Estimation of sampling uncertainty for determination of pesticide residues in plant commodities

In order to provide residue data for refining the estimated sampling uncertainty, a coordinated research program was initiated for performing field studies on residues in individual items of leafy vegetables, small and large crops. The trials were carried out in 13 countries with 3 small fruits, 5 large crops, 2 medium/large crops and 3 leafy vegetables. The 25 pesticide active ingredients applied represented the dicarboximide (3), organophosphorus (8), synthetic pyrethroids (5), phthalimides (2), organochlorine (1) and other types of pesticides (6). In addition, 11 supervised field trials were performed in grapes and lettuce by the pesticide manufacturers, and their results were provided for evaluation. The studies represented actual agriculture practice around the world, and provide reliable data for estimation of sampling uncertainty. Based on the 12346 residue data, the best estimate for the relative sampling uncertainty for composite samples, assuming sample size of 10 for small crops and leafy vegetables and 5 for large crops, with 95% confidence limits in brackets are: small commodities: 0.25 (0.20–0.29); Brassica leafy vegetables: 0.20 (0.16–0.24); large commodities: 0.33 (0.29–0.38).     

Characterization of distribution of pesticide residues in crop units

The characteristic features of distribution of pesticide residues in crop units and single sample increments were studied based on more than 19,000 residue concentrations measured in root vegetables, leafy vegetables, small-, medium- and large-size fruits representing 20 different crops and 46 pesticides. Log-normal, gamma and Weibull distributions were found to provide the best fit for the relative frequency distributions of individual residue data sets. The overall best fit was provided by lognormal distribution. The relative standard deviation of residues (CV) in various crops ranged from 15–170%. The 100–120 residue values being in one data set was too small to identify potential effects of various factors such as the chemical and physical properties of pesticides and the nature of crops. Therefore, the average of CV values, obtained from individual data sets, were calculated and considered to be the best estimate for the likely variability of unit crop residues for treated field (CV = 0.8) and market samples (CV = 1.1), respectively. The larger variation of residues in market samples was attributed to the potential mixing of lots and varying proportion of non-detects. The expectable average variability of residues in composited samples can be calculated from the typical values taking into account the sample size.     

Polycyclic aromatic hydrocarbons: bees, honey and pollen as sentinels for environmental chemical contaminants

Three beehive matrices, sampled in six different apiaries from West France, were analyzed for the presence of four polycyclic aromatic hydrocarbons (PAH4: benzo[a]pyrene, benzo[a]anthracene, benzo[b]fluoranthene and chrysene). Samples were collected during four different periods in both 2008 and 2009. Honey samples showed the lowest levels of PAH4 contamination (min = 0.03 μg kg⁻¹; max = 5.80 μg kg⁻¹; mean = 0.82 μg kg⁻¹; Sd = 1.17). Bee samples exhibited higher levels of PAH4 contamination (min = 0.32 μg kg⁻¹; max = 73.83 μg kg⁻¹; mean = 7.03 μg kg⁻¹; Sd = 17.83) with a great dispersion of the concentrations due to four main events of high concentrations. Pollen samples showed only one major episode with the highest PAH4 concentration found (min = 0.33 μg kg⁻¹; max = 129.41 μg kg⁻¹; mean = 7.10 μg kg⁻¹; Sd = 22.28). The PAH4 concentrations found were significantly influenced by the landscape context for all beehive samples.     

Propiconazole inhibits the sterol 14α-demethylase in Glomus irregulare like in phytopathogenic fungi

The increasing concentrations impact (0.02, 0.2 and 2 mg L⁻¹) of a Sterol Biosynthesis Inhibitor (SBI) fungicide, propiconazole, was evaluated on development and sterol metabolism of two non-target organisms: mycorrhizal or non-mycorrhizal transformed chicory roots and the arbuscular mycorrhizal fungus (AMF) Glomus irregulare using monoxenic cultures. In this work, we provide the first evidence of a direct impact of propiconazole on the AMF by disturbing its sterol metabolism. A significant decrease in end-products sterols contents (24-methylcholesterol and in 24-ethylcholesterol) was observed concomitantly to a 24-methylenedihydrolanosterol accumulation indicating the inhibition of a key enzyme in sterol biosynthesis pathway, the sterol 14α-demethylase like in phytopathogenic fungi. A decrease in end-product sterol contents in propiconazole-treated roots was also observed suggesting a slowing down of the sterol metabolism in plant. Taken together, our findings suggest that the inhibition of the both AM symbiotic partners development by propiconazole results from their sterol metabolism alterations.     

Ecotoxicity and biodegradability of antielectrostatic dicephalic cationic surfactants

Four series of dicephalic cationic surfactants, considered as new antielectrostatic agents have been investigated in order to establish their toxicity and biodegradability. Among them N,N-bis[3,3′-(dimethylamine)propyl]alkylamides, N,N-bis[3,3′-(dimethylamine)propyl]alkylamide dihydrochlorides, N,N-bis[3,3′-(trimethylammonio)propyl]alkylamide dibromides and N,N-bis[3,3′-(trimethylammonio)propyl]alkylamide dimethylsulphates with different hydrophobic chain length (n-C₉H₁₉ to n-C₁₅H₃₁) and type of counterion (chloride, bromide and methylsulfate) have been studied. The inhibitory effect against microorganisms has been examined using model gram-positive and gram-negative bacteria, and yeasts. None of the tested surfactants have shown antimicrobial activity against gram-negative bacteria (Escherichia coli, Pseudomonas putida) and yeasts (Saccharomyces cerevisiae, Rhodotorula glutinis) at a concentration below 1000 μg mL⁻¹, however some of them were moderately active against gram-positive bacteria (Staphylococcus aureus, Bacillus subtilis). The Microtox® test was successfully applied to measure EC₅₀ values of the studied dicephalic cationic surfactants. Their toxicity to Vibrio fischeri depended upon the alkanoyl chain length with the EC₅₀ values in a range of 2.6-980 mg L⁻¹. N,N-bis[3,3′-(dimethylamine)propyl]alkylamide dihydrochlorides 2a-b and N,N-bis[3,3′-(trimethylammonio)propyl]alkylamide dibromides 3a-b comprising n-decanoyl and n-dodecanoyl hydrophobic tails appeared to be the least toxic. Furthermore, the biodegradability under aerobic conditions of 2a-b, 3a-b was evaluated using OECD Method 301F. According to the obtained results 2a, 3a-3b can be considered as almost readily biodegradable and they are not expected to be persistent in the environment. Additionally, partial biodegradation was observed for 2b, indicating its possible biodegradation in wastewater treatment systems.     

Bioaccessibility of trace elements as affected by soil parameters in smelter-contaminated agricultural soils: a statistical modeling approach

An investigation was undertaken to identify the most significant soil parameters that can be used to predict Cd, Pb, and Zn bioaccessibility in smelter-contaminated agricultural soils. A robust model was established from an extended database of soils by using: (i) a training set of 280 samples to select the main soil parameters, to define the best population to be taken into account for the model elaboration, and to construct multivariate regression models, and (ii) a test set of 110 samples to validate the ability of the regression models. Total carbonate, organic matter, sand, P(2)O(5), free Fe-Mn oxide, and pseudototal Al and trace element (TE) contents appeared as the main variables governing TE bioaccessibility. The statistical modeling approach was reasonably successful, indicating that the main soil factors influencing the bioaccessibility of TEs were taken into account and the predictions could be applicable for further risk evaluation in the studied area.     

In situ stabilization of trace metals in a copper-contaminated soil using P-spiked Linz-Donawitz slag

Purpose  

A former wood exploitation revealing high Cu and As concentration of the soils served as a case study for assisted phytoextraction.     

The Efficacy of a Programme of Landslide Risk Reduction in Areas of Unplanned Housing in the Eastern Caribbean

Poor countries are disproportionately affected by the cost of disasters. Yet there is evidence of the benefits of seeking to mitigate the impact of a disaster, compared with the costs incurred in ‘making good’ after a major event has occurred. This article reviews a programme of landslide risk reduction in unplanned communities in the Eastern Caribbean. The construction of appropriate surface water management measures, based on the application of scientific and engineering principles, has been demonstrated to reduce the hazard from rainfall-triggered landslides. Adopting a community-based approach additionally delivers social and environmental benefits relating to employment generation, improvements in the environmental conditions within the community, and improvements slope management practices. The sustained implementation of the community-based projects has provided the necessary evidence-base for these practices to influence Government policy and practice, and gain recognition from regional development agencies. The strategic and incremental uptake of the community-based methodology is demonstrated to be an effective means for delivering physical landslide risk reduction measures in the most ‘at risk’ areas of unplanned housing.     

Effects of silicon and copper on bamboo grown hydroponically

Due to its high growth rate and biomass production, bamboo has recently been proven to be useful in wastewater treatment. Bamboo accumulates high silicon (Si) levels in its tissues, which may improve its development and tolerance to metal toxicity. This study investigates the effect of Si supplementation on bamboo growth and copper (Cu) sensitivity. An 8-month hydroponic culture of bamboo Gigantocloa sp. “Malay Dwarf ” was performed. The bamboo plants were first submitted to a range of Si supplementation (0–1.5 mM). After 6 months, a potentially toxic Cu concentration of 1.5 μM Cu²⁺ was added. Contrary to many studies on other plants, bamboo growth did not depend on Si levels even though it absorbed Si up to 218 mg g^?1 in leaves. The absorption of Cu by bamboo plants was not altered by the Si supplementation; Cu accumulated mainly in roots (131 mg kg^?1), but was also found in leaves (16.6 mg kg^?1) and stems (9.8 mg kg^?1). Copper addition did not induce any toxicity symptoms. The different Cu and Si absorption mechanisms may partially explain why Si did not influence Cu repartition and concentration in bamboo. Given the high biomass and its absorption capacity, bamboo could potentially tolerate and accumulate high Cu concentrations making this plant useful for wastewater treatment.     

Photodegradation of sulfonamides and their N 4-acetylated metabolites in water by simulated sunlight irradiation: kinetics and identification of photoproducts

Once released into the aquatic environment, pharmaceuticals may undergo different degradation processes. Photodegradation, for example, might be an important elimination process for light-sensitive pharmaceuticals, such as antibiotics. In this study, the fate of sulfonamides (sulfamethazine, sulfadiazine, and sulfamethoxazole) and their N ⁴-acetylated metabolites (N ⁴-acetylsulfadiazine, N ⁴-acetylsulfamethazine, and N ⁴-acetylsulfamethoxazole) under simulated sunlight irradiation was investigated. The irradiation resulted in total or almost total degradation (88 to 98 %) of the pharmaceuticals tested, except for sulfamethazine (52 %), during 24 h of irradiation. The photoproducts of all investigated pharmaceuticals have been analyzed using high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry. Structure elucidation performed from photodegradation products of both, sulfonamides and their N ⁴-acetylated metabolites, clearly showed two major formation pathways. These were cleavage of the sulfonamide bond as well as SO₂ extrusion. In total, nine photoproducts were elucidated. Among these photoproducts, the tautomers of sulfamethoxazole and desulfonated products of sulfadiazine and sulfamethazine were also present. Tautomers of sulfadiazine and sulfamethazine have been characterized here for the first time as well as some photoproducts of sulfadiazine, sulfametoxazole, and their metabolites N ⁴-acetylsulfadiazine and N ⁴-acetylsulfametoxazole. The obtained results are an important piece in the complex puzzle for assessing the environmental fate of sulfonamides and their metabolites in the environment.