Gas phase reactions of unsaturated esters with Cl atoms

Background, aim, and scope  

Acrylate and methacrylate esters are α,β-unsaturated esters that contain vinyl groups directly attached to the carbonyl carbon (CH₂=CHCOO– and CH₂=CCH₃COO–, respectively) and are widely used in the polymer plastic and resin production. Rate coefficients for Cl reactions for most of the unsaturated esters have not been previously determined, and a good understanding is needed of all the atmospheric oxidation processes of these compounds in order to determine lifetimes in the atmosphere and to evaluate the impact of these reactions on the formation of photo-oxidants and therefore on health and environment.     

Atmospheric chemistry of HFE-7000 (CF(3)CF (2)CF (2)OCH (3)) and 2,2,3,3,4,4,4-heptafluoro-1-butanol (CF (3)CF (2)CF (2)CH (2)OH): kinetic rate coefficients and temperature dependence of reactions with chlorine atoms

Background, aim, and scope  The adverse environmental impacts of chlorinated hydrocarbons on the Earth’s ozone layer have focused attention on the effort to replace these compounds by nonchlorinated substitutes with environmental acceptability. Hydrofluoroethers (HFEs) and fluorinated alcohols are currently being introduced in many applications for this purpose. Nevertheless, the presence of a great number of C–F bonds drives to atmospheric long-lived compounds with infrared absorption features. Thus, it is necessary to improve our knowledge about lifetimes and global warming potentials (GWP) for these compounds in order to get a complete evaluation of their environmental impact. Tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atoms reaction may also be important since rate constants are generally larger than those of OH. In the present work, we report the results obtained in the study of the reactions of Cl radicals with HFE-7000 (CF₃CF₂CF₂OCH₃) (1) and its isomer CF₃CF₂CF₂CH₂OH (2). Materials and methods  Kinetic rate coefficients with Cl atoms have been measured using the discharge flow tube–mass spectrometric technique at 1 Torr of total pressure. The reactions of these chlorofluorocarbons (CFCs) substitutes have been studied under pseudo-first-order kinetic conditions in excess of the fluorinated compounds over Cl atoms. The temperature ranges were 266–333 and 298–353 K for reactions of HFE-7000 and CF₃CF₂CF₂CH₂OH, respectively. Results  The measured room temperature rate constants were k(Cl+CF₃CF₂CF₂OCH₃) = (1.24 ± 0.28) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹and k(Cl+CF₃CF₂CF₂CH₂OH) = (8.35 ± 1.63) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹ (errors are 2σ + 10% to cover systematic errors). The Arrhenius expression for reaction 1 was k ₁(266–333 K) = (6.1 ± 3.8) × 10⁻¹³exp[−(445 ± 186)/T] cm³ molecule⁻¹ s⁻¹ and k ₂(298–353 K) = (1.9 ± 0.7) × 10⁻¹²exp[−(244 ± 125)/T] cm³ molecule⁻¹ s⁻¹ (errors are 2σ). The reactions are reported to proceed through the abstraction of an H atom to form HCl and the corresponding halo-alkyl radical. At 298 K and 1 Torr, yields on HCl of 0.95 ± 0.38 and 0.97 ± 0.16 (errors are 2σ) were obtained for CF₃CF₂CF₂OCH₃ and CF₃CF₂CF₂CH₂OH, respectively. Discussion  The obtained kinetic rate constants are related to the previous data in the literature, showing a good agreement taking into account the error limits. Comparing the obtained results at room temperature, k ₁ and k ₂, HFE-7000 is significantly less reactive than its isomer C₃F₇CH₂OH. A similar behavior has been reported for the reactions of other fluorinated alcohols and their isomeric fluorinated ethers with Cl atoms. Literature data, together with the results reported in this work, show that, for both fluorinated ethers and alcohols, the kinetic rate constant may be considered as not dependent on the number of –CF₂– in the perfluorinated chain. This result may be useful since it is possible to obtain the required physicochemical properties for a given application by changing the number of –CF₂– without changes in the atmospheric reactivity. Furthermore, lifetimes estimations for these CFCs substitutes are calculated and discussed. The average estimated Cl lifetimes are 256 and 38 years for HFE-7000 and C₃H₇CH₂OH, respectively. Conclusions  The studied CFCs’ substitutes are relatively short-lived and OH reaction constitutes their main reactive sink. The average contribution of Cl reactions to global lifetime is about 2% in both cases. Nevertheless, under local conditions as in the marine boundary layer, τ _Cl values as low as 2.5 and 0.4 years for HFE-7000 and C₃H₇CH₂OH, respectively, are expected, showing that the contribution of Cl to the atmospheric degradation of these CFCs substitutes under such conditions may constitute a relevant sink. In the case of CF₃CF₂CF₂OCH₃, significant activation energy has been measured, thus the use of kinetic rate coefficient only at room temperature would result in underestimations of lifetimes and GWPs. Recommendations and perspectives  The results obtained in this work may be helpful within the database used in the modeling studies of coastal areas. The knowledge of the atmospheric behavior and the structure–reactivity relationship discussed in this work may also contribute to the development of new environmentally acceptable chemicals. New volatile materials susceptible of emission to the troposphere should be subject to the study of their reactions with OH and Cl in the range of temperature of the troposphere. The knowledge of the temperature dependence of the kinetic rate constants, as it is now reported for the case of reactions 1 and 2, will allow more accurate lifetimes and related magnitudes like GWPs. Nevertheless, a better knowledge of the vertical Cl tropospheric distribution is still required.     

Fenton-like oxidation and mineralization of phenol using synthetic Fe(II)–Fe(III) green rusts

Background, aim, and scope  

In literature, the environmental applications of green rust (GR) have mainly been pointed out through the reduction of inorganic contaminants and the reductive dechlorination of chlorinated organics. However, reactions involving GR for the oxidation and mineralization of organic pollutants remain very scantly described. In this study, the ability of three synthetic Fe(II)–Fe(III) green rusts, GR(CO₃²⁻), GR(SO₄²⁻), and GR(Cl⁻), to promote Fenton-like reaction was examined by employing phenol as a model pollutant. Unlike the traditional Fenton’s reagent (dissolved Fe(II) + H₂O₂), where the pH values have to be lowered to less than 4, the proposed reaction can effectively oxidize the organic molecules at neutral pH and could avoid the initial acidification which may be costly and destructive for the in situ remediation of contaminated groundwater and soils. The green rust reactivity towards the oxidative transformation of phenol was thoroughly evaluated by performing a large kinetic study, chemical analyses, and spectroscopic investigations.     

Interaction of Cr(VI) species with thermally treated brick clay

Purpose  

The purpose this research is to investigate the interaction of Cr(VI) species, present as Cr₂O₇²⁻, at ambient temperature with brick clay pre-fired at different temperatures.     

Effect of Pb toxicity on leaf growth, antioxidant enzyme activities, and photosynthesis in cuttings and seedlings of Jatropha curcas L

Background  

Cuttings and seedlings of Jatropha curcas L. were exposed to different regimes of lead (Pb) stress as Pb(NO₃)₂ at 0 (CK), 0.5, 1, 2, 3, and 4 mM kg⁻¹ soil.     

The Cl-initiated oxidation of CH3C(O)OCH=CH2, CH3C(O)OCH2CH=CH2, and CH2=CHC(O)O(CH2)3CH3 in the troposphere

Background, aim, and scope  

Unsaturated esters are emitted to the atmosphere from biogenic and anthropogenic sources, including those from the polymer industry. Little information exists concerning the atmospheric degradation of unsaturated esters, which are mainly initiated by OH radicals. Limited information is available on the degradation of alkenes by Cl atoms and almost no data exists for the reactions of unsaturated esters with Cl atoms. This data is necessary to assess the impact of such reactions in maritime environments where, under circumstances, OH radical- and Cl atom-initiated oxidation of the compounds can be important. Rate coefficients for the reactions of chlorine atoms with vinyl acetate, allyl acetate, and n-butyl acrylate have been determined at 298 ± 3 K and atmospheric pressure. The kinetic data have been used in combination with that for structurally similar compounds to infer the kinetic contributions from the possible reaction channels to the overall reaction rate.     

Factors that have an effect on degradation of diclofenac in aqueous solution by gamma ray irradiation

Purpose  

Gamma ray irradiation is considered as an effective way to degrade diclofenac. However, due to the extensive coexisting substances in natural waters, the use of gamma ray irradiation for degradation is often influenced by multiple factors. The various factors that affect degradation efficiency, such as initial diclofenac concentration, initial pH, and the concentration of the additives including H₂O₂ (·OH radical promoter), CH₃OH (·OH radical scavenger), thiourea (·OH, H·, and e_aq⁻ scavenger), humic acid, and NO₃⁻ (coexisting substances in natural waters), are investigated. Furthermore, possible intermediate products are identified and corresponding transformation pathways are proposed.     

Water-soluble main ions in precipitation over the southeastern Adriatic region: chemical composition and long-range transport

Background, aim and scope  

Precipitation samples collected from 1995 to 2000 at meteorological station in the eastern outskirts of Herceg Novi (Montenegro) were analysed on Na⁺, K⁺, Mg²⁺, Ca²⁺, Cl^–, SO₄ ^2–, NO₃ ^– and NH₄ ⁺. Four-day backward trajectory simulations were conducted during the precipitation period to investigate the regional transport of main ions and their deposition in the region of the southeastern Adriatic Sea. The air mass trajectories were classified into six trajectory categories by the origin and direction of their approach to Herceg Novi.     

Removal of alkylphenols from polluted sites using surfactant-assisted soil washing and photocatalysis

Background and purpose  

Surfactant-assisted soil washing and photocatalysis are well-known remediation processes of environmental concern. The application of photocatalysis to treat soil washing extracts containing 4-methylphenol, 4-ethylphenol and 4–tert-butylphenol in the presence of nonionic (C₁₂E₈ and C₁₂E₂₃) and anionic (SDS) surfactants and some of their binary mixtures was investigated in this work by studying the pollutants degradation in the presence of TiO₂ dispersions irradiated with simulated solar light.     

Degradation of 1,2-dichloroethane from wash water of ion-exchange resin using Fenton’s oxidation

Background, aim, and scope  

Chlorinated volatile organic compounds (CVOCs), widely used in industry as solvents and chemical intermediates in the production of synthetic resins, plastics, and pharmaceuticals, are highly toxic to the environment and public health. Various studies reported that Fenton’s oxidation could degrade a variety of chlorinated VOCs in aqueous solutions. In acidic conditions, ferrous ion catalyzes the decomposition of H₂O₂ to form a powerful ^•OH radical. In this study, wastewater from wash of ion-exchange resin containing typical CVOC, 1,2-dichloroethane, was treated using Fenton’s oxidation. To reduce environmental load and processing costs of wastewater, Fenton process as a simple and efficient treatment method was applied to degrade 1,2-dichloroethane of wash water.     

Behaviour and dynamics of di-ammonium phosphate in bauxite processing residue sand in Western Australia—II. Phosphorus fractions and availability

Background, aim and scope  

Australia is the largest producer of bauxite in the world, with an annual output of approximately 62 million metric dry tons in 2007. For every tonne of alumina, about 2 tonnes of highly alkaline and highly saline bauxite-processing residue are produced. In Western Australia, Alcoa World Alumina, Australia (Alcoa) produces approximately 15 MT of residue annually from its refineries (Kwinana, Pinjarra and Wagerup). The bauxite-processing residue sand (BRS) fraction represents the primary material for rehabilitating Alcoa’s residue disposal areas (RDAs). However, the inherently hostile characteristics (high alkalinity, high salinity and poor nutrient availability) of BRS pose severe limitations for establishing sustainable plant cover systems. Alcoa currently applies 2.7 t ha⁻¹ of di-ammonium phosphate ((NH₄)₂HPO₄; DAP)-based fertiliser as a part of rehabilitation of the outer residue sand embankments of its RDAs. Limited information on the behaviour of the dominant components of this inorganic fertiliser in highly alkaline BRS is currently available, despite the known effects of pH on ammonium (NH₄) and phosphorus (P) behaviour. The aim of this study was to quantify the effects of pH on NH₃ volatilisation and residual nitrogen (N) in BRS following DAP applications.     

Platinum,palladium, and rhodium deposition to the <Emphasis Type="Italic">Prunus laurus cerasus</Emphasis> leaf surface as an indicator of the vehicular traffic pollution in the city of Varese area

Background, aim, and scope  

The widespread use of some platinum group elements as catalysts to minimize emission of pollutants from combustion engines produced a constantly growing increase of the concentration of these elements in the environment; their potential toxicological properties explain the increasing interest in routine easy monitoring. We have found that leaves of Prunus laurus cerasus are efficient collectors of particulate with a dimension <60–80 μm, and a simple and reliable procedure was developed to reveal traces of platinum, palladium, and rhodium released from automotive catalysts. The analysis of the dust deposited on the foliage is a direct indicator of traffic pollution.     

Humic acids as reducing agents: the involvement of quinoid moieties in arsenate reduction

Purpose  

Dissolved humic acids abiotically reduced inorganic arsenic to varying degrees, depending on solution pH, ionic strength, and type of humate used. The functionalities of dissolved organic matter responsible for these redox reactions remained in question, but quinoid moieties undoubtedly played an important role. It is not fully understood whether the quinoids are solely responsible for arsenate reduction, and what the kinetics of the relevant processes are.     

Effect of factors on decolorization of azo dye methyl orange by oxone/natural sunlight in aqueous solution

Purpose  

The oxone process for azo dye decolorization has drawbacks such as difficulties with reuse, risks of secondary pollution, and high costs associated with UV irradiation. This study aims to explore the use of oxone for decolorization in the absence of catalyst and under natural sunlight conditions (i.e., oxone/natural sunlight system) and evaluate the impacts of operating parameters (reagent dosage, initial methyl orange (MO) concentration, and initial pH) and coexisting substances (humic acid, NO₃⁻, metal ions) on the system’s decolorization efficiency.     

Transformation of atmospheric ammonia and acid gases into components of PM<Subscript>2.5</Subscript>: an environmental chamber study

Introduction  

The kinetics of the transformation of ammonia and acid gases into components of PM_2.5 has been examined. The interactions of existing aerosols and meteorology with the transformation mechanism have also been investigated. The specific objective was to discern the kinetics for the gas-to-particle conversion processes where the reactions of NH₃ with H₂SO₄, HNO₃, and HCl take place to form (NH₄)₂SO₄, NH₄NO₃, and NH₄Cl, respectively, in PM_2.5.     

Ferrate(VI) enhanced photocatalytic oxidation of pollutants in aqueous TiO<Subscript>2</Subscript> suspensions

Background, aim and scope  

Photocatalytic oxidation using UV irradiation of TiO₂ has been studied extensively and has many potential industrial applications, including the degradation of recalcitrant contaminants in water and wastewater treatment. A limiting factor in the oxidation process is the recombination of conduction band electrons (e ⁻ _cb) with electron holes (h_vb⁺) on the irradiated TiO₂ surface; thus, in aqueous conditions, the presence of an effective electron scavenger will be beneficial to the efficiency of the oxidation process. Ferrate (FeO₄²⁻) has received much recent attention as a water treatment chemical since it behaves simultaneously as an oxidant and coagulant. The combination of ferrate [Fe(VI)] with UV/TiO₂ photocatalysis offers an oxidation synergism arising from the Fe(VI) scavenging of e ⁻ _cb and the corresponding beneficial formation of Fe(V) from the Fe(VI) reduction. This paper reviews recent studies concerning the photocatalytic oxidation of problematic pollutants with and without ferrate.     

A new approach for chemical oxygen demand (COD) measurement at high salinity and low organic matter samples

Background, aim, and scope  

Chemical oxygen demand (COD) is used as a discharge standard parameter in wastewater treatment plant design, environmental modelling and many other applications. Chloride interference is an important problem of COD measurement for wastewaters containing low organic matter and high chloride concentrations. In case of chloride concentrations up to 2,000 mg/L, mercury sulphate addition at a ratio of 10:1 (HgSO₄:Cl⁻) can adequately mask the interference. When chloride concentration exceeds 2,000 mg/L, this ratio becomes ineffective to hinder the interference. At this point, it is proposed to use a greater and constant ratio of mercury sulphate addition. However, this application sometimes results in extra mercury sulphate addition which is not necessary. Even in some cases, greater addition of mercury sulphate alone is not a solution to erroneous measurement results. The purpose of the study is to determine optimum HgSO₄:Cl⁻ ratios according to the chloride concentrations of the samples and to show the importance of the strength of the digestion solution for the correct determination of the COD parameter.     

Turning calcium carbonate into a cost-effective wastewater-sorbing material by occluding waste dye

Background, aim, and scope  

Over the years, organic pollution in the environment has aroused people’s concern worldwide, especially persistent organic pollutants (POPs). Particularly in developing countries, plenty of concentrated organic wastewaters treated noneffectively are discharged into aquatic environments from chemical, textile, paper-making, and other industries to seriously threaten the surface and drinking water. The conventional wastewater treatment techniques are often helpless due to high cost with multilevel processing. Adsorption as an efficient method is often applied to the treatment of wastewater. The aim of this work is to develop an eco-friendly and cost-effective wastewater-sorbing material with weak acidic pink red B (APRB) and calcium carbonate (CaCO₃) by reusing highly concentrated dye wastewater.     

Seasonal variation of HCH isomers in open soil and plant-rhizospheric soil system of a contaminated environment

Background, aim, and scope  

Lindane, technically 1, 2, 3, 4, 5, 6-hexachlorocyclohexane (γ- HCH), is the most commonly detected organochlorine pesticide from diverse environmental compartments. Currently, India is the largest consumer and producer of lindane in the world. The production of lindane results in the generation of large quantities of waste HCH isomers (mainly α-, β- and δ-). All these isomers are toxic and have a long-range environmental transport potential. The aim of this study was to monitor the seasonal variation of HCH isomers in an open soil–plant–rhizospheric soil system of a contaminated industrial area. For this, selected plant species and their rhizospheric soil (soil samples collected at a depth range of 0–45 cm near to the root system) and open soil samples (soil samples collected (0–30 cm depth) from 1–1.5 m away from the plant root system) were collected for 2 years (two summer seasons and two winter seasons).     

Fallout traces of the Fukushima NPP accident in southern West Siberia (Novosibirsk,Russia)

Background  

The fallout of artificially produced radioactive isotopes has been recorded at a site in southern West Siberia (54°50′43.6″ N, 083°06′22.4″ E, Novosibirsk, Russia).