Alexandra ter Halle

Understanding the Fragmentation Pattern of Marine Plastic Debris

The global estimation of microplastic afloat in the ocean is only approximately 1% of annual global plastic inputs. This reflects fundamental knowledge gaps in the transformation, fragmentation, and fates of microplastics in the ocean. In order to better understand microplastic fragmentation we proceeded to a thorough physicochemical characterization of samples collected from the North Artlantic subtropical gyre during the sea campaign Expedition seventh Continent in May 2014. The results were confronted with a mathematical approach. The introduction of mass distribution in opposition to the size distribution commonly proposed in this area clarify the fragmentation pattern. The mathematical analysis of the mass distribution points out a lack of debris with mass lighter than 1 mg. Characterization by means of microscopy, microtomography, and infrared microscopy gives a better understanding of the behavior of microplastic at sea. Flat pieces of debris (2 to 5 mm in length) typically have one face that is more photodegraded (due to exposure to the sun) and the other with more biofilm, suggesting that they float in a preferred orientation. Smaller debris, with a cubic shape (below 2 mm), seems to roll at sea. All faces are evenly photodegraded and they are less colonized. The breakpoint in the mathematical model and the experimental observation around 2 mm leads to the conclusion that there is a discontinuity in the rate of fragmentation: we hypothesized that the smaller microplastics, the cubic ones mostly, are fragmented much faster than the parallelepipeds.

Photodegradation of bentazon, clopyralid, and triclopyr on model leaves: importance of a systematic evaluation of pesticide photostability on crops.

Photolyses of three herbicides, bentazon, clopyralid, and triclopyr, were studied on plant leaves after crop treatment. The experiments were carried out on cuticular wax films, which are good models for leaf surfaces. The pure compounds and their commercial formulations were investigated under simulated solar light. At the recommended agricultural application rates, the three formulated herbicides photolyzed more rapidly on films than on soil or in water. Their photolysis is likely to be an important dissipation path from crops after treatment. The effects induced by the adjuvants in formulations were varied. Adjuvants slowed the photodegradation of bentazon slightly. In Garlon, in which triclopyr and clopyralid are combined, the adjuvants did not affect the photolysis of clopyralid even though they accelerated the rate of photolysis of triclopyr by a factor of 7. The kinetics were also affected by the application rates. This work also underscores the importance of assessing the photoreactivity of active ingredients in conditions similar to those of their application.

The effect of mixing two herbicides mesotrione and nicosulfuron on their photochemical reactivity on cuticular wax film

There are growing concerns about the environmental impacts of pesticides with a consequent increasing demand for meaningful and accurate information on their consumption and use pattern. Pesticides reactivity towards light is rarely considered at the leaf surface after crop treatment although it is directly impacting the pesticide efficiency. We have established a test on thin wax films which mimic well the leaf surface. Under simulated solar light herbicides mesotrione and nicosulfuron as well as their mixture are photoreactive. For both herbicides considered separately, there is a strong accelerating effect of adjuvants compared to the pure active ingredient. Mesotrione, a triketonic herbicide was very reactive with a half-life of photolysis of 2h. Nicosulfuron, a sulfonylurea, has a half-life of photolysis of 32 h. The mixing of the two formulated herbicides had an accelerating effect on both herbicide decay rates. The products formed when considering the pure molecule were mainly the result of photohydrolysis, oxidation and cyclisation. While pesticide photostability on crops is not evaluated for registration, this study demonstrates that these photochemical tests could be useful to improve the pesticide effectiveness and reduce the applied dose.

Grape marc extract acts as elicitor of plant defence responses

Plant protection based on novel alternative strategies is a major concern in agriculture to sustain pest management. The marc extract of red grape cultivars reveals plant defence inducer properties. Treatment with grape marc extract efficiently induced hypersensitive reaction-like lesions with cell death evidenced by Evans Blue staining of tobacco leaves. Examination of the infiltration zone and the surrounding areas under UV light revealed the accumulation of autofluorescent compounds. Both leaf infiltration and a foliar spray of the red grape extract on tobacco leaves induced defence gene expression. The PR1 and PR2 target genes were upregulated locally and systemically in tobacco plants following grape marc extract treatment. The grape extract elicited an array of plant defence responses making this natural compound a potential phytosanitary product with a challenging issue and a rather attractive option for sustainable agriculture and environmentally friendly practices.

Rates of production of hydroxyl radicals and singlet oxygen from irradiated compost

The use of organic matter from compost to promote the catalytic photodegradation of micropollutants by solar light appears to be environmentally promising. However, quantitative evaluation of the photodegradation potential of the compost is needed. Our goal was to measure the formation rate of hydroxyl radicals and singlet oxygen, two strongly oxidant species, from irradiated compost organic matter. These two reactive species were photogenerated in all of our extracts regardless of the origin of the compost or the extraction procedure; however, their formation rates increased with composting time. Two herbicides and a fungicide were successfully photodegraded when irradiated with simulated or natural solar light in the presence of the compost organic matter or compost suspensions. For reasons of simplification and ease, the use of the latter is recommended in practice.

Nanoplastic in the North Atlantic Subtropical Gyre

Plastics can be found in all ecosystems across the globe. This type of environmental pollution is important, even if its impact is not fully understood. The presence of small plastic particles at the micro- and nanoscales is of growing concern, but nanoplastic has not yet been observed in natural samples. In this study, we examined four size fractions (meso-, large micro-, small micro-, and nanoplastics) of debris collected in the North Atlantic subtropical gyre. To obtain the nanoplastic portion, we isolated the colloidal fraction of seawater. After ultrafiltration, the occurrence of nanoscale particles was demonstrated using dynamic light scattering experiments. The chemical fingerprint of the colloids was obtained by pyrolysis coupled with gas chromatography-mass spectrometry. We demonstrated that the signal was anthropogenic and attributed to a combination of plastics. The polymer composition varied among the size classes. At the micro- and nanoscales, polyvinyl chloride, polyethylene terephthalate, polystyrene and polyethylene were observed. We also observed changes in the pyrolytic signals of polyethylene with decreasing debris size, which could be related to the structural modification of this plastic as a consequence of weathering.

Photoprotection by plant extracts: a new ecological means to reduce pesticide photodegradation.

A pesticides reactivity toward light at the leaf surface after crop treatment is rarely considered, although such degradation reactions directly affect the pesticides effectiveness. To overcome these limitations, the use of plant pigments was proposed as a new class of photoprotecting agent. The photoprotecting properties of seven plant pigments were tested under controlled conditions over herbicide sulcotrione. Grape wine extracts were tested over a panel of pesticides from distinct chemical families. The addition of plant extracts almost systematically reduced the pesticides photoreactivity. The grape wine extracts improve at least by 38% the half-life of photolysis of almost all of the active ingredients tested, except for the herbicide triclopyr. Fustictree extract increases by 82% the photostability of the herbicide sulcotrione. Plant extracts mainly act as sunscreens; that is, the photostabilization of the active ingredient is due to the competitive energy absorption of UV photon. The use of natural plant extracts is a promising strategy to limit pesticide photodegradation. It is a way to develop sustainable and innovative technology for the plant protection industry, being beneficial from both economic and ecological points of view.

Inhibition of Herbicide Photodegradation by Plant Products

Pesticide reactivity toward light is rarely considered at the leaf surface after crop treatment; regardless, these degradation reactions directly impact the pesticide effectiveness. The use of sunscreen adjuvants to overcome photodegradation has presented some limitations so far. Raw hydroalcoholic plant extracts have been recently proposed to be used as photoprotecting adjuvants; on a model system they significantly decreased the photodegradation of pesticide. Here it is demonstrated that their use makes possible a dose reduction. Sulcotrione, a selective herbicide for use in maize, was tested in a growth chamber equipped with simulated solar light against a typical weed in maize. Sprayed weeds were monitored by biometrical and physiological parameters. Sulcotrione minimum dose required for a good herbicidal efficacy (ED(50), corresponding to 50% of chlorophyll content decay) was estimated to be 55 g ha(-1). In the presence of grape extract added in a 3-fold excess compared to the herbicide, the ED(50) decreased to 34 g ha(-1). The use of grape extract allows extension of sulcotrione herbicidal activity and reduction of the dose by 35% in controlled conditions. This is a promising result for the effective dose field adjustment.

Effect of a Spreading Adjuvant on Mesotrione Photolysis on Wax Films

There is little information about pesticide photostability on plants, especially when considering the effects of the formulation. We evaluated the photostability of a herbicide, mesotrione, on wax films. These surfaces are good systems to mimic the outer layer of the leaf. Within the range of recommended agricultural rates, pure mesotrione half-life on cuticular wax films was between 100 and 160 min. Formulated, the phototransformation rate was multiplied by a factor of 4.8. We assume that the acceleration is mainly due to the surfactants, agents that allow a better spreading of the active ingredient at the leaf surface. Since mesotrione photolysis is a fast process on wax films, we can assume that this process would be significant in the field after treatment.

Understanding mesotrione photochemistry when applied on leaves

Environmental context. Pesticide has greatly contributed to the increased yields and regular production in agriculture; however, its use is nowadays more and more being questioned. Current authorisation procedures are more and more comprehensive (evaluating their environmental fate and impact on ecosystems and on human health) but are not yet fully satisfactory. Here we demonstrate the utility of evaluating the stability of pesticide towards sunlight when applied on crops. Abstract. We developed a methodology to perform laboratory studies that approach field conditions. To demonstrate our methods, we used the herbicide mesotrione. Simulated solar light irradiation experiments were conducted on several cuticular wax films. Adjuvants greatly favoured the rate of mesotrione photolysis. Specifically, the photolytic transformation of formulated mesotrione was 15 times faster than that of pure mesotrione. The morphology and composition of the wax films had a greater effect on the photolysis of formulated mesotrione than of pure mesotrione, which formed aggregates on the waxes. This shows the importance of considering the formulation when studying pesticide photolysis on crops. To corroborate our model, we conducted experiments on detached leaves. The rates of photolysis on leaves and on wax films were of the same order of magnitude. Finally, the mesotrione rate of photolysis on leaves is much higher compared with data from the literature in water and on soils. Photolysis is likely to be a fast dissipation process on crops. The photodegradation of pesticide on crops should be systematically evaluated.