Kinetics of simazine advanced oxidation in water

Abstract

Comparison of the effects and kinetics of UV photolysis and four advanced oxidation systems (ozone, ozone/hydrogen peroxide, ozone/UV radiation and UV radiation/hydrogen peroxide) for the removal of simazine from water has been investigated. At the conditions applied, the order of reactivity was ozone < ozone/hydrogen peroxide < UV radiation < ozone/UV radiation and UV radiation/hydrogen peroxide. Rate constants of the reactions between ozone and simazine and hydroxyl radical and simazine were found to be 8.7 M^‐1s^‐1 and 2.1x10⁹ M^‐1s^‐1, respectively. Also, a quantum yield of 0.06 mol.photon^‐1 was found for simazine at 254 nm UV radiation. The high value of the quantum yield corroborated the importance of the direct photolysis process. Percentage contributions of direct reaction with ozone, reaction with hydroxyl radicals and direct photolysis were also quantified.     

A new approach to quantify the degradation kinetics of linuron with UV, ozonation and UV/O3 processes

The degradation of linuron, one of phenylurea herbicides, was investigated for its reaction kinetics by different treatment processes including ultraviolet irradiation (UV), ozonation (O₃), and UV/O₃. The decay rate of linuron by UV/O₃ process was found to be around 3.5 times and 2.5 times faster than sole-UV and ozone-alone, respectively. Experimental results also indicate overall rate constants increased exponentially with pH above 9.0 while the increase of rate constants with pH below 9 is insignificant in O₃ system. All dominant parameters involved in the three processes were determined in the assistant of proposed linear models in this study. The approach was found useful in predicting the process performances through the quantification of quantum yield (rate constant for the formation of free radical HOO⁻ from ozone decomposition at high pH), rate constant of linuron with ozone (k_O3,LNR), rate constant of linuron with hydroxyl radical (k_OH,LNR), and α (the ratio of the production rate of OH and the decay rate of ozone in UV/O₃ system).     

Hydroxyl (OH) radical production rates in snowpacks from photolysis of hydrogen peroxide (H2O2) and nitrate (NO3−)

Atmospheric chemistry directly above snowpacks is strongly influenced by ultraviolet (UV) radiation initiated emissions of chemicals from the snowpack. The emission of gases from the snowpack to the atmosphere is in part due to chemical reactions between hydroxyl radical, OH (produced from photolysis of hydrogen peroxide (H₂O₂) or nitrate (NO₃⁻)) and impurities in the snowpack. The work presented here is a radiative-transfer modelling study to calculate the depth-integrated production rates of hydroxyl radical from the photolysis of hydrogen peroxide and nitrate anion in snow for four different snowpacks and for solar zenith angles 30°–90°. This work also demonstrates the importance of hydrogen peroxide photolysis to produce hydroxyl radical relative to nitrate photolysis with (a) different snowpacks, (b) different ozone column depths, and (c) snowpack depths. The importance of hydrogen peroxide photolysis over nitrate photolysis for hydroxyl radical production increases with increasing depth in snowpack, column ozone depth, and solar zenith angle. With a solar zenith angle of 60° the production of hydroxyl radical from hydrogen peroxide photolysis accounts for 91–99% of all hydroxyl radical production from hydrogen peroxide and nitrate photolysis.     

Kinetics of simazine advanced oxidation in water

Comparison of the effects and kinetics of UV photolysis and four advanced oxidation systems (ozone, ozone/hydrogen peroxide, ozone/UV radiation and UV radiation/hydrogen peroxide) for the removal of simazine from water has been investigated. At the conditions applied, the order of reactivity was ozone < ozone/hydrogen peroxide < UV radiation < ozone/UV radiation and UV radiation/hydrogen peroxide. Rate constants of the reactions between ozone and simazine and hydroxyl radical and simazine were found to be 8.7 M-1s-1 and 2.1 x 10(9) M-1s-1, respectively. Also, a quantum yield of 0.06 mol.photon-1 was found for simazine at 254 nm UV radiation. The high value of the quantum yield corroborated the importance of the direct photolysis process. Percentage contributions of direct reaction with ozone, reaction with hydroxyl radicals and direct photolysis were also quantified.     

水体中酮硝基麝香的臭氧氧化降解研究

采用臭氧氧化水体中的酮硝基麝香,考察pH、H2O2等因素对降解程度的影响,结果表明提高初始pH能加快酮硝基麝香的氧化降解,当pH为12时,反应时间1 h,酮硝基麝香几乎完全去除,浓度为2 mol/L和5 mol/L的H2O2存在有利于O3分解生成·OH自由基,使得酮硝基麝香的氧化降解速率加快,当H2O2浓度超过5 mol/L,H2O2会成为·OH的清除剂,降低·OH利用率;无论O3单独作用和O3/H2O2协同作用,酮硝基麝香降解符合准一级动力学规律;酮硝基麝香氧化降解产物包括甲酸、二乙酸和硝酸根等,其中硝基从苯环上脱落降低了硝基麝香对环境的风险.     

Oxidative properties of ambient PM2.5 and elemental composition: Heterogeneous associations in 19 European cities

We assessed the extent to which constituents of PM_2.5 (transition metals, sodium, chloride) contribute to the ability to generate hydroxyl radicals (OH) in vitro in PM_2.5 sampled at 20 locations in 19 European centres participating in the European Community Respiratory Health Survey. PM_2.5 samples (n = 716) were collected on filters over one year and the oxidative activity of particle suspensions obtained from these filters was then assessed by measuring their ability to generate OH in the presence of hydrogen peroxide. Associations between OH formation and the studied PM constituents were heterogeneous. The total explained variance ranged from 85% in Norwich to only 6% in Albacete. Among the 20 centres, 15 showed positive correlations between one or more of the measured transition metals (copper, iron, manganese, lead, vanadium and titanium) and OH formation. In 9 of 20 centres OH formation was negatively associated with chloride, and in 3 centres with sodium. Across 19 European cities, elements which explained the largest variations in OH formation were chloride, iron and sodium.     

O3/H2O2法去除浮选药剂丁基黄药

采用O3/H2O2法去除水中丁基黄药,考察了H2O2/O3摩尔比、pH值、丁基黄药初始浓度、温度和自由基抑制剂对丁基黄药的去除效果的影响。结果表明,在相同O3投加量下,H2O2量越大,丁基黄药去除率越高。pH值为7～9,温度在293～303 K的范围内,O3/H2O2对丁基黄药都有很高的去除率。碳酸氢根和叔丁醇能在一定程度上降低丁基黄药的降解效率。研究还发现,在O3和H2O2投加量相同的条件下,H2O2多次投加对水中丁基黄药的处理效果明显优于一次性投加。GC/MS分析表明,O3/H2O2氧化丁基黄药氧化产物为羧酸类物质。     

O3/H2O2法去除浮选药剂丁基黄药

采用O3/H2O2法去除水中丁基黄药,考察了H2O2/O3摩尔比、pH值、丁基黄药初始浓度、温度和自由基抑制剂对丁基黄药的去除效果的影响。结果表明,在相同O3投加量下,H2O2量越大,丁基黄药去除率越高。pH值为7～9,温度在293～303 K的范围内,O3/H2O2对丁基黄药都有很高的去除率。碳酸氢根和叔丁醇能在一定程度上降低丁基黄药的降解效率。研究还发现,在O3和H2O2投加量相同的条件下,H2O2多次投加对水中丁基黄药的处理效果明显优于一次性投加。GC/MS分析表明,O3/H2O2氧化丁基黄药氧化产物为羧酸类物质。     

Evaluating the performance of a turbulent wet scrubber for scrubbing particulate matter

A turbulent wet scrubber was designed and developed to scrub particulate matter (PM) at micrometer and submicrometer levels from the effluent gas stream of an industrial coal furnace. Experiments were conducted to estimate the particle removal efficiency of the turbulent scrubber with different gas flow rates and liquid heads above the nozzle. Particles larger than 1 µm were removed very efficiently, at nearly 100%, depending upon the flow rate, the concentration of the dust-laden air stream, and the water level in the reservoir. Particles smaller than 1 µm were also removed to a greater extent at higher gas flow rates and for greater liquid heads. Pressure-drop studies were also carried out to estimate the energy consumed by the scrubber for the entire range of particle sizes distributed in the carrier gas. A maximum pressure drop of 217 mm H₂O was observed for a liquid head of 36 cm and a gas flow rate of 7 m³/min. The number of transfer units (NTU) analysis for the efficiencies achieved by the turbulent scrubber over the range of particles also reveals that the contacting power achieved by the scrubber is better except for smaller particles. The turbulent scrubber is more competent for scrubbing particulate matter, in particular PM_2.5, than other higher energy or conventional scrubbers, and is comparable to other wet scrubbers of its kind for the amount of energy spent.

Implications: The evaluation of the turbulent scrubber is done to add a novel scrubber in the list of wet scrubbers for industrial applications, yet simple in design, easy to operate, with better compactness, and with high efficiencies at lower energy consumption. Hence the turbulent scrubber can be used to combat particulate from industrial gaseous effluents and also has a scope to absorb gaseous pollutants if the gases are soluble in the medium used for particles capture.     

Kinetics and mechanism for omethoate degradation by catalytic ozonation with Fe(III)-loaded activated carbon in water

The kinetics and mechanism for degradation of omethoate (OMT) by catalytic ozonation with Fe(III)-loaded activated carbon (Fe@AC) were investigated in this study with focus on identification of degradation byproducts. The rate constants of OMT reacting with ozone and hydroxyl radical (OH) were determined to be 0.04 and 5.3 × 10⁸ M^?1 s^?1 at pH 7.5 and 20 °C, respectively. OMT was predominantly degraded by OH in the catalytic ozonation with Fe@AC. The high-molecular-weight degradation byproducts identified were O,O,O-trimethyl phosphoric ester (TMP), pyrrolidin-2-one, N-methyl-2-sulfanylacetamide, 2-(methylthio)acetamide, O,O,S-trimethylthiophosphate (STMP), and N-methyl-2-(methylthio)acetamide. Besides, low-molecular-weight organic acids and inorganic anions were also detected and quantified, including formic, acetic and oxalic acids as well as nitrate, sulfate and phosphate ions. In the catalytic ozonation, TMP and phosphate were two major P-containing byproducts resulting from OMT degradation. The toxicity of OMT solution gradually decreased during the catalytic ozonation, indicating that Fe@AC is a safe catalyst for OMT removal by ozone in water.     

Release of gaseous bromine from the photolysis of nitrate and hydrogen peroxide in simulated sea-salt solutions

We have carried out a series of laboratory experiments to investigate the oxidation of bromide (Br⁻) by hydroxyl radical (OH) in solutions used to mimic sea-salt particles. Aqueous halide solutions with nitrate or hydrogen peroxide (HOOH) as a photochemical source of OH were illuminated with 313 nm light and the resulting gaseous bromine (Br*(g)) was collected. While illumination of these solutions nearly always formed gaseous bromine (predominantly Br₂ based on modeling results), there was no evidence for the release of gaseous chlorine. The rate of Br*(g) release increased (up to a plateau value) with increasing concentrations of bromide and was enhanced at lower pH values for both nitrate and HOOH solutions. Increased ionic strength in nitrate solutions inhibited Br*(g) release and the extent of inhibition was dependent upon the salt used. In HOOH solutions, however, no ionic strength effects were observed and the presence of Cl⁻ strongly enhanced Br*(g) release.Overall, for conditions typical of aged, deliquesced, sea-salt particles, the efficiencies of gaseous bromine release, expressed as mole of Br*(g) released per mole of OH photochemically formed, were typically 20–30%. Using these reaction efficiencies, we calculated the Br₂(g) release rate from aged, ambient sea-salt particles due to OH oxidation to be approximately 0.07 pptv h⁻¹ with the main contributions from nitrate photolysis and partitioning of gas-phase OH into the particle. While our solution conditions are simplified compared to ambient particles, this estimated rate of Br₂ release is high enough to suggest that OH-mediated reactions in sea-salt particles could be a significant source of reactive bromine to the marine boundary layer.     

Oxidation of diethylene glycol with ozone and modified Fenton processes

This paper describes a study of oxidation of diethylene glycol (DEG) by ozone and modified Fenton process (hydrogen peroxide and ferric salt mixture) in aqueous solution. Both oxidation processes were able to oxidize relatively high concentrations of DEG effectively. DEG reacted primarily through hydroxyl radical produced by decomposition of ozone, and about 3 mol of ozone were consumed per mole of DEG removed during the process. For modified Fenton oxidation, stepwise addition of hydrogen peroxide (H2O2) and ferric salt (Fe(III)) resulted in much higher removal of DEG than one-time pulse addition of the chemicals. The extent of DEG removal increased with increasing concentrations of both H2O2 and Fe(III). Oxidant consumption per mole of DEG oxidized was one order of magnitude higher for hydrogen peroxide than those observed for ozone. Overall, ozonation produced higher concentrations of aldehydes, and modified Fenton treatment produced higher concentrations of carboxylic acids for the same levels of DEG oxidation. The major products of ozonation were glycolaldehyde, glyoxal, formaldehyde, acetaldehyde, and acetic, formic, pyruvic, oxalic and glyoxalic acids. The major products of modified Fenton oxidation were formaldehyde, and formic and acetic acids.     

SIMAZINE REMOVAL FROM WATER IN A CONTINUOUS BUBBLE COLUMN BY O3 AND O3/H2O2

Simazine, [2-chloro, 4,6-bis(ethylamino)-1,3,5-s-triazine], a common herbicide found in surface and ground water has been ozonized in continuous flow mode. Typical operating variables in ozonation processes have been investigated. Thus, the ozone dose fed to the system exerted a positive effect, while the gas flow rate did not influence the efficiency of the process provided ozone mass flow rate was kept constant. Increasing the pH led to a higher extension of the free radical degradation of simazine and, therefore, to a higher efficiency of the process. Also, addition of free radical promoters, i.e. hydrogen peroxide, did result in a significant improvement of the simazine removal rate. A first approach to process economy showed the system ozone/hydrogen peroxide as the most advantageous in terms of electrical energy requirements.     

Simazine removal from water in a continuous bubble column by O3 and O3/H2O2.

Simazine, [2-chloro, 4,6-bis(ethylamino)-1,3,5-s-triazine], a common herbicide found in surface and ground water has been ozonized in continuous flow mode. Typical operating variables in ozonation processes have been investigated. Thus, the ozone dose fed to the system exerted a positive effect, while the gas flow rate did not influence the efficiency of the process provided ozone mass flow rate was kept constant. Increasing the pH led to a higher extension of the free radical degradation of simazine and, therefore, to a higher efficiency of the process. Also, addition of free radical promoters, i.e. hydrogen peroxide, did result in a significant improvement of the simazine removal rate. A first approach to process economy showed the system ozone/hydrogen peroxide as the most advantageous in terms of electrical energy requirements.     

Photosensitized degradation of caffeine: role of fulvic acids and nitrate

The photolysis of caffeine was studied in solutions of fulvic acid isolated from Suwannee River, GA (SRFA) and Old Woman Creek Natural Estuarine Research Reserve, OH (OWCFA) with different chemical amendments (nitrate and iron). Caffeine degrades slowly by direct photolysis (>170 h in artificial sunlight), but we observed enhanced photodegradation in waters containing the fulvic acids. At higher initial concentrations (10 μM) the indirect photolysis of caffeine occurs predominantly through reaction with the hydroxyl radical (OH) generated by irradiated fulvic acids. Both rate constant estimates based upon measured OH steady-state concentrations and quenching studies using isopropanol corroborate the importance of this pathway. Further, OH generated by irradiated nitrate at concentrations present in wastewater effluent plays an important role as a photosensitizer even in the presence of fulvic acids, while the photo-Fenton pathway does not at neutral or higher pH. At lower initial concentrations (0.1 μM) caffeine photolysis reactions proceed even more quickly in fulvic acid solutions and are influenced by both short- and long-lived reactive species. Studies conducted under suboxic conditions suggest that an oxygen dependent long-lived radical e.g., peroxyl radicals plays an important role in the degradation of caffeine at lower initial concentration.     

The importance of atmospheric ozone and hydrogen peroxide in oxidising sulphur dioxide in cloud and rainwater

The process by which sulphur dioxide is oxidised in atmospheric droplets has been studied in laboratory experiments designed to collect a large amount of chemical data pertinent to the atmospheric situation. Thus the oxidation of sodium sulphite solutions by oxygen, ozone and hydrogen peroxide has been studied at different pH's and temperatures. In all cases the reaction is first order with respect to sulphite ion but the order with respect to oxidant differs. For oxygen the order is zero whereas the order for ozone and hydrogen peroxide is one. Varying the hydrogen ion concentration has little effect on the oxygen reaction rate between pH 6 and 9; the ozone reaction rate is inversely proportional to the square root of the hydrogen ion concentration and the hydrogen peroxide rate is almost directly proportional to the hydrogen ion concentration. These last two observations are very important since in the case of ozone it indicates that the reaction proceeds via a free radical mechanism involving hydroxyl radicals and in the case of hydrogen peroxide it is the only oxidation process of sodium sulphite so far investigated that shows a positive response to the presence of hydrogen ions.The experimental data was used to calculate the rate of sulphate formation in water droplets under atmospheric conditions for each of the three oxidants. If it is assumed that the ozone and hydrogen peroxide gas phase concentrations are initially 50 parts in 10⁹ and 1 part in 10⁹ by volume respectively, then the rates of sulphate formation are equal in cloud water at pH 5.8. Above this pH the ozone reaction is faster and below it the hydrogen peroxide reaction is faster due to the positive catalysis by hydrogen ions; the oxygen rate is unimportant by comparison at all pH's below 7. The rate of hydrogen peroxide reaction is such that substantial amounts of sulphate can still be formed rapidly in water droplets at pH values from 3 to 5, and thus this process will be very important in creating acidity in rainwater.     

The importance of atmospheric ozone and hydrogen peroxide in oxidising sulphur dioxide in cloud and rainwater

The process by which sulphur dioxide is oxidised in atmospheric droplets has been studied in laboratory experiments designed to collect a large amount of chemical data pertinent to the atmospheric situation. Thus the oxidation of sodium sulphite solutions by oxygen, ozone and hydrogen peroxide has been studied at different pH's and temperatures. In all cases the reaction is first order with respect to sulphite ion but the order with respect to oxidant differs. For oxygen the order is zero whereas the order for ozone and hydrogen peroxide is one. Varying the hydrogen ion concentration has little effect on the oxygen reaction rate between pH 6 and 9; the ozone reaction rate is inversely proportional to the square root of the hydrogen ion concentration and the hydrogen peroxide rate is almost directly proportional to the hydrogen ion concentration. These last two observations are very important since in the case of ozone it indicates that the reaction proceeds via a free radical mechanism involving hydroxyl radicals and in the case of hydrogen peroxide it is the only oxidation process of sodium sulphite so far investigated that shows a positive response to the presence of hydrogen ions.The experimental data was used to calculate the rate of sulphate formation in water droplets under atmospheric conditions for each of the three oxidants. If it is assumed that the ozone and hydrogen peroxide gas phase concentrations are initially 50 parts in 10⁹ and 1 part in 10⁹ by volume respectively, then the rates of sulphate formation are equal in cloud water at pH 5.8. Above this pH the ozone reaction is faster and below it the hydrogen peroxide reaction is faster due to the positive catalysis by hydrogen ions; the oxygen rate is unimportant by comparison at all pH's below 7. The rate of hydrogen peroxide reaction is such that substantial amounts of sulphate can still be formed rapidly in water droplets at pH values from 3 to 5, and thus this process will be very important in creating acidity in rainwater.     

Advanced oxidation of alkylphenol ethoxylates in aqueous systems

Alkylphenols and alkylphenol ethoxylates are ubiquitous wastewater contaminants. In this study the oxidation of nonylphenol ethoxylates (NPEO) and octylphenol ethoxylates (OPEO) by oxidant systems generating hydroxide radicals was evaluated. The reaction of each oxidant with a technical mixture of NPEO (Tergitol™) and OPEO (Triton X-100™) in ultrapure laboratory water and four aqueous environmental matrices was carried out in order to develop an understanding of reaction kinetics. The oxidation of APEOs was evaluated by hydroxyl radical generated by (1) hydrogen peroxide in the presence of ultraviolet light, (2) Fenton’s reagent, and (3) a photo-Fenton’s process. The second order kinetic rate constant for both NPEO and OPEO with hydroxyl radical was calculated to be 1.1 × 10¹⁰ M⁻¹ s⁻¹. The efficacy of the AOPs within an aqueous environmental matrix was dependent on the rate of formation of hydroxyl radical and the scavenging capacity of the matrix. A model based on the hydroxyl radical formation, scavenging capacity and the kinetic rate constant of target APEO was developed from the existing literature and applied to predict the concentration of APEOs in solution during advanced oxidation in different aqueous environmental matrices.