(Non)targeted Chemical Analysis and Risk Assessment of Organic Contaminants in Darkibor Kale Grown at Rural and Urban Farms.

This study investigated the presence and human hazards associated with pesticides and other anthropogenic chemicals identified in kale grown in urban and rural environments. Pesticides and related compounds (i.e., surfactants and metabolites) in kale samples were evaluated using a nontargeted data acquisition for targeted analysis method which utilized a pesticide mixture containing >1,000 compounds for suspect screening and quantification. We modeled population-level exposures and assessed noncancer hazards to DEET, piperonyl butoxide, prometon, secbumeton, terbumeton, and spinosyn A using nationally representative estimates of kale consumption across life stages in the US. Our findings indicate even sensitive populations (e.g., pregnant women and children) are not likely to experience hazards from these select compounds were they to consume kale from this study. However, a strictly nontargeted chemical analytical approach identified a total of 1,822 features across all samples, and principal component analysis revealed that the kale chemical composition may have been impacted by agricultural growing practices and environmental factors. Confidence level 2 compounds that were ≥5 times more abundant in the urban samples than in rural samples (p < 0.05) included chemicals categorized as "flavoring and nutrients" and "surfactants" in the EPA's Chemicals and Products Database. Using the US-EPA's Cheminformatics Hazard Module, we identified that many of the nontarget compounds have predicted toxicity scores of "very high" for several end points related to human health. These aspects would have been overlooked using traditional targeted analysis methods, although more information is needed to ascertain whether the compounds identified through nontargeted analysis are of environmental or human health concern. As such, our approach enabled the identification of potentially hazardous compounds that, based on their hazard assessment score, merit follow-up investigations.

Extracting Structural Information from Physicochemical Property Measurements Using Machine Learning─A New Approach for Structure Elucidation in Non-targeted Analysis.

Non-targeted analysis (NTA) has made critical contributions in the fields of environmental chemistry and environmental health. One critical bottleneck is the lack of available analytical standards for most chemicals in the environment. Our study aims to explore a novel approach that integrates measurements of equilibrium partition ratios between organic solvents and water (KSW) to predictions of molecular structures. These properties can be used as a fingerprint, which with the help of a machine learning algorithm can be converted into a series of functional groups (RDKit fragments), which can be used to search chemical databases. We conducted partitioning experiments using a chemical mixture containing 185 chemicals in 10 different organic solvents and water. Both a liquid chromatography quadrupole time-of-flight mass spectrometer (LC-QTOF MS) and a LC-Orbitrap MS were used to assess the feasibility of the experimental method and the accuracy of the algorithm at predicting the correct functional groups. The two methods showed differences in log KSW with the QTOF method showing a mean absolute error (MAE) of 0.22 and the Orbitrap method 0.33. The differences also culminated into errors in the predictions of RDKit fragments with the MAE for the QTOF method being 0.23 and for the Orbitrap method being 0.31. Our approach presents a new angle in structure elucidation for NTA and showed promise in assisting with compound identification.

Assessing the fate of antibiotics and agrochemicals during anaerobic digestion of animal manure.

Antibiotics and pesticides are used extensively by the livestock industry. Agricultural chemicals can pose potential human and environmental health risks due to their toxicity and through their contributions to antimicrobial resistance, and strategies to reduce their emission into the environment are urgently needed. Anaerobic digestion (AD) is a sustainable technology for manure management that produces biogas while also providing an opportunity to degrade agricultural chemicals that are present in manure. While the effects of selected chemicals on biogas production have been investigated previously, little is known about chemical transformations during AD. Using lab-scale AD batch reactors containing dairy manure, degradation kinetics and transformation products (TPs) were investigated for twenty compounds that are likely to be present in manure management systems and that we hypothesized would transform during AD. Digestate samples were extracted using a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method and analyzed using liquid chromatography - high-resolution mass spectrometry. Eleven of the tested chemicals degraded, leading to the formation of 47 TPs. Three compounds degraded abiotically only, two degraded biotically only, and six degraded both abiotically and biotically. These results suggest that in addition to renewable energy generation, AD contributes to the degradation of chemical contaminants present in agricultural waste streams. However, the potential toxic effects of TPs require further investigation.

Evidence for a mutualistic relationship between the cyanobacteria Nostoc and fungi Aspergilli in different environments.

Symbiotic partnerships are widespread in nature and in industrial applications yet there are limited examples of laboratory communities. Therefore, using common photobionts and mycobionts similar to those in natural lichens, we create an artificial lichen-like symbiosis. While Aspergillus nidulans and Aspergillus niger could not obtain nutrients from the green algae, Chlorella, and Scenedesmus, the cyanobacteria Nostoc sp. PCC 6720 was able to support fungal growth and also elevated the accumulation of total biomass. The Nostoc-Aspergillus co-cultures grew on light and CO2 in an inorganic BG11 liquid medium without any external organic carbon and fungal mycelia were observed to peripherally contact with the Nostoc cells in liquid and on solid media at lower cell densities. Overall biomass levels were reduced after implementing physical barriers to indicate that physical contact between cyanobacteria and heterotrophic microbes may promote symbiotic growth. The synthetic Nostoc-Aspergillus nidulans co-cultures also exhibited robust growth and stability when cultivated in wastewater over days to weeks in a semi-continuous manner when compared with axenic cultivation of either species. These Nostoc-Aspergillus consortia reveal species-dependent and mutually beneficial design principles that can yield stable lichen-like co-cultures and provide insights into microbial communities that can facilitate sustainability studies and broader applications in the future. KEY POINTS: • Artificial lichen-like symbiosis was built with wild-type cyanobacteria and fungi. • Physical barriers decreased biomass production from artificial lichen co-cultures. • Artificial lichen adapted to grow and survive in wastewater for 5 weeks.

Changes in Arabidopsis thaliana gene expression in response to silver nanoparticles and silver ions.

The release of silver nanoparticles (AgNPs) in the environment has raised concerns about their effects on living organisms, including plants. In this study, changes in gene expression in Arabidopsis thaliana exposed to polyvinylpyrrolidone-coated AgNPs and silver ions (Ag(+)) were analyzed using Affymetrix expression microarrays. Exposure to 5 mg/L AgNPs (20 nm) for 10 days resulted in upregulation of 286 genes and downregulation of 81 genes by reference to nonexposed plants. Exposure to 5 mg/L Ag(+) for 10 days resulted in upregulation of 84 genes and downregulation of 53 genes by reference to nonexposed plants. Many genes differentially expressed by AgNPs and Ag(+) were found to be involved in the response of plants to various stresses: upregulated genes were primarily associated with the response to metals and oxidative stress (e.g., vacuolar cation/proton exchanger, superoxide dismutase, cytochrome P450-dependent oxidase, and peroxidase), while downregulated genes were more associated with response to pathogens and hormonal stimuli [e.g., auxin-regulated gene involved in organ size (ARGOS), ethylene signaling pathway, and systemic acquired resistance (SAR) against fungi and bacteria]. A significant overlap was observed between genes differentially expressed in response to AgNPs and Ag(+) (13 and 21% of total up- and downregulated genes, respectively), suggesting that AgNP-induced stress originates partly from silver toxicity and partly from nanoparticle-specific effects. Three highly upregulated genes in the presence of AgNPs, but not Ag(+), belong to the thalianol biosynthetic pathway, which is thought to be involved in the plant defense system. Results from this study provide insights into the molecular mechanisms of the response of plants to AgNPs and Ag(+).