Continuous UV-C/H2O2 and UV-C/Chlorine applied to municipal secondary effluent and nanofiltration retentate: Removal of contaminants of emerging concern, ecotoxicity, and reuse potential.

As global effects of water scarcity raise concerns and environmental regulations evolve, contemporary wastewater treatment plants (WWTPs) face the challenge of effectively removing a diverse range of contaminants of emerging concern (CECs) from municipal effluents. This study focuses on the assessment of advanced oxidation processes (AOPs), specifically UV-C/H2O2 and UV-C/Chlorine, for the removal of 14 target CECs in municipal secondary effluent (MSE, spiked with 10 µg L-1 of each CEC) or in the subsequent MSE nanofiltration retentate (NFR, no spiking). Phototreatments were carried out in continuous mode operation, with a hydraulic retention time of 3.4 min, using a tube-in-tube membrane photoreactor. For both wastewater matrices, UV-C photolysis (3.3 kJ L-1) exhibited high efficacy in removing CECs susceptible to photolysis, although lower treatment performance was observed for NFR. In MSE, adding 10 mg L-1 of H2O2 or Cl2 enhanced treatment efficiency, with UV-C/H2O2 outperforming UV-C/Chlorine. Both UV-C/AOPs eliminated the chronic toxicity of MSE toward Chlorella vulgaris. In the NFR, not only was the degradation of target CECs diminished, but chronic toxicity to C. vulgaris persisted after both UV-C/AOPs, with UV-C/Chlorine increasing toxicity due to potential toxic by-products. Nanofiltration permeate (NFP) exhibited low CECs and microbial content. A single chlorine addition effectively controlled Escherichia coli regrowth for 3 days, proving NFP potential for safe reuse in crop irrigation (<1 CFU/100 mL for E. coli; <1 mg L-1 for free chlorine). These findings provide valuable insights into the applications and limitations of UV-C/H2O2 and UV-C/Chlorine for distinct wastewater treatment scenarios.

Hydroxy esters atmospheric degradation: OH and Cl reactivity, products distribution and fate of the alkoxy radicals formed.

Kinetic studies of the reaction of ethyl glycolate HOCH2C(O)OCH2CH3 with OH radicals (kOH) and Cl atoms (kCl) have been conducted by the relative method using a glass atmospheric reactor by "in situ" Fourier Transform Infrared (FTIR) and Gas Chromatography equipped with flame ionization detection by Solid Phase Micro Extraction (GC-FID/SPME) at room temperature and atmospheric pressure. The following relative rate coefficients were determined using several reference compounds and two different techniques: kEG + OH-FTIR = (4.36 ± 1.21) × 10-12; kEG + OH-GC-FID= (3.90 ± 0.74) × 10-12; and kEG + Cl-GC-FID= (6.40 ± 0.72) × 10-11 all values in units of cm3.molecule-1.s-1. Complementary product studies were performed under comparable conditions to the kinetic tests, in order to identify the reaction products and to postulate their tropospheric oxidation mechanisms. The reaction of OH radicals and Cl atoms with ethyl glycolate initiates via H-atom abstraction from alkyl groups of the molecule. Formic acid was positively identified as a reaction product by FTIR. On the other hand, formaldehyde, acetaldehyde, glycolic acid; and formic acid were identified by the GC-MS technique. The Structure-Activity Relationship, (SAR) calculations were also implemented to estimate the more favorable reaction pathways and compare them with the products identified. Tropospheric lifetimes of τOH = 34 h and τCl = 5.5 days were estimated to determine how these investigated reactions might affect the air quality. In this sense, average ozone production of [O3] = 0.75 and a Photochemical Ozone Creation Potential, POCP, of 38 were calculated for the hydroxyl ester studied.

Atmospheric oxidation of furanones by •OH and •Cl radicals: In situ FTIR rate coefficient determinations, SAR and theoretical studies.

Gas-phase kinetics of the overall reactions of •OH and •Cl radicals with dihydrofuran-3(2H)-one (oxolan-3-one) and dihydro-2-methyl-3(2H)-furanone (2MTHF-3-one) were studied at 298 K and atmospheric pressure. The rate coefficients were determined using the relative method in a 480 L multipass glass reactor coupled to an FT-IR detection system. The rate coefficients found for oxolan 3-one and 2MTHF-one with •OH radicals (k1 and k2) and with •Cl atoms (k3 and k4) at 298 K and atmospheric pressure (in cm3 molecule-1 s-1) were: k1 = (1.86 ± 0.29) × 10-11, k2 = (2.64 ± 0.47) × 10-11, k3= (1.15 ± 0.28) × 10 -10, and k4 = (1.33 ± 0.32) × 10-10, respectively. Reactivity trends were developed by comparison with other similar structures and Fukui indices employed to determine the reactivity of different sites on the ring. The singularity of the reaction with •OH was assessed by computational studies which showed the formation of several stable hydrogen bonded complexes, explaining the difference with the reaction with the •Cl atom. SAR estimations of the rate coefficients were calculated and compared to the experimental values.

Electrodegradation of cyclophosphamide in artificial urine by combined methods.

The degradation of the chemotherapeutic drug cyclophosphamide in artificial urine was evaluated by Electrochemical Advanced Oxidation Processes (EAOP). The system consisted of an electrochemical flow reactor with a commercial DSA® electrode (nominal composition Ti / Ru0,3Ti0,7O2) and Ti-mesh cathode. In order to assess the best parameters, the effect of current density, time and flow rate were analyzed using an initial 23 factorial design. The chosen response variable was the energy efficiency to produce free chlorine species (HClO/ClO-). After obtaining the most significant factors, the Central Composite Design (CCD) was performed, where the optimum conditions were determined for the current density range (11.714 mA cm-2 and 66.57 mA cm-2), flow rate (31.33 mL min-1) and time range (19 and 37 min). Under an optimized condition, the efficiency of other combined methods (photo-assisted electrochemical, photochemical, sonoelectrochemical and photo-assisted sonoelectrochemical) was evaluated. The efficiency of degradation processes was determined by removal of Chemical Oxygen Demand (COD), creatinine and urea. Analysis by HPLC demonstrates that the cyclophosphamide was substantially removed during the treatment process of ∼77%. Based on these results, it can be observed that the coupling between electrochemical and photochemical processes is a promising alternative for the treatment of this effluent, as a marked reduction of organic matter is observed (63, 94% of creatinine, 29.62% of urea, 39.1% of TOC) and a low treatment cost ratio.

Ultrasound, Acetic Acid, and Peracetic Acid as Alternatives Sanitizers to Chlorine Compounds for Fresh-Cut Kale Decontamination.

Chlorinated compounds are usually applied in vegetable sanitization, but there are concerns about their application. Thus, this study aimed to evaluate ultrasound (50 kHz), acetic acid (1000; 2000 mg/L), and peracetic acid (20 mg/L) and their combination as alternative treatments to 200 mg/L sodium dichloroisocyanurate. The overall microbial, physicochemical, and nutritional quality of kale stored at 7 °C were assessed. The impact on Salmonella enterica Typhimurium was verified by plate-counting and scanning electron microscopy. Ultrasound combined with peracetic acid exhibited higher reductions in aerobic mesophiles, molds and yeasts, and coliforms at 35 °C (2.6; 2.4; 2.6 log CFU/g, respectively). Microbial counts remained stable during storage. The highest reduction in Salmonella occurred with the combination of ultrasound and acetic acid at 1000 mg/L and acetic acid at 2000 mg/L (2.8; 3.8 log CFU/g, respectively). No synergistic effect was observed with the combination of treatments. The cellular morphology of the pathogen altered after combinations of ultrasound and acetic acid at 2000 mg/L and peracetic acid. No changes in titratable total acidity, mass loss, vitamin C, or total phenolic compounds occurred. Alternative treatments presented equal to or greater efficacies than chlorinated compounds, so they could potentially be used for the decontamination of kale.

Use of tannin-based coagulant and chlorine dioxide in treating brewing water: reduction of trihalomethanes and impact on physicochemical and sensory quality.

This study aimed to evaluate an alternative to reduce trihalomethane (THM) formation in brewing water. THM affects the organoleptic properties of water and, consequently, the produced beer. Water treatment based on common chemicals such as alum and free chlorine could potentially form THM. Therefore, we studied the replacement of chemicals used in water treatment: aluminum sulfate by a tannin-based coagulant and sodium hypochlorite by chlorine dioxide. Experimentally, jar tests were conducted, and the role of coagulants and oxidizing agents was evaluated for: the removal of apparent color, turbidity, natural organic matter (NOM) and microorganisms; the formation of trihalomethanes (THM); and the sensory quality of the water. Using tannin-based coagulant with chlorine dioxide was associated with the lowest THM in treated water (1.7 µg/L) and higher satisfaction in the sensory analysis. However, using these chemicals make the water treatment more expensive than the current strategy. Overall, using the tannin-based coagulant and chlorine dioxide treatment is an alternative to produce water with a lower THM concentration, better physical-chemical, and sensory quality. These findings motivate further brewing experiments and a deeper economics evaluation considering the process's sustainability.

Structural design, synthesis and anti-Trypanosoma cruzi profile of the second generation of 4-thiazolidinones chlorine derivatives.

Chagas disease causes more deaths in the Americas than any other parasitic disease. Initially confined to the American continent, it is increasingly becoming a global health problem. In fact, it is considered to be an "exotic" disease in Europe, being virtually undiagnosed. Benznidazole, the only drug approved for treatment, effectively treats acute-stage Chagas disease, but its effectiveness for treating indeterminate and chronic stages remains uncertain. Previously, our research group demonstrated that 4-thiazolidinones presented anti-T. cruzi activity including in the in vivo assays in mice, making this fragment appealing for drug development. The present work reports the synthesis and anti-T. cruzi activities of a novel series of 4-thiazolidinones derivatives that resulted in an increased anti-T. cruzi activity in comparison to thiosemicarbazones intermediates. Compounds 2c, 2e, and 3a showed potent inhibition of the trypomastigote form of the parasite at low cytotoxicity concentrations in mouse splenocytes. Besides, all the 2c, 2e, and 3a tested concentrations showed no cytotoxic activity on macrophages cell viability. When macrophages were submitted to T. cruzi infection and treated with 2c and 3a, compounds reduced the release of trypomastigote forms. Results also showed that the increased trypanocidal activity induced by 2c and 3a is independent of nitric oxide release. Flow cytometry assay showed that compound 2e was able to induce necrosis and apoptosis in trypomastigotes. Parasites treated with the compounds 2e, 3a, and 3c presented flagellum shortening, retraction and curvature of the parasite body, and extravasation of the internal content. Together, these data revealed a novel series of 4-thiazolidinones fragment-based compounds with potential effects against T. cruzi and lead-like characteristics.

An unprecedented chlorine-containing piperamide from Piper pseudoarboreum as potential leishmanicidal agent.

A phytochemical investigation of the ethanolic extract of leaves from Piper pseudoarboreum led to the isolation of 3-chlorosintenpyridone 1, an unprecedented chlorinated piperamide, together with the known compounds 2-12. Their structures were established based on 1D and 2D (COSY, ROESY, HMQC, and HMBC) NMR spectroscopy, in addition to high resolution mass spectrometry. The proposed biosynthetic pathway of compound 1 is discussed. Compounds 1-12 were tested in vitro for their leishmanicidal potential against promastigote stages of Leishmania amazonensis, L braziliensis, L. guyanensis and L. infantum. Two compounds from this series, the alkamide 1 (IC50 3.4-5.2 µM) and the fatty acid 9 (IC50 18.7-29.6 µM) displayed higher or similar potency to Miltefosine, used as the reference drug.

Efficient cephalexin degradation using active chlorine produced on ruthenium and iridium oxide anodes: Role of bath composition, analysis of degradation pathways and degradation extent.

The elimination of cephalexin (CPX) using electro-generated Cl2-active on Ti/RuO2-IrO2 anode was assessed in different effluents: deionized water (DW), municipal wastewater (MWW) and urine. Single Ti/RuO2 and Ti/IrO2 catalysts were prepared to compare their morphologies and electrochemical behavior against the binary DSA. XRD and profile refinement suggest that Ti/RuO2-IrO2 forms a solid solution, where RuO2 and IrO2 growths are oriented by the TiO2 substrate through substitution of Ir by Ru atoms within its rutile-type structure. SEM reveals mud-cracked structures with flat areas for all catalysts, while EDS analysis indicates atomic ratios in the range of the oxide stoichiometries in the nominal concentrations used during synthesis. A considerably higher CPX degradation is achieved in the presence of NaCl than in Na2SO4 or Na3PO4 media due to the active chlorine generation. A faster CPX degradation is reached when the current density is increased or the pH value is lowered. This last behavior may be ascribed to an acid-catalyzed reaction between HClO and CPX. Degradation rates of 22.5, 3.96, and 0.576 µmol L-1 min-1 were observed for DW, MWW and urine, respectively. The lower efficiency measured in these last two effluents was related to the presence of organic matter and urea in the matrix. A degradation pathway is proposed based on HPLC-DAD and HPLC-MS analysis, indicating the fast formation (5 min) of CPX-(S)-sulfoxide and CPX-(R)-sulfoxide, generated due the Cl2-active attack at the CPX thioether. Furthermore, antimicrobial activity elimination of the treated solution is reached once CPX, and the initial by-products are considerably eliminated. Finally, even if only 16% of initial TOC is removed, BOD5 tests prove the ability of electro-generated Cl2-active to transform the antibiotic into biodegradable compounds. A similar strategy can be used for the abatement of other recalcitrant compounds contained in real water matrices such as urine and municipal wastewaters.

Keto-ether and glycol-ethers in the troposphere: reactivity toward OH radicals and Cl atoms, global lifetimes, and atmospheric implications.

Rate coefficients for the gas-phase reactions of OH radicals and Cl atoms with 1-methoxy-2-propanone (1-M-2-PONE), 1-methoxy-2-propanol (1-M-2-POL), and 1-methoxy-2-butanol (1-M-2-BOL) were determined at room temperature and atmospheric pressure using a conventional relative-rate technique. The following absolute rate coefficients were derived: k 1(OH + 1-M-2-PONE) = (0.64 ± 0.13) × 10-11, k 2(OH + 1-M-2-BOL) = (2.19 ± 0.23) × 10-11, k 3(Cl + 1-M-2-PONE = (1.07 ± 0.24) × 10-10, k 4(Cl + 1-M-2-POL) = (2.28 ± 0.21) × 10-10, and k 5 (Cl + 1-M-2-BOL) = (2.79 ± 0.23) × 10-10, in units of cm3 molecule-1 s-1. This is the first experimental determination of k 2-k 5. These rate coefficients were used to discuss the influence of the structure on the reactivity of the studied polyfunctional organic compounds. The atmospheric implications for 1-M-2-PONE, 1-M-2-POL, and 1-M-2-BOL and their reactions were investigated estimating atmospheric parameters such as lifetimes, global warming potentials, and average photochemical ozone production. The approximate nature of these values was stressed considering that the studied oxygenated volatile organic compounds are short-lived compounds for which the calculated parameters may vary depending on chemical composition, location, and season at the emission points.

Electrochemical treatment of penicillin, cephalosporin, and fluoroquinolone antibiotics via active chlorine: evaluation of antimicrobial activity, toxicity, matrix, and their correlation with the degradation pathways.

Antibiotics are pharmaceuticals widely consumed and frequently detected in environmental water, where they can induce toxic effects and development of resistant bacteria. Their structural variety makes the problem of antibiotics in natural water more complex. In this work, six highly used antibiotics (at 40 µmol L-1) belonging to three different classes (penicillins, cephalosporins, and fluoroquinolones) were treated using an electrochemical system with a Ti/IrO2 anode and a Zr cathode in the presence of NaCl (0.05 µmol L-1). The attack of electrogenerated active chlorine was found to be the main degradation route. After only 20 min of treatment, the process decreased more than 90% of the initial concentration of antibiotics, following the degradation order: fluoroquinolones > penicillins > cephalosporins. The primary interactions of the degrading agent with fluoroquinolones occurred at the cyclic amine (i.e., piperazyl ring) and the benzene ring. Meanwhile, the cephalosporins and penicillins were initially attacked on the ß-lactam and sulfide groups. However, the tested penicillins presented an additional reaction on the central amide. In all cases, the transformations of antibiotics led to the antimicrobial activity decreasing. On the contrary, the toxicity level showed diverse results: increasing, decreasing, and no change, depending on the antibiotic type. In fact, due to the conservation of quinolone nucleus in the fluoroquinolone by-products, the toxicity of the treated solutions remained unchanged. With penicillins, the production of chloro-phenyl-isoxazole fragments increased the toxicity level of the resultant solution. However, the opening of ß-lactam ring of cephalosporin antibiotics decreased the toxicity level of the treated solutions. Finally, the application of the treatment to synthetic hospital wastewater and seawater containing a representative antibiotic showed that the high amount of chloride ions in seawater accelerates the pollutant degradation. In contrast, the urea and ammonium presence in the hospital wastewater retarded the removal of this pharmaceutical.

Ultrasound improves chemical reduction of natural contaminant microbiota and Salmonella enterica subsp. enterica on strawberries.

New sanitization methods have been evaluated to improve food safety and food quality and to replace chlorine compounds. However, these new methods can lead to physicochemical and sensory changes in fruits and vegetables. The present study evaluated the effects of acetic acid, peracetic acid, and sodium dodecylbenzenesulfonate isolated or combined with 5min of ultrasound treatment (40kHz, 500W) on strawberry quality over 9days of storage at 8°C. The strawberry natural contaminant microbiota (molds and yeasts, mesophilic aerobic and lactic acid bacteria), physicochemical quality (pH, total titratable acidity, total soluble solids, vitamin C, and color), sensory quality (triangle test) and inactivation of Salmonella enterica subsp. enterica intentionally inoculated onto strawberries were analyzed. Ultrasound increased the effect of all chemical compounds in the reduction of aerobic mesophilic, molds and yeasts. The best treatment for those groups of microorganisms was ultrasound combined with peracetic acid (US+PA) that reduced 1.8 and 2.0logcfu/g during 9days of storage. Bactericidal effect of peracetic acid was also improved by ultrasound inactivation of S. enterica, reaching a decimal reduction of 2.1logcfu/g. Moreover, synergistic effects were observed in contaminant natural microbiota inactivation for all tested compounds during storage, without any major physicochemical or sensory alteration to the strawberries. Therefore, ultrasound treatment can improve the effect of sanitizers that are substitutes of chlorine compounds without altering the quality of strawberries during storage. Acetic acid (PubChem CID: 176); Peracetic acid (PubChem CID: 6585); Sodium dodecylbenzenesulfonate (PubChem CID: 18372154).

Photo-assisted electrochemical degradation of simulated textile effluent coupled with simultaneous chlorine photolysis.

The influence of chloride ion concentration during the photo-assisted electrochemical degradation of simulated textile effluent, using a commercial Ti/Ru0.3Ti0.7O2 anode, was evaluated. Initially, the effect of applied current and supporting electrolyte concentration on the conversion of chloride ions to form reactive chlorine species in 90 min of experiment was analyzed in order to determine the maximum production of reactive chlorine species. The optimum conditions encountered (1.5 A and 0.3 mol dm(-3) NaCl) were subsequently employed for the degradation of simulated textile effluent. The efficiency of the process was determined through the analysis of chemical oxygen demand (COD), total organic carbon (TOC), of the presence of organochlorine products and phytotoxicity. Photo-assisted electrochemical degradation was more efficient for COD and TOC removal than the electrochemical technique alone. With simultaneous UV irradiation, a reduced quantity of reactive chlorine was produced, indicating that photolysis of the chlorine species led to the formation of hydroxyl radicals. This fact turns a simple electrochemical process into an advanced oxidation process.

Comparação do teor de cloro ativo e pH do hipoclorito de sódio 0, 5% fabricado e manipulado / Comparison of active chlorine and pH of manufactured and manipulated sodium hypochlorite 0.5%

O objetivo deste estudo foi verificar a real concentração de cloro ativo e pH do hipoclorito de sódio a 0,5% fabricado e manipulado. Foram analisadas 10 amostras de hipoclorito de sódio 0,5%, sendo 5 adquiridas em comércio e outros 5 em farmácias de manipulação. As amostras foram armazenadas em frascos de vidro âmbar e mantidas em caixa de isopor. Assim, foi realizada a medição de pH com um pHmetro, e o cloro ativo por titulometria. Os dados foram submetidos ao teste de Mann-Whitney (p=0.05). A medição de pH variou de 7.7 a 11.5, com média de 9.45, e em relação à concentração de cloro ativo houve uma variação de 0,04% a 0,45%. A análise estatística não apresentou diferença significante entre os grupos. Pode-se concluir que hipoclorito de sódio 0,5% manipulado e vendido comercialmente não se diferiu entre si em relação à sua concentração, no entanto, há falta de controle entre alguns fabricantes/manipuladores quanto à real concentração de cloro ativo. Maior parte dos produtos comercializados possui pH dentro do proposto na literatura...

The aim of this study was to verify the actual concentration of active chlorine and pH of manufactured and manipulated sodium hypochlorite 0.5%. Ten samples of the sodium hypochlorite 0.5% were analyzed, 5 manufactured and other 5 manipulated. The samples were stored in amber glass bottles and styrofoam box. Then, it was performed the pH measurement using a pHmeter, and the active chlorine by titrimetry. The data were submitted to Mann-Whitney test (p=0.05). PH measuring ranged from 7.7 to 11.5, with a mean of 9.45, and active chlorine concentration ranged from 0.04% to 0.45%. There was no significant difference between the groups. It can be concluded that manufactured and manipulated sodium hypochlorite 0.5% did not differ regarding concentration, and there is no control of concentration for both manufacturer and manipulator. Most of manufactured and manipulated products presented pH in accordance to that proposed in the literature...

UASB reactor effluent disinfection by ozone and chlorine.

This research studied the sequential ozone and chlorine process with respect to, the inactivation of indicator bacteria and the formation of ozone disinfection byproducts in sanitary wastewater effluent. The applied ozone doses were 5, 8 and 10 mg.O3.L(-1), followed by chlorine doses of 10, 20 and 30 mg.L(-1), respectively. After the sequential ozone/chlorine process, the mean reduction in chemical oxygen demand ranged from 9 to 37%. Total coliform inactivation ranged from 1.59 to 3.73 log10, and E. coli was always <1 CFU 100 mL(-1). Ozonation resulted in the formation of aldehydes, which were not significantly impacted by the subsequent chlorine dose (P ≤ 0.05).

Traditional and ion-pair halogen-bonded complexes between chlorine and bromine derivatives and a nitrogen-heterocyclic carbene.

A theoretical study of the halogen-bonded complexes (A-X···C) formed between halogenated derivatives (A-X; A = F, Cl, Br, CN, CCH, CF3, CH3, H; and X = Cl, Br) and a nitrogen heterocyclic carbene, 1,3-dimethylimidazole-2-ylidene (MeIC) has been performed using MP2/aug'-cc-pVDZ level of theory. Two types of A-X:MeIC complexes, called here type-I and -II, were found and characterized. The first group is described by long C-X distances and small binding energies (8-54 kJ·mol(-1)). In general, these complexes show the traditional behavior of systems containing halogen-bonding interactions. The second type is characterized by short C-X distances and large binding energies (148-200 kJ·mol(-1)), and on the basis of the topological analysis of the electron density, they correspond to ion-pair halogen-bonded complexes. These complexes can be seen as the interaction between two charged fragments: A(-) and (+)[X-CIMe] with a high electrostatic contribution in the binding energy. The charge transfer between lone pair A(LP) to the σ* orbital of C-X bond is also identified as a significant stabilizing interaction in type-II complexes.

Investigation of rainwater contamination sources in the southern part of Brazil.

Rainwater quality is influenced by air pollutants and can affect sensitive ecosystems. This study was conducted to identify the sources of rainwater contamination in a receptor investigated in the southern part of Brazil. A total of 22 rainwater samples were collected at Florianópolis, Brazil. The sampling station is influenced by continental emissions (soil resuspension, traffic emissions and combustion) and marine aerosols. Over the sampling period, the average pH and electrical conductivity (EC) of the precipitation was found to be 4.97 +/- 0.41 and 14.68 microS cm(-1) +/- 13.47, respectively. In addition topH and EC, ions and trace metals in the collected rainwater were quantified. The results were investigated by a combination of techniques including principal component analysis (PCA), a back trajectory model and other statistical and graphical interpretation methodologies. A PCA showed that Cl(-), Na+, Mg2+ and part of the K+ and SO4(2-) content were mainly contributed by marine aerosols, whereas the contribution from continental sources (combustion, traffic emissions and other urban activities) was dominant in the content of NO3(-) and part of the SO4(2-) and Mn content. Soil resuspension was responsible for the concentrations of most of the trace metals (apart from Mn) and Ca2+ in the rainwater. An inverse correlation among the elemental concentrations, amount of rainfall and wind speed was observed. The northern transport pathway was identified as being associated with high concentrations of NO3(-) and slightly decreased pH values. However, the low standard deviation observed for the pH values during the sampling campaign also showed a small variation in the data, suggesting that the acidity is most probably being constantly sourced from a natural origin, such as organic acids.

Products and mechanism of the reactions of OH radicals and Cl atoms with methyl methacrylate (CH2═C(CH3)C(O)OCH3) in the presence of NOx.

The OH radical and Cl atom initiated photodegradation of methyl methacrylate has been investigated in a 1080 L quartz-glass environmental chamber at 298 ± 2 K and atmospheric pressure of synthetic air using in situ FTIR spectroscopy to monitor the reactants and products. The major products observed in the OH reaction were methyl pyruvate (92 ± 16%) together with formaldehyde (87 ± 12%) as a coproduct from the C1-C2 bond cleavage channel of the intermediate 1,2-hydroxyalkoxy radical, formed by the addition of OH to the terminal carbon of the double bond which is designated C1. For the Cl atom reaction, the products identified were chloroacetone (41 ± 6%) together with its coproduct formaldehyde (35 ± 5%) and methyl pyruvate (24 ± 4%) together with its coproduct formylchloride (25 ± 4%). The results show that the fate of the intermediate 1,2-chloroalkoxy radical involves not only cleavage of the C1-C2 bond but also quite substantial cleavage of the C2-C3 bond. The present results are compared with previous studies of acrylates, showing different branching ratios for the OH and Cl addition reactions in the presence of NOx. Atmospheric implications are discussed.