A critical review on the accumulation of neonicotinoid insecticides in pollen and nectar: Influencing factors and implications for pollinator exposure.

Neonicotinoids are a class of neuro-active insecticides widely used to protect major crops, primarily because of their broad-spectrum insecticidal activity and low vertebrate toxicity. Owing to their systemic nature, plants readily take up neonicotinoids and translocate them through roots, leaves, and other tissues to flowers (pollen and nectar) that serve as a critical point of exposure to pollinators foraging on treated plants. The growing evidence for potential adverse effects on non-target species, especially pollinators, and persistence has raised serious concerns, as these pesticides are increasingly prevalent in terrestrial and aquatic systems. Despite increasing research efforts, our understanding of the potential toxicity of neonicotinoids and the risks they pose to non-target species remains limited. Therefore, this critical review provides a succinct evaluation of the uptake, translocation, and accumulation processes of neonicotinoids in plants and the factors that may affect the eventual build-up of neonicotinoids in pollen and nectar. The role of plant species, as well as the physicochemical properties and application methods of neonicotinoids is discussed. Potential knowledge gaps are identified, and questions meriting future research are suggested for improving our understanding of the relationship between neonicotinoid residues in plants and exposure to pollinators.

Pharmaceutical and Personal Care Products: From Wastewater Treatment into Agro-Food Systems.

Irrigation with treated wastewater (TWW) and application of biosolids introduce numerous pharmaceutical and personal care products (PPCPs) into agro-food systems. While the use of TWW and biosolids has many societal benefits, introduction of PPCPs in production agriculture poses potential food safety and human health risks. A comprehensive risk assessment and management scheme of PPCPs in agro-food systems is limited by multiple factors, not least the sheer number of investigated compounds and their diverse structures. Here we follow the fate of PPCPs in the water-soil-produce continuum by considering processes and variables that influence PPCP transfer and accumulation. By analyzing the steps in the soil-plant-human diet nexus, we propose a tiered framework as a path forward to prioritize PPCPs that could have a high potential for plant accumulation and thus pose greatest risk. This article examines research progress to date and current research challenges, highlighting the potential value of leveraging existing knowledge from decades of research on other chemicals such as pesticides. A process-driven scheme is outlined to derive a short list that may be used to refocus our future research efforts on PPCPs and other analogous emerging contaminants in agro-food systems.

Direct Conjugation of Emerging Contaminants in Arabidopsis: Indication for an Overlooked Risk in Plants?

Agricultural use of treated wastewater, biosolids, and animal wastes introduces a multitude of contaminants of emerging concerns (CECs) into the soil-plant system. The potential for food crops to accumulate CECs depends largely on their metabolism in plants, which at present is poorly understood. Here, we evaluated the metabolism of naproxen and ibuprofen, two of the most-used human drugs from the Profen family, in Arabidopsis thaliana cells and the Arabidopsis plant. The complementary use of high-resolution mass spectrometry and 14C labeling allowed the characterization of both free and conjugated metabolites, as well as nonextractable residues. Naproxen and ibuprofen, in their parent form, were conjugated quickly and directly with glutamic acid and glutamine, and further with peptides, in A. thaliana cells. For example, after 120 h, the metabolites of naproxen accounted for >90% of the extractable chemical mass, while the intact parent itself was negligible. The structures of glutamate and glutamine conjugates were confirmed using synthesized standards and further verified in whole plants. Amino acid conjugates may easily deconjugate, releasing the parent molecule. This finding highlights the possibility that the bioactivity of such CECs may be effectively preserved through direct conjugation, a previously overlooked risk. Many other CECs are also carboxylic acids, such as the profens. Therefore, direct conjugation may be a common route for plant metabolism of these CECs, making it imperative to consider conjugates when assessing their risks.

Spot drip application of dimethyl disulfide as a post-plant treatment for the control of plant parasitic nematodes and soilborne pathogens in grape production.

BACKGROUND: Plant parasitic nematodes and soilborne pathogens can reduce the overall productivity in grape production. Not all grape growers apply soil fumigants before planting, and there is no single rootstock resistant to all nematode species. The aim of this investigation was to evaluate the effect of dimethyl disulfide (DMDS) applied at 112, 224, 448 and 897 kg ha(-1) as a post-plant treatment against soilborne plant parasitic nematodes and pathogens on the grape yield in established grapevines. RESULTS: In microplot and field trials, post-plant fumigation with DMDS controlled citrus (Tylenchulus semipenetrans), root-knot (Meloidogyne spp.), pin (Paratylenchus spp.) and ring (Mesocriconema xenoplax) nematodes in established Thomson Seedless grapevines. However, DMDS did not control the soilborne pathogens Pythium ultimum and Fusarium oxysporum. No indications of phytotoxicity were detected after post-plant fumigation with DMDS. In the field trial, grape yield was significantly higher with the lowest DMDS rate, but no difference among other rates was observed in comparison with the untreated control. CONCLUSION: Post-plant fumigation with DMDS controlled plant parasitic nematodes in established grapevines but was less efficacious against soilborne pathogens. Low rates of DMDS were sufficient for nematode control and increased the grape yield, probably without affecting beneficial soil organisms. Further research on evaluating the potential effect of DMDS against beneficial soil organisms is needed.

Enhancing soil sorption capacity of an agricultural soil by addition of three different organic wastes.

This study evaluated the ability of three unmodified organic residues (composted sewage sludge, RO1; chicken manure, RO2; and a residue from olive oil production called 'orujillo', RO3) and a soil to sorb six pesticides (atrazine, lindane, alachlor, chlorpyrifos, chlorfenvinphos and endosulfan sulfate) and thereby explored the potential environmental value of these organic residues for mitigating pesticide pollution in agricultural production and removing contaminants from wastewater. Pesticide determination was carried out using gas chromatography coupled with mass spectrometry. Adsorption data were analyzed by the Langmuir and Freundlich adsorption approaches. Experimental results showed that the Freundlich isotherm model best described the adsorption process and that Kf values increased with an increase in organic matter (OM) content of the amended soil. The order of adsorption of pesticides on soils was: chlorpyrifos≥endosulfan sulfate>chlorfenvinphos≥lindane>alachlor≥atrazine. The sorption was greater for the most hydrophobic compounds and lower for the most polar ones, as corroborated by a negative correlation between Kf values and solubility. Sorption increased with an increase in organic matter. Sorption capacity was positively correlated with the organic carbon (OC) content. The organic amendment showing the maximum sorption capacity was RO3 in all cases, except for chlorfenvinphos, in which it was RO2. The order of adsorption capacity of the amendments depended on the pesticide and the organic dosage. In the case of the 10% amendment the order was RO3>RO2>RO1>soil, except for chlorfenvinphos, in which it was RO2>RO3>RO1>soil, and atrazine, where RO2 and RO3 amendments had the same effect on the soil sorption capacity (RO2≥RO3>RO1>soil).

Stereoisomeric separation and toxicity of the nematicide fosthiazate.

Considerable attention has been paid to the enantiomeric resolution and toxicity of some chiral organophosphorous pesticides (OPs) with one asymmetric center, but research concerning chiral OPs with two asymmetric centers is still limited. In the present study, the stereoisomeric separation and toxicity of fosthiazate, a chiral OP with two asymmetric centers on phosphorus and carbon atoms, was investigated. All four stereoisomers of fosthiazate were separated successfully with a Chiralpak(R) AD [amylase tris(3,5-dimethyl-phenyl carbamate)] column on high-performance liquid chromatography. The resolved isomers and the pairs of enantiomers were further distinguished using a circular dichroism detector and an optical rotation detector, designating the first (pk1) and third (pk3) eluted peaks as one pair of enantiomers and the second (pk2) and fourth (pk4) peaks as the other pair. The developed method was used to prepare microquantities of individual stereoisomers that were used for in vitro and in vivo bioassays. The inhibition potencies of the stereoisomers against acetylcholinesterase of Electrophorus electricus were slightly stereoselective, with a maximum difference of 1.4-fold among the isomers. A 3.1-fold difference, however, was observed in the acute toxicity of isomers to Daphnia magna. The 48-h toxicity of isomers to D. magna followed the order pk1 > pk2 > pk4 > racemate approximately pk3. The stereoselective toxicity to D. magna found in fosthiazate suggests that the environmental safety of fosthiazate should be evaluated on the basis of its individual isomers.