Environmental photochemistry on plants: recent advances and new opportunities for interdisciplinary research.

Plants play a central role in the photochemistry of chemicals in the environment. They represent a major atmospheric source of volatile organic compounds (VOCs) but also an important environmental surface for the deposition and photochemical reactions of pesticides, gaseous and particulate pollutants. In this review, we point out the role of plant leaves in these processes, as a support affecting the reactions physically and chemically and as a partner through the release of natural constituents (water, secondary metabolites). We discuss the influence of the chosen support (leaves, needle surfaces or fruit cuticles, extracted cuticular waxes and model surfaces) and other factors (additives, pesticides mixture, and secondary metabolites) on the photochemical degradation kinetics and mechanisms. We also show how plants can be a source of photochemically reactive species which can act as photosensitizers promoting the photodegradation of pesticides or the formation and aging of secondary organic aerosols (SOA) and secondary organic materials (SOM). Understanding the fate of chemicals on plants is a research area located at the interface between photochemistry, analytical chemistry, atmospheric chemistry, microbiology and vegetal physiology. Pluridisciplinary approaches are needed to deeply understand these complex phenomena in a comprehensive way. To overcome this challenge, we summarize future research directions which have been clearly overlooked until now.

Photolysis of the herbicide dicamba in aqueous solutions and on corn (Zea mays) epicuticular waxes.

Dicamba, 3,6-dichloro-2-methoxybenzoic acid, has been used in agriculture as an herbicide for over fifty years, and has seen an increase in use in the past decade due to the development of glyphosate resistant weeds and soybeans genetically modified to resist dicamba. Despite the previous use of dicamba, many questions remain regarding its environmental fate, especially the new commercial formulations used on genetically modified crops. Here, the photolysis of dicamba, including the commercial formulation Diablo®, is examined in aqueous solutions of varying water quality and on the surface of corn epicuticular waxes. Dicamba is stable to hydrolysis but degrades under UV light. The photolytic half-life for dicamba photolysis in aqueous solutions at pH 7 irradiated with Rayonet UVB lamps (280-340 nm) was t1/2 = 43.3 min (0.72 hours), in aqueous solutions at pH 7 in a Q-Sun solar simulator (λ > 300 nm) was t1/2 = 13.4 hours, and on epicuticular waxes irradiated in the Q-Sun solar simulator was t1/2 = 105 hours. Experiments with adjuvants, compounds added into the commercial formulations of dicamba, led to increases in rate constants for both aqueous and wax experiments. In addition to kinetic rate constants, photoproducts were tentatively assigned for the aqueous solution experiments. This work deepens the knowledge of the environmental fate of dicamba including the role surfactants play in chemical reactions and in providing new applications of current methods to examine the photolysis of chemicals sorbed to surfaces.

Comparison of the Photodegradation of Imazethapyr in Aqueous Solution, on Epicuticular Waxes, and on Intact Corn (Zea Mays) and Soybean (Glycine Max) Leaves.

A direct, controlled comparison of the photodegradation of imazethapyr has been made between imazethapyr in aqueous solutions, imazethapyr on the surface of epicuticular waxes of corn and soybean plants, and imazethapyr on the surface of intact corn and soybean plant leaves. In some experiments, the imazethapyr solutions were allowed to evaporate partially or fully after application to better model environmental conditions. The photodegradation of imazethapyr was fastest in aqueous solutions (k = 0.16 ± 0.02 h-1) and slowest on the surface of corn and soybean plants (kcorn = 0.00048 ± 0.001 h-1 and ksoy = 0.00054 ± 0.003 h-1). Experiments allowing evaporation during irradiation have intermediate rate constants (e.g., kcorn = 0.082 ± 0.005 h-1). Finally, identification of photoproducts was also examined on epicuticular waxes of corn and soybean plants for the first time.

Statistical analysis of the photodegradation of imazethapyr on the surface of extracted soybean (Glycine max) and corn (Zea mays) epicuticular waxes.

The photodegradation rate of the herbicide imazethapyr on epicuticular waxes of soybean and corn plants was investigated. Plant age, relative humidity, temperature, and number of light banks were varied during plant growth, analyzed statistically, and examined to determine if these factors had an effect on the photodegradation of imazethapyr. Through ultraviolet/visible (UV-Vis) and fluorescence spectroscopy, epicuticular wax characteristics of soybean and corn plants were explored, were used to confirm observations determined statistically, and explain correlations between the rate constants and the composition of the epicuticular waxes. Plant age, the interaction between plant age and light, and the quadratic dependence on temperature were all determined to have a significant impact on the photodegradation rate of imazethapyr on the epicuticular waxes of soybean plants. As for the photodegradation rate on the epicuticular waxes of corn plants, the number of light banks used during growing and temperature were significant factors.

Analysis of the Photodegradation of the Imidazolinone Herbicides Imazamox, Imazapic, Imazaquin, and Imazamethabenz-methyl in Aqueous Solution.

The photodegradation of the imidazolinone herbicides imazamox, imazapic, imazaquin, and imazamethabenz-methyl has been investigated in phosphate-buffered solutions and buffered solutions containing natural organic matter (NOM). The hydrolysis of imazamethabenz-methyl, the only imidazolinone herbicide susceptible to hydrolysis, was also examined. The rate of hydrolysis of imazamethabenz-methyl increased with increasing pH, with the para isomer degrading more rapidly than the meta isomer. All photodegradation rate constants increased with pH and plateaued after pH 5.2. All imidzaolinones degraded more quickly under 253.7 nm lamps as compared to degradation under 310 nm lamps. Imazamox and imazapic degraded more rapidly than imazaquin at all pH values and had higher quantum yields. In addition, imazamox and imazapic quantum yields increased as a function of pH, whereas imazaquin quantum yields showed no trend as a function of pH. Photodegradation reaction rate constants decreased as the concentration of NOM was increased in the solutions due to the effect of light screening. Formulas for the proposed photoproducts for imazamox, imazapic, and imazaquin in pH 7 phosphate buffers were identified, and structures for the photoproducts are proposed.

Photodegradation of the herbicide imazethapyr in aqueous solution: effects of wavelength, pH, and natural organic matter (NOM) and analysis of photoproducts.

The photodegradation of imazethapyr, 5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-4,5-dihydroimidazol-1H-3-yl)nicotinic acid, has been investigated in phosphate buffers and in buffered solutions containing natural organic matter (NOM). Imazethapyr degrades most quickly under 253.7 nm light and at pH values >4. The presence of NOM in solution caused the reaction rate constants for the photodegradation to decrease, with higher concentrations of NOM having a larger effect. Calculations suggest light screening is the major effect of the NOM. Seven photoproducts have been identified, and a photodegradation mechanism is proposed.

Hydrolysis and H2O2-assisted UV photolysis of 3-chloro-1,2-propanediol.

3-Chloro-1,2-propanediol (3-MCPD) is a chlorinated alcohol that is often formed as a by-product in the manufacturing of food products. In addition, 3-MCPD may be a disinfection by-product from wastewater treatment by chlorine and may be present in drinking waters from purification plants using epichlorohydrin-linked cationic polymer resins as flocculants. Due to concerns about the toxicity of 3-MCPD and its potential presence in water samples, the removal of 3-MCPD from water should be addressed and examined. For the first time a systematic examination of the removal of 3-MCPD via hydrolysis and photolysis processes is presented. 3-MCPD is shown to undergo hydrolysis at near neutral pH values, but at much slower rates than can be obtained by UV/H2O2 processes. 3-MCPD does not undergo rapid direct photolysis. Re-evaluation of temperature and pH dependent hydrolysis rate data indicates that hydrolysis is first order with respect to [OH(-)].

Hydrogen peroxide-assisted UV photodegradation of Lindane.

Aqueous solutions of gamma-hexachlorocyclohexane (Lindane) were photolyzed (lambda=254 nm) under a variety of solution conditions. The initial concentrations of hydrogen peroxide (H(2)O(2)) and Lindane varied from 0 to 20 mM and 0.21 to 0.22 microM, respectively, the pH ranged from 3 to 11, and several concentration ratios of Suwannee River humic acid and fulvic acid were dissolved in the irradiated solutions. Lindane rapidly reacted, and the maximum reaction rate constant (9.7 x 10(-3) s(-1)) was observed at pH 7 and initial [H(2)O(2)]=1 mM. Thus, 90% of the Lindane is destroyed in approximately 4 min under these conditions. In addition, within 15 min, all chlorine atoms were converted to chloride ion, indicating that chlorinated organic by-products do not accumulate. The reactor was characterized by measuring the photon flux (7.04 x 10(-6) E s(-1)) and the cumulative production of *OH during irradiation. The cumulative *OH production during irradiation was fastest at an initial [H(2)O(2)]=5 mM (k=0.77 micro M s(-1)).

Heterogeneous chemistry of carbon aerosols.

Atmospheric carbon particles originate from natural sources and from human activity. The processes that lead to their formation are varied and include fossil fuel combustion, biomass burning, and mechanical stress and wear of carbonaceous materials. In this review, we examine recent work on the structure and composition of carbon aerosol particles, and we describe how they react with the atmospherically abundant gases ozone, oxygen, sulfur dioxide, nitric acid, and nitrogen oxides. The study of carbon particles in the laboratory has shown that chemical reactivity depends strongly on the type of carbon used and on experimental conditions such as temperature and humidity. The variability in the results demonstrates the difficulty in extrapolating laboratory results to atmospheric conditions and in explaining the role of carbon particles in processes such as global warming and environmental chemical cycling.

Surface chemistry of aerosolized nanoparticles:thermal oxidation of silicon.

The kinetics of reaction between silicon nanoparticles and molecular oxygen were studied by tandem differential mobility analysis. Aerosolized silicon nanoparticles were extracted from a low-pressure silane plasma into an atmospheric pressure aerosol flow tube reactor. Particles were initially passed through a differential mobility analyzer that was set to transmit only those particles having mobility diameters of approximately 10 nm. The monodisperse particle streams were mixed with oxygen/nitrogen mixtures of different oxygen volume fractions and allowed to react over a broad temperature range (600-1100 degrees C) for approximately one second. Particles were size-classified after reaction with a second differential mobility analyzer. The particle mobility diameters increased upon oxidation by up to 1.3 nm, depending on the oxygen volume fraction and the reaction temperature. Oxidation is described by a kinetic model that considers both oxygen diffusion and surface reaction, with diffusion becoming important after formation of a 0.5 nm thick oxide monolayer.

Surface chemistry of nanometer-sized aerosol particles: reactions of molecular oxygen with 30 nm soot particles as a function of oxygen partial pressure.

The kinetics of the reaction between soot nanoparticles and molecular oxygen were studied by tandem differential mobility analysis (TDMA). The particles were extracted from the tip of an ethene diffusion flame. Reactions were studied at atmospheric pressure in mixtures of nitrogen and oxygen. The studies involved particles of an initial mobility diameter of 30 nm over broad ranges of temperature (500-1100 degrees C) and oxygen volume fraction (0-1). Measurements as a function of oxygen partial pressure establish that the oxidation kinetics are not first-order in oxygen volume fraction (F(O2)). Rather, the oxidation rate increases rapidly and linearly with F(O2) between 0 and 0.05 and then more slowly but still linearly between 0.05 and 1. Temperature dependent measurements are consistent with a reaction pathway involving two kinetically distinguishable oxidation sites which interconvert thermally and through oxidation. Results and conclusions are compared to those of earlier studies on the oxidation of soot.