. This shows that chlorine atoms in the structure of chlorophenol had a significant influence on the oxidation of chlorophenols by potassium permanganate. Permanganate can be used for the treatment of chlorophenol-contaminated soil and groundwater.     

Photo-Assisted Degradation,Toxicological Assessment,and Modeling Using Artificial Neural Networks of Reactive Gray BF-2R Dye

This work investigates the degradation of Reactive Gray BF-2R dye (a blend of reactive yellow 145, reactive orange 122 and reactive black 5 dyes) using UV/H₂O₂, Fenton, and photo-Fenton-advanced oxidative processes, with artificial sunlight and UV-C radiations. The photo-Fenton process employing UV-C radiation was the most efficient under the conditions studied. The ideal conditions for the degradation of the dye, determined using a factorial design 2³ and a study of the concentration of hydrogen peroxide ([H₂O₂]), were [H₂O₂] equal to 40 mg L^?1, iron concentration [Fe] of 1 mg L^?1, and pH between 3 and 4. The Chan and Chu non-linear kinetic model predicted the kinetic data with a degradation of over 98% for color and 68% for aromatics after 60 min. The behavior of the chemical oxygen demand fitted the first-order kinetic model well, with a degradation of 64% after 60 min. The Multilayer Perceptron 7-11-2 artificial neural network model enabled to model the degradation process of the aromatics and accurately predict the experimental data. Toxicity tests indicated that the post-treatment samples were non-toxic for Escherichia coli bacteria, and Portulaca grandiflora and Basil sabory seeds. However, they inhibited the growth of Lactuca sativa seeds and Salmonella enteritidis bacteria. The photo-Fenton process with UV-C radiation degraded the dye studied efficiently and the degradation percentages were, on average, 7% and 5% higher for color than those observed when employing the Fenton and UV/H₂O₂ processes, respectively. With the aromatic, however, they were 84% and 62% higher, thus justifying the use of this process.     

Effect of Soil Organic Matter on Adsorption and Insecticidal Activity of Toxins from Bacillus thuringiensis

With the large-scale cultivation of transgenic crops expressing Bacillus thuringiensis (Bt) insecticidal toxin in the world, the problem of environmental safety caused by these Bt crops has received extensive attention. The effects of soil organic matter (SOM) on the adsorption and insecticidal activity of Bt toxin in variable- and constant-charge soils (red and brown soils, respectively) were studied. Organic carbon in the soils was removed using hydrogen peroxide (H_2O_2). After H_2O_2 treatment, the SOM in the red and brown soils decreased by 71.26% and 82.82%, respectively. Mineral composition of the H_2O_2-treated soils showed no significant changes,but soil texture showed a slight change. After SOM removal, the cation exchange capacity (CEC) and pH decreased, while the specific surface area (SSA), point of zero charge (PZC), and zeta potential increased. The adsorption isotherm experiment showed that the Bt toxin adsorption on the natural and H_2O_2-treated soils fitted both the Langmuir model (R~2≥ 0.985 7) and the Freundlich model (R~2≥ 0.984 1), and the amount of toxin adsorbed on the H_2O_2-treated soils was higher than that on the natural soils. There was a high correlation between the maximum adsorption of Bt toxin and the PZC of soils (R~2= 0.935 7); thus, Bt toxin adsorption was not only influenced by SOM content, but also by soil texture, as well as the SSA, CEC, PZC, and zeta potential. The LC_(50) (lethal concentration required to kill 50% of the larvae) values for Bt toxin in the H_2O_2-treated soils were slightly lower than those in the natural soils, suggesting that the environmental risk from Bt toxin may increase if SOM decreases. As the measurement of insecticidal activity using insects is expensive and time consuming, a rapid and convenient in vitro method of enzyme-linked immunosorbent assays is recommended for evaluating Bt toxin degradation in soils in future studies.     

The Oxidation of Di-(2-Ethylhexyl) Phthalate (DEHP) in Aqueous Solution by UV/H2O2 Photolysis

The oxidation of di-(2-ethylhexyl) phthalate (DEHP) in solution using UV/H₂O₂ and direct UV photolysis are analyzed in this study. It was found that DEHP was 100% removal in the solution by 180-min UV/H₂O₂ treatment and 73.5% removal by 180-min direct UV photolysis. The effect of different factors, such as DEHP concentration, H₂O₂ concentration, and UV light intensity, on photochemical degradation was investigated. The degradation mechanism of DEHP and the acute toxicity of intermediates were also studied. The photochemical degradation process was found to follow pseudo-first-order kinetics. The results of our study suggested that the concentration with 40 mg/L H₂O₂ and 5 μg/mL DEHP in the solution at pH 7 with 10.0?×?10^?6 Einstein l^?1?s^?1 UV was the optimal condition for the photochemical degradation of DEHP. The photochemical degradation with UV/H₂O₂ can be an efficient method to remove DEHP in wastewater.     

Biotreatment of Melanoidin-Containing Distillery Spent Wash Effluent by Free and Immobilized Aspergillus oryzae MTCC 7691

Humic acids (HA) are known as the precursors of carcinogenic compounds formed by the disinfection of drinking water. While conventional treatments were found to be inefficient HA removal processes in drinking water, advanced oxidation processes have been proven to have a significant effect in the treatment of HA. The degradation of HA was investigated using nano-sized zinc oxide (ZnO)/laponite composite (NZLC). The reactions occurred in a UVC reactor by considering following variables: pH, initial HA concentration, catalyst loading, addition of hydrogen peroxide (H₂O₂), and catalyst reuse. Water samples containing HA were analysed by ultraviolet/visible spectrophotometer and high-performance size-exclusion chromatography. Initial HA concentrations were tested by the Langmuir–Hinshelwood model with k and K _ads values, determined to be 0.126 mg/L.min and 0.0257 L/mg, respectively. The change in pH affected the HA degradation efficiency by the photocatalytic activity where it was higher under acidic conditions rather than alkaline ones. Optimal catalyst loading was proved to be a constrained factor in influencing the photocatalytic efficiency: the increase of catalyst concentration enhanced the HA decomposition efficiency up to an optimum value of 20 g/L, where there was no further degradation with excess loading. The addition of H₂O₂ was investigated through homogenous and heterogeneous photocatalysis, and, heterogeneous photocatalysis showed higher removal efficiency due to the combined effect of both catalysts and H₂O₂. Finally, NZLC was effective for reuse and exhibited an excellent stability after six times of usage.     

2,4-Dichlorophenoxyacetic acid metabolism in transgenic tolerant cotton (Gossypium hirsutum)

The metabolic fate of 2,4-dichlorophenoxyacetic acid (2,4-D) was studied in leaves of transgenic 2,4-D-tolerant cotton (Gossypium hirsutum), which is obtained by transfer of the tfdA gene from the bacterium Alcaligenes eutrophus. The tdfA gene codes for a dioxygenase catalyzing the degradation of 2,4-D to 2, 4-dichlorophenol (2,4-DCP). [phenyl-(14)C]-2,4-D was administered by petiolar absorption followed by an 18 h water chase or converted to the isopropyl ester and sprayed onto the leaf surface; the leaves were harvested 48 h later. The herbicide was degraded to 2,4-DCP by the bacterial enzyme expressed in the plants. 2,4-DCP was rapidly converted to more polar metabolites and was never found in detectable amounts. Metabolite structures were deduced from enzymatic hydrolysis studies and mass spectrometric analyses. The first metabolite was the glucoside conjugate of 2,4-DCP (2, 4-DCP-beta-O-glucoside). The major terminal metabolites were two more complex glucosides: 2,4-DCP-(6-O-malonyl)glucoside and 2, 4-DCP-(6-O-sulfate)glucoside.     

Response surface methodology to understand the anaerobic biodegradation of organochlorine pesticides (OCPs) in contaminated soil—significance of nitrate concentration and bioaccessibility

Purpose

Problems associated with Organochlorine pesticide (OCP)-contaminated soils have received wide attention. To understand the anaerobic biodegradation process constraints, innovative mathematical analysis methods are effective.

Materials and methods

Response surface methodology (RSM) and Tenax TA extraction method combined with the first-three-compartment model were employed to systematically investigate the role of nitrate concentration and bioaccessibility enhancer (methyl-β-cyclodextrin, MCD) in the anaerobic biodegradation of OCPs in contaminated soil.

Results and discussion

The sole addition of either KNO₃ or MCD could facilitate the anaerobic biodegradation of OCPs. The highest biodegradation for total OCPs, hexachlorocyclohexanes, endosulfans, and chlordanes were 71.6, 82.1, 68.3, and 55.6 %, respectively, when 20 mM KNO₃ and 3.0 % (w/w) MCD were applied simultaneously. As predicted by RSM, the theoretical maximum biodegradation for total OCPs ranged from 60 to 80 % when 20 to 25 mM KNO₃ and >2.5 % (w/w) MCD were applied simultaneously. Tenax TA extraction method demonstrated the enhancement of OCP bioaccessibility caused by MCD addition. Changes in the soil microbial activities also suggested the positive effects of adding suitable amounts of KNO₃ as a cosubstrate to facilitate the anaerobic biodegradation of OCPs.

Conclusions

The amount of KNO₃ and MCD are crucial in influencing OCP biodegradation. RSM was demonstrated to be a powerful tool to estimate and predicting the optimal OCP biodegradation under KNO₃ and MCD application simultaneously.     

Metabolic fate of [14C] chlorophenols in radish (Raphanus sativus), lettuce (Lactuca sativa), and spinach (Spinacia oleracea)

Chlorophenols are potentially harmful pollutants that are found in numerous natural and agricultural systems. Plants are a sink for xenobiotics, which occur either intentionally or not, as they are unable to eliminate them although they generally metabolize them into less toxic compounds. The metabolic fate of [ (14)C] 4-chlorophenol (4-CP), [ (14)C] 2,4-dichlorophenol (2,4-DCP), and [ (14)C] 2,4,5-trichlorophenol (2,4,5-TCP) was investigated in lettuce, spinach, and radish to locate putative toxic metabolites that could become bioavailable to food chains. Radish plants were grown on sand for four weeks before roots were dipped in a solution of radiolabeled chlorophenol. The leaves of six-week old lettuce and spinach were treated. Three weeks after treatments, metabolites from edible plant parts were extracted and analyzed by high performance liquid chromatography (HPLC) and characterized by mass spectrometry (MS), and nuclear magnetic resonance spectroscopy (NMR). Characterization of compounds highlighted the presence of complex glycosides. Upon hydrolysis in the digestive tract of animals or humans, these conjugates could return to the toxic parent compound, and this should be kept in mind for registration studies.     

Kinetic and Thermodynamic Studies of Chlorinated Organic Compound Degradation by Siderite-Activated Peroxide and Persulfate

The efficacy of two oxidant systems, iron-activated hydrogen peroxide (H₂O₂) and iron-activated hydrogen peroxide coupled with persulfate (S₂O₈ ^2?), was investigated for treatment of two chlorinated organic compounds, trichloroethene (TCE) and 1,2-dichloroethane (DCA). Batch tests were conducted at multiple temperatures (10–50 °C) to investigate degradation kinetics and reaction thermodynamics. The influence of an inorganic salt, dihydrogen phosphate ion (H₂PO₄ ^?), on oxidative degradation was also examined. The degradation of TCE was promoted in both systems, with greater degradation observed for higher temperatures. The inhibition effect of H₂PO₄ ^? on the degradation of TCE increased with increasing temperature for the iron-activated H₂O₂ system but decreased for the iron-activated hydrogen peroxide-persulfate system. DCA degradation was limited in the iron-activated hydrogen peroxide system. Conversely, significant DCA degradation (87% in 48 h at 20 °C) occurred in the iron-activated hydrogen peroxide-persulfate system, indicating the crucial role of sulfate radical (SO₄ ^??) from persulfate on the oxidative degradation of DCA. The activation energy values varied from 37.7 to 72.9 kJ/mol, depending on the different reactants. Overall, the binary hydrogen peroxide-persulfate oxidant system exhibited better performance than hydrogen peroxide alone for TCE and DCA degradation.     

A Stable Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>/Expanded Perlite Composite Catalyst for Degradation of Rhodamine B in Heterogeneous Photo-Fenton System

A stable and efficient Fe₂O₃/expanded perlite (Fe₂O₃-Ep) composite catalyst was synthesized by a simple hydrothermal method for degradation of refractory contaminants in heterogeneous photo-Fenton system. X-ray diffraction and FT-IR analyses confirmed the presence of the Fe₂O₃ in the synthesized catalyst. The catalytic activity of the Fe₂O₃-Ep catalyst was evaluated by the degradation of rhodamine B (RhB, 5 mg/L) and metronidazole (MET, 5 mg/L) in the presence of H₂O₂ under visible light irradiation. The Fe₂O₃-Ep catalyst exhibited high efficiency for degradation of RhB at a wide pH range from 2 to 10 and showed excellent catalytic property for decomposition of MET as well. The degradation ratio of RhB was achieved 99%, and the removal ratio of COD was 62% within 90 min at the best experimental conditions (0.5 g/L of Fe₂O₃-Ep catalyst, 2 mL/L of H₂O₂). Furthermore, iron leaching of the Fe₂O₃-Ep catalyst during the catalytic degradation reaction was negligible and the catalyst still exhibited high catalytic activity and stability after five cycles. These results show that the catalyst can be used as a highly efficient heterogeneous photo-Fenton catalyst for the degradation of non-biodegradable refractory pollutants in water.     

Role of Hydrogen Peroxide Produced by Baker's Yeast on Dough Rheology

Baker's yeast, Saccharomyces cerevisiae, has a well-known effect on dough rheology during breadmaking. During a 3-hr fermentation, hydrogen peroxide (H₂O₂) produced by yeast (0.76%, fwb) increased from 1.09 to 2.32 μmol/g of flour. The spread test, a measure of a dough's rheological properties, showed that yeast had an effect on dough rheology similar to that of H₂O₂, an oxidant that makes flour-water dough more elastic. In additional experiments (spread test and H₂O₂ measurement), glucose oxidase, an enzyme that produces H₂O₂, gave results similar to those with yeast. The fact that catalase, an enzyme that destroys H₂O₂, reversed the rheological effect of added H₂O₂ but did not reverse the effect of either yeast or glucose oxidase suggested that either wheat flour contains an inhibitor to catalase or H₂O₂ was not the active component. A series of experiments, including use of defatted flour, remixing, and mixing dough under nitrogen, all indicated that catalase was inhibited by peroxides in the lipid fraction of flour. These results also suggested that H₂O₂ is responsible for the effects of yeast and glucose oxidase on dough.     

The effects of acid perturbation on a controlled ecosystem

Duplicate, 8-compartment, continuous-flow microcosms were used to study the effects of acid addition on community function, algal community structure, and degradation of a plasticizer, diethyl phthalate. Inputs of HCl decreased the alkalinity (measured as CaC0₃) from 25 to 8 mg 1^?1, creating diurnal H⁺ activity curves that indicated that the ecosystem was being severely stressed. Removal of excess acid was accompanied by a return to a normal diurnal pH cycle. Nutrient concentrations and O₂ production did not give a definite indication of stress resulting from the addition of acid. Algal community structure and total biomass were not affected by acid inputs. Also, degradation rates of diethyl phtalate by the aquatic bacteria were similar for the control and the acid-stressed systems. These studies indicate that acid inputs can significantly disrupt normal ecosystem function, such as diurnal pH cycling, without having a measurable impact on other parameters usually monitored in aquatic ecosystems.