Dye-sensitized photodegradation of the fungicide carbendazim and related benzimidazoles

The present work studies the visible-light-promoted photodegradation of the colorless fungicide carbendazim (methyl 2-benzimidazolecarbamate) and several 2-substituted benzimidazoles (SBZ's), in water or water-methanol solution, in the presence of air and, as a photosensitizer, the synthetic xanthene dye Rose Bengal (RB) or the natural pigment riboflavin (Rf). The results indicate that the degradation of each particular SBZ depends on its chemical structure and on the sensitizer employed. In the presence of RB, the degradation always operates via a singlet molecular oxygen (O(2)((1)Delta(g)))-mediated mechanism, through a highly efficient process, as deduced from the comparison of the rate constants for physical and chemical quenching of O(2)((1)Delta(g)). In the presence of Rf, the visible-light irradiation of any of the studied SBZ's produces a series of competitive processes that depend on the relative concentrations of Rf and SBZ. These processes include the quenching of excited singlet and triplet Rf states by the SBZ and the generation of both O(2)((1)Delta(g)) and superoxide radical anion (O(2)(-)), the latter generated by electron transfer from excited Rf species to the dissolved oxygen. The overall result is the photodegradation of the SBZ and the photoprotection of the sensitizer.     

Photodegradation of the herbicide Norflurazon sensitised by Riboflavin. A kinetic and mechanistic study

The kinetics and mechanism of the Riboflavin (Rf)-promoted photochemical degradation with visible light of the herbicide Norflurazon (NF) has been studied by time-resolved and stationary techniques. Using light of wavelength higher than 400 nm--a region where NF is totally transparent--and with concentrations of Rf and NF of ca. 0.02 and 1 mM, respectively, only the excited triplet state of Rf ((3)Rf*) is quenched by NF, in competition with dissolved ground state triplet oxygen, O(2)((3)Sigma(g)(-)). NF degradation mainly occurs by reaction with superoxide radical anion O(2)(-) formed through two electron transfer steps: from NF to (3)Rf*, yielding Rf radical anion, and from this anion to O(2)((3)Sigma(g)(-)), regenerating ground state Rf. Although singlet molecular oxygen is also produced, NF only quenches this oxidative species in a physical mode. The global result is the photoprotection of the sensitiser and the photodegradation of NF.     

Model of stomatal ammonia compensation point (STAMP) in relation to the plant nitrogen and carbon metabolisms and environmental conditions

Agricultural crops can be either a source or a sink of ammonia (NH₃). Most NH₃ exchange models developed so far do not account for the plants nitrogen (N) metabolism and use prescribed compensation points. We present here a leaf-scale simplified NH₃ stomatal compensation point model related to the plants N and carbon (C) metabolisms, for C₃ plants. Five compartments are considered: xylem, cytoplasm, apoplasm, vacuole and sub-stomatal cavity. The main processes accounted for are the transport of ammonium (NH₄⁺), NH₃ and nitrate (NO₃⁻) between the different compartments, NH₄⁺ production through photorespiration and NO₃⁻ reduction, NH₄⁺ assimilation, chemical and thermodynamic equilibriums in all the compartments, and stomatal transfer of NH₃.The simulated compensation point is sensitive to paramaters related to the apoplastic compartment: pH, volume and active transport rate. Determining factors are leaf temperature, stomatal conductance and NH₄⁺ flux to the leaf. Atmospheric NH₃ concentration seem to have very little effect on the compensation point in conditions of high N fertilization. Comparison of model outputs to experimental results show that the model underestimates the NH₃ compensation point for high N fertilization and that a better parametrisation of sensitive parameters especially active trasport rate of NH₄⁺ may be required.     

Phthalates and the aquatic environment: Part II The bioconcentration and depuration of di-2-ethylhexyl phthalate (DEHP) and di-isodecyl phthalate (DIDP) in mussels (Mytilus edulis)

Mussels ($\text{Mytilus edulis}$) were exposed to di-2-ethylhexyl phthalate (DEHP) and to di-isodecyl phthalate (DIDP) over a period of 28 days. The bioconcentration factor (BCF) as measured by ¹⁴C analysis, reached estimated plateau levels corresponding to mean BCF values of approximately 2500 and 3500 for the DEHP and DIDP respectively. The mussels were then held in clean seawater for a further 14 days and ¹⁴C analysis showed a depuration half-life of approximately 3.5 days for both phthalates. During the whole 42 days of the experiment general observations on the health of the animals showed no evidence of any adverse effects.     

Ammonia stomatal compensation point of young oilseed rape leaves during dark/light cycles under various nitrogen nutritions

The plant can be a source or a sink of ammonia (NH₃) depending on its nitrogen (N) supply, metabolism and on the background atmospheric concentrations. Thus plants play a major role in regulating atmospheric NH₃ concentrations. For a better understanding of the factors influencing the NH₃ stomatal compensation point, it is important to analyse the dynamics of leaf NH₃ fluxes. The relationship between the leaf NH₃ fluxes and the leaf apoplast ammonium and nitrate concentrations, N nutrition and the light and dark periods was studied here.We designed an experiment to quantitatively assess leaf-atmosphere NH₃ exchange and the stomatal compensation point and to identify the main factors affecting the variation of NH₃ fluxes in oilseed rape. We tested day and night dynamics as well as the effect of five different N treatments. Two experimental methods were used: a dynamic open flux chamber and extraction of the apoplastic solution.Chamber measurements showed that there was a good correlation between plant NH₃ fluxes and water fluxes. Compensation points were calculated by two different methods and ranged between 0.8 and 12.2 μg m⁻³ NH₃ (at 20 °C) for the different N treatments. Apoplastic solution measurements showed that there was no significant differences in the apoplastic NH₄⁺ concentrations ([NH₄⁺]_apo) extracted in dark and light periods for the same N treatment. Statistical analysis also showed that [NH₄⁺]_apo was correlated with [NH₄⁺] in the nutrient solution and weakly correlated with [NO₃⁻]. Apoplast NH₄⁺ concentrations ranged between 0.1 and 2.1 mM, bulk tissue NH₄⁺ concentrations between 3.9 and 6.6 mM and xylem concentrations between 2.4 and 6.1 mM depending on the N supply.Calculated NH₃ emission potential from the extraction measurements were over-estimated when compared with the value calculated from chamber measurements. Errors related to chamber measurements included separation of the cuticular and stomatal fluxes and the calculation of total resistance to NH₃ exchange. Errors related to the extraction measurements included assessing the amount of cytoplasmic contamination. We do not have another method to assess the NH₃ stomatal compensation point and the choice between these two measurement techniques should depend on the scales to which the measurements apply and the processes to be studied.     

Cross-sectional biomonitoring study of pesticide exposures in Queensland,Australia, using pooled urine samples

A range of pesticides are available in Australia for use in agricultural and domestic settings to control pests, including organophosphate and pyrethroid insecticides, herbicides, and insect repellents, such as N,N-diethyl-meta-toluamide (DEET). The aim of this study was to provide a cost-effective preliminary assessment of background exposure to a range of pesticides among a convenience sample of Australian residents. De-identified urine specimens stratified by age and sex were obtained from a community-based pathology laboratory and pooled (n = 24 pools of 100 specimens). Concentrations of urinary pesticide biomarkers were quantified using solid-phase extraction coupled with isotope dilution high-performance liquid chromatography–tandem mass spectrometry. Geometric mean biomarker concentrations ranged from <0.1 to 36.8 ng/mL for organophosphate insecticides, <0.1 to 5.5 ng/mL for pyrethroid insecticides, and <0.1 to 8.51 ng/mL for all other biomarkers with the exception of the DEET metabolite 3-diethylcarbamoyl benzoic acid (4.23 to 850 ng/mL). We observed no association between age and concentration for most biomarkers measured but noted a “U-shaped” trend for five organophosphate metabolites, with the highest concentrations observed in the youngest and oldest age strata, perhaps related to age-specific differences in behavior or physiology. The fact that concentrations of specific and non-specific metabolites of the organophosphate insecticide chlorpyrifos were higher than reported in USA and Canada may relate to differences in registered applications among countries. Additional biomonitoring programs of the general population and focusing on vulnerable populations would improve the exposure assessment and the monitoring of temporal exposure trends as usage patterns of pesticide products in Australia change over time.     

The development and application of remote sensing to monitor sand dune habitats

Sand dunes are complex systems that contain several habitats, often as mosaics or transitions between types. Several of these habitats are afforded protection under European Legislation and in the UK nationally within Special Areas of Conservation (SAC) and Sites of Special Scientific Interest (SSSI). Natural England has a statutory duty to report to Europe on the conservation status and condition of sand dunes; and is required to report to the UK Government on designated sites. To achieve this we have sought ways of capturing, analysing and interpreting data on the extent and location of sand dune habitats. This requires an ability to be able to obtain data over large areas of coastline in an efficient way. Natural England and Environment Agency Geomatics have worked collaboratively for over 16 years, sharing data and ecological knowledge. In 2012 work started to evaluate the use of remote sensing to map UK BAP and Annex I sand dune habitats. A methodology has now been developed and tested to map sand dune habitats. The key objective was to provide an operational tool that will help to map these habitats and understand change on sites around England. This has been achieved through analysis of LIDAR and Compact Airborne Spectrographic Imager (CASI) data using Object Orientated Image Analysis. Quality Control (QC) and accuracy assessments have shown this approach to be successful and 11 sites have been mapped to date. These techniques are providing a new approach to monitoring change in coastal vegetation communities and informing management of protected sites.     

Relationship between ammonia stomatal compensation point and nitrogen metabolism in arable crops: current status of knowledge and potential modelling approaches

The ammonia stomatal compensation point of plants is determined by leaf temperature, ammonium concentration ([NH4+]apo) and pH of the apoplastic solution. The later two depend on the adjacent cells metabolism and on leaf inputs and outputs through the xylem and phloem. Until now only empirical models have been designed to model the ammonia stomatal compensation point, except the model of Riedo et al. (2002. Coupling soil-plant-atmosphere exchange of ammonia with ecosystem functioning in grasslands. Ecological Modelling 158, 83-110), which represents the exchanges between the plant's nitrogen pools. The first step to model the ammonia stomatal compensation point is to adequately model [NH4+]apo. This [NH4+]apo has been studied experimentally, but there are currently no process-based quantitative models describing its relation to plant metabolism and environmental conditions. This study summarizes the processes involved in determining the ammonia stomatal compensation point at the leaf scale and qualitatively evaluates the ability of existing whole plant N and C models to include a model for [NH4+]apo.