A new approach for the modelling of chestnut wood photo-degradation monitored by different spectroscopic techniques

The aim of this work is to study the colour and chemical modifications of the surfaces in chestnut wood samples as a consequence of irradiating in a controlled environment. The changes were investigated by a new analytical approach by combining traditional techniques such as reflectance spectrophotometry in the visible range and Fourier transform infrared spectroscopy with new hyperspectral imaging, in order to obtain forecast models to describe the phenomenon. The statistical elaboration of the experimental data allowed to validate the measurements and to obtain models enabling to relate the investigated parameters; the elaboration of the hyperspectral images by chemometric methods allowed for studying the changes in the reflectance spectra. A result of great importance is the possibility to correlate the oxidation of wood chemical components with the colour change in a totally non-invasive modality. This result is particularly relevant in the field of cultural heritage and in general in the control processes of wooden materials.     

Sublethal effects of epoxiconazole on the earthworm <Emphasis Type="Italic">Aporrectodea icterica</Emphasis>

Earthworms play a key role in agroecosystem soil processes. This study aims to assess the effects of different doses of a commercial formulation of epoxiconazole (Opus®), a persistent and widely used fungicide, on the earthworm Aporrectodea icterica. A laboratory study was conducted in a natural soil in order to measure effects of Opus® on earthworm mortality, uptake, weight gain, enzymatic activities (catalase and glutathione-S-transferase), and energy resources (lipids and glycogens). The estimated LC50 was 45.5 mg kg^?1, or 268 times the recommended dose. Weight gains were 28, 19, and 13 % of the initial weight after 28 days of exposure in the control and D1 and D10 (1 and 10 times the recommended dose) treatments, respectively. No difference was observed for catalase activity between the three treatments, at 7, 14, or 28 days. The glutathion-S-transferase (GST) activity was two times as high in D1 as in D0 at 14 days. At 28 days, glycogen concentration was lower in D10 than in the D1 treatment. This study highlighted moderate sublethal effects of the commercial formulation Opus® for earthworms. Considering that these effects were observed on a species found in cultivated fields, even at recommended rates, much more attention should be paid to this pesticide.     

How to assess the feeding activity in ecotoxicological laboratory tests using enchytraeids?

The risk assessment of pesticides on soil fauna is an issue to protect agroecosystem sustainability. Enchytraeids are recognized as relevant soil bioindicators of chemical stress in agroecosystems. In laboratory, the reproduction test was found to be sensitive to reveal chemical impacts on enchytraeids. However, it does not allow to assess the impacts on ecological functions in which enchytraeids are involved. The objectives of this study were (i) to explore the feasibility of the bait-lamina test with enchytraeids under laboratory conditions and (ii) to compare its sensitivity with the Enchytraeid Reproduction Test. We exposed individuals of Enchytraeus albidus to two commercial formulations of fungicides widely used in Europe. The EC50 reproduction for the Swing^® Gold (50 g L^?1 epoxiconazole and 133 g L^?1 dimoxystrobin) and the Cuprafor micro^® (50% copper oxychloride) were respectively estimated at 1.66?±?0.93 times the recommended dose and >?496 mg kg^?1 of copper. However, no impact was found on the feeding activity of enchytraeids. The bait-lamina test thus appeared less sensitive than the Enchytraeid Reproduction Test to the tested fungicides. Despite that, this test which is achievable under laboratory conditions and allows assessing indirect effects of pesticides is quick, cheap, and easy to perform. It would deserve to be used to explore longer-exposure effects through the repeated addition of bait-lamina sticks.     

Solid-phase extraction for multi-residue analysis of pesticides in honey

A fast and simple multi-residue method for the analysis of 15 organophosphorus (OP), 17 organochlorine (OC), 8 pyrethroids (PYR), 12 N-methyl-carbamate (NMC) pesticide residues and bromopropylate in honey is presented. Ready-to-use EXtrelutNT 20 column, eluted with dichloromethane, was used to extract the pesticide residues from the aqueous-acetone honey sample, obtaining a clean extract directly analyzable. Determination was carried out by gas chromatography (GC) coupled with flame photometric detector (FPD) for OP compounds and by GC coupled with mass spectrometry detector (MSD) for OC and PYR pesticides and bromopropylate. The NMC pesticides were analysed by liquid chromatography-double derivatization coupled with spectrofluorimetric detector (LC/DD/Fl). This method allows the determination of the 53 pesticide residues at low concentrations (0.0005-0.074 mg/kg) and can be used to assess the compliance with the Maximum Residues Levels (MRLs) set by the European Union. The performance of the method was evaluated and specificity, linearity, recovery, repeatability, reproducibility, limit of quantification (LOQ) and limit of detection (LOD) were determined. A good linearity (r(2)≥ 0.99) was found in the range 0.0005-0.074 mg/kg for the majority of the compounds studied. Most of the pesticides had recoveries in the range 70-103 % and values of relative standard deviation (RSD) < 20 for repeatability and reproducibility, showing good accuracy and precision of the method. Aldicarb partially degraded in aldicarb sulphoxide during the analytical procedure, giving anomalous values. The LOQ for all pesticides investigated was from 0.0005 to 0.025 mg/kg while the LOD ranged from 0.0002 to 0.008 mg/kg.     

Historical maps and satellite images as tools for shoreline variations and territorial changes assessment: the case study of Volturno Coastal Plain (Southern Italy)

Anthropic pressure has caused severe variations of Mediterranean coastal areas currently hosting about 480 million people. The replacement of natural land covers with crops and urban environment coupled with the reduction of sediment supply to the coast, subsidence, Relative Sea Level Rise and the high frequency of storm events, have caused severe shoreline erosion. In this paper, we stress the key role of historical maps, topographic maps and free satellite images to forecast the rates of coastline changes and to recognize the main features of past landscapes as tools for risk reduction. This data was recorded into a Geographical Information System dedicated to coastal management that allows to compare different coastal zones and elaborate maps. The analysis was applied to the case study of Volturno Coastal Plain (VCP), extending from the town of Mondragone to Patria Lake (Campania Region, Southern Italy). Indeed, the intense territorial modification that occurred between the seventies and eighties, coupled with the exposure to coastal erosion, make the VCP a good test area. The spatial analysis algorithms allowed to outline the main features of past landscapes and how they changed from roman times to present while the coastal evolution (erosion, accretion) and possible future coastal trend was assessed with the Digital Shoreline Analysis System (DSAS) software. Starting from the Bourbon domain, the reclamation caused the first great territorial change (e.g. wetlands were transformed into agricultural lands, regimentation of surperficial water) but the negative effects of antrophic pressure, as the intense urbanization of the coastal belt, emerged in the seventies of the last century. The shoreline position was defined for 9 time intervals (from 1817 to 2012) as the ratio of the distance between two shorelines and the relative elapsed time. Moreover, for the 1957–1998 and 1998–2012 time windows, the shoreline trends were calculated with the weighted linear regression method. The first trend pointed out an intensive erosional phase (mean value: 5 m/yr) for a wide sector close to the Volturno River mouth, the eroded sediment nourished the beaches of other coastal sectors. This phase was related to the reduction of River sediment supply mainly due to the construction of the Ponte Annibale dam on the Volturno River. The second (1998–2012) showed an alternation of erosion and accretion sectors due to a sediment starved condition to deltaic zone and to a sequence of 52 sea protection works in the Gaeta Gulf. Furthermore, the regression values of more recent time interval, was assumed as a scenario to draw the probable shoreline position in 2022. The overlay of this shoreline on the Technical Maps of Campania Region at 1:5000 scale highlighted the urban area that could be exposed to damages.     

<Emphasis Type="Italic">Aporrectodea caliginosa</Emphasis>, a relevant earthworm species for a posteriori pesticide risk assessment: current knowledge and recommendations for culture and experimental design

Ecotoxicological tests with earthworms are widely used and are mandatory for the risk assessment of pesticides prior to registration and commercial use. The current model species for standardized tests is Eisenia fetida or Eisenia andrei. However, these species are absent from agricultural soils and often less sensitive to pesticides than other earthworm species found in mineral soils. To move towards a better assessment of pesticide effects on non-target organisms, there is a need to perform a posteriori tests using relevant species. The endogeic species Aporrectodea caliginosa (Savigny, 1826) is representative of cultivated fields in temperate regions and is suggested as a relevant model test species. After providing information on its taxonomy, biology, and ecology, we reviewed current knowledge concerning its sensitivity towards pesticides. Moreover, we highlighted research gaps and promising perspectives. Finally, advice and recommendations are given for the establishment of laboratory cultures and experiments using this soil-dwelling earthworm species.     

Evaluation of epoxiconazole bioavailability in soil to the earthworm <Emphasis Type="Italic">Aporrectodea icterica</Emphasis>

In soil, the determination of total concentration using an exhaustive extraction method has little relevance to evaluate the exposure of an organism to a chemical, because of sorption processes. This study aims to propose a mild extraction method to evaluate the bioavailability of the fungicide epoxiconazole to the earthworm Aporrectodea icterica. Experiments were conducted in soils presenting various textures and organic carbon contents, spiked with formulated epoxiconazole 7 to 56 days prior to their extraction. In parallel, the epoxiconazole concentration was determined in exposed earthworms and the fungicide’s effects were evaluated by measuring weight gain, enzymatic activities and total protein contents. Among the various mild chemical solvents tested to evaluate the environmental availability of the fungicide, the 50 mM hydroxypropyl-β-cyclodextrin solution allowed to extract around 30 % of epoxiconazole. This percentage corresponded to the ratio determined in exposed A. icterica under similar soil conditions. Furthermore, this mild method was demonstrated to be sensitive to soil sorption capacities and to ageing. The mild extraction method was then applied to explore the relationship between total and (bio)available concentrations in soil and in A. icterica, over 7- or 28-day exposure time. This demonstrated the proportionality between epoxiconazole concentration in earthworm and available in soil (up to 96 %, with regression coefficient R ²?=?0.98). Sublethal effects on earthworm remained not significant.     

Solid-phase extraction for multi-residue analysis of pesticides in honey

A fast and simple multi-residue method for the analysis of 15 organophosphorus (OP), 17 organochlorine (OC), 8 pyrethroids (PYR), 12 N-methyl-carbamate (NMC) pesticide residues and bromopropylate in honey is presented. Ready–to–use EXtrelut®NT 20 column, eluted with dichloromethane, was used to extract the pesticide residues from the aqueous-acetone honey sample, obtaining a clean extract directly analyzable. Determination was carried out by gas chromatography (GC) coupled with flame photometric detector (FPD) for OP compounds and by GC coupled with mass spectrometry detector (MSD) for OC and PYR pesticides and bromopropylate. The NMC pesticides were analysed by liquid chromatography-double derivatization coupled with spectrofluorimetric detector (LC/DD/Fl). This method allows the determination of the 53 pesticide residues at low concentrations (0.0005–0.074 mg/kg) and can be used to assess the compliance with the Maximum Residues Levels (MRLs) set by the European Union. The performance of the method was evaluated and specificity, linearity, recovery, repeatability, reproducibility, limit of quantification (LOQ) and limit of detection (LOD) were determined. A good linearity (r²? 0.99) was found in the range 0.0005–0.074 mg/kg for the majority of the compounds studied. Most of the pesticides had recoveries in the range 70–103 % and values of relative standard deviation (RSD) < 20 for repeatability and reproducibility, showing good accuracy and precision of the method. Aldicarb partially degraded in aldicarb sulphoxide during the analytical procedure, giving anomalous values. The LOQ for all pesticides investigated was from 0.0005 to 0.025 mg/kg while the LOD ranged from 0.0002 to 0.008 mg/kg.     

A critical review of effect modeling for ecological risk assessment of plant protection products

Environmental Science and Pollution Research - A wide diversity of plant protection products (PPP) is used for crop protection leading to the contamination of soil, water, and air, which can have...