Alternating water sources to minimize contaminant accumulation in food plants from treated wastewater irrigation.

The use of treated wastewater (TWW) for agricultural irrigation is a critical measure in advancing sustainable water management and agricultural production. However, TWW irrigation in agriculture serves as a conduit to introduce many contaminants of emerging concern (CECs) into the soil-plant-food continuum, posing potential environmental and human health risks. Currently, there are few practical options to mitigate the potential risk while promoting the safe reuse of TWW. In this greenhouse study, the accumulation of 11 commonly occurring CECs was evaluated in three vegetables (radish, lettuce, and tomato) subjected to two different irrigation schemes: whole-season irrigation with CEC-spiked water (FULL), and half-season irrigation with CEC-spiked water, followed by irrigation with clean water for the remaining season (HALF). Significant decreases (57.0-99.8 %, p < 0.05) in the accumulation of meprobamate, carbamazepine, PFBS, PFBA, and PFHxA in edible tissues were found for the HALF treatment with the alternating irrigation scheme. The CEC accumulation reduction was attributed to reduced chemical input, soil degradation, plant metabolism, and plant growth dilution. The structural equation modeling showed that this mitigation strategy was particularly effective for CECs with a high bioaccumulation potential and short half-life in soil, while less effective for those that are more persistent. The study findings demonstrate the effectiveness of this simple and on-farm applicable management strategy that can be used to minimize the potential contamination of food crops from the use of TWW and other marginal water sources in agriculture, while promoting safe reuse and contributing to environmental sustainability.

Methylation and Demethylation of Emerging Contaminants in Plants.

Many contaminants of emerging concern (CECs) have reactive functional groups and may readily undergo biotransformations, such as methylation and demethylation. These transformations have been reported to occur during human metabolism and wastewater treatment, leading to the propagation of CECs. When treated wastewater and biosolids are used in agriculture, CECs and their transformation products (TPs) are introduced into soil-plant systems. However, little is known about whether transformation cycles, such as methylation and demethylation, take place in higher plants and hence affect the fate of CECs in terrestrial ecosystems. In this study, we explored the interconversion between four common CECs (acetaminophen, diazepam, methylparaben, and naproxen) and their methylated or demethylated TPs in Arabidopsis thaliana cells and whole wheat seedlings. The methylation-demethylation cycle occurred in both plant models with demethylation generally taking place at a greater degree than methylation. The transformation rate of demethylation or methylation was dependent on the bond strength of R-CH3, with demethylation of methylparaben or methylation of acetaminophen being more pronounced. Although not explored in this study, these interconversions may exert influences on the behavior and biological activity of CECs, particularly in terrestrial ecosystems. The study findings demonstrated the prevalence of transformation cycles between CECs and their methylated or demethylated TPs in higher plants, contributing to a more complete understanding of risks of CECs in the human-wastewater-soil-plant continuum.

Distribution of pyrethroid insecticides in urban storm drain structures: Catch basins, open channels, and outfalls.

Surface water runoff can transport contaminants offsite to downstream aquatic ecosystems. The prevalence of impervious surfaces in urban areas enhances surface runoff and contributes to contamination of urban surface streams. Urban areas have complex drainage systems for the conveyance of drainage water, however, there is a dearth of information on the distribution of contaminants within storm drain system structures. Pyrethroid insecticides are among the most used insecticides in urban areas, and trace levels of pyrethroids are known to exert toxicity to aquatic invertebrates. To investigate pyrethroid occurrence and distribution throughout an urban drainage system, samples of water, sediment, algae, and biofilm were collected from catch basins, open channels, and outfalls in Los Angeles County, California, during the dry season. From 3 catch basins, 7 open channels, and 7 outfalls, a total of 28 water samples, 4 sediment samples, 8 algae samples, and 4 biofilm samples were collected and analyzed. Pyrethroid concentrations above the reporting limit were detected in 89% of water samples and all sediment, algae, and biofilm samples, with bifenthrin and cyfluthrin being the most frequently detected compounds. The median total pyrethroid concentrations in water, sediments, algae, and biofilms were 27 ng/L, 88 ng/g, 356 ng/g, and 3556 ng/g, respectively. Bifenthrin concentrations in catch basins were found to be significantly higher than those in open channels or outfalls. Significant correlations were found for various metrics, including between pyrethroid partitioning in water samples and total suspended solids. These findings highlight the role of underground catch basins as a sink as well as a secondary source for contaminants such as pyrethroid insecticides. Prevention of the input of these urban originated contaminants to catch basins is crucial for protecting the water quality of urban surface waters.

Methylation and Demethylation of Emerging Contaminants Changed Bioaccumulation and Acute Toxicity in Daphnia magna.

Contaminants of emerging concern (CECs) in the environment undergo various transformations, leading to the formation of transformation products (TPs) with a modified ecological risk potential. Although the environmental significance of TPs is increasingly recognized, there has been relatively little research to understand the influences of such transformations on subsequent ecotoxicological safety. In this study, we used four pairs of CECs and their methylated or demethylated derivatives as examples to characterize changes in bioaccumulation and acute toxicity in Daphnia magna, as a result of methylation or demethylation. The experimental results were further compared to quantitative structure-activity relationship (QSAR) predictions. The methylated counterpart in each pair generally showed greater acute toxicity in D. magna, which was attributed to their increased hydrophobicity. For example, the LC50 values of methylparaben (34.4 ± 4.3 mg L-1) and its demethylated product (225.6 ± 17.3 mg L-1) differed about eightfold in D. magna. The methylated derivative generally exhibited greater bioaccumulation than the demethylated counterpart. For instance, the bioaccumulation of methylated acetaminophen was about 33-fold greater than that of acetaminophen. In silico predictions via QSARs aligned well with the experimental results and suggested an increased persistence of the methylated forms. The study findings underline the consequences of simple changes in chemical structures induced by transformations such as methylation and demethylation and highlight the need to consider TPs to achieve a more holistic understanding of the environmental fate and risks of CECs.

Influence of methylation and demethylation on plant uptake of emerging contaminants.

Contaminants of emerging concern (CECs) as well as their transformation products (TPs) are often found in treated wastewater and biosolids, raising concerns about their environmental risks. Small changes in chemical structure, such as the addition or loss of a methyl group, as the result of methylation or demethylation reaction, may significantly alter a chemical's physicochemical properties. In this study, we evaluated the difference in accumulation and translocation between four CECs and their respective methylated or demethylated derivatives in plant models. Suspended Arabidopsis thaliana cell culture and wheat seedlings were cultivated in nutrient solutions containing individual compounds at 1 mg/L. The methylated counterparts were generally more hydrophobic and showed comparative or greater accumulation in both plant models. For example, after 1 h incubation, methylparaben was found in A. thaliana cells at levels two orders of magnitude greater than demethylated methylparaben. In contrast, the demethylated counterparts, especially those with the addition of a hydroxyl group after demethylation, showed decreased plant uptake and limited translocation. For example, acetaminophen and demethylated naproxen were not detected in the shoots of wheat seedlings after hydroponic exposure. Results from this study suggest that common transformations such as methylation and demethylation may affect the environmental fate of CECs, and should be considered to obtain a more comprehensive understanding of risks of CECs in the environment.

Pyrethroid insecticides in urban catch basins: A potential secondary contamination source for urban aquatic systems.

Pesticide contamination is a threat to many aquatic habitats, and runoff from residential homes is a major contributor of these chemicals in urban surface streams and estuaries. Improved understanding of their fate and transport can help identify areas of concern for monitoring and management. In many urban areas, runoff water congregates in numerous underground catch basins before draining into the open environment; however, at present essentially no information is available on pesticide presence in these systems. In this study, we collected water samples from a large number of underground urban catch basins in different regions of California during the active pest management season to determine the occurrence and profile of the widely used pyrethroid insecticides. Detectable levels of pyrethroids were found in 98% of the samples, and the detection frequency of individual pyrethroids ranged from no detection for fenpropathrin to 97% for bifenthrin. In the aqueous phase, total pyrethroid concentrations ranged from 3 to 726 ng/L, with a median value of 32 ng/L. Pyrethroids were found to be enriched on suspended solids, with total concentrations ranging from 42 to 93,600 ng/g and a median value of 2,350 ng/g. In approximately 89% of the samples, whole water concentrations of bifenthrin were predicted to have toxic units >1 for sensitive aquatic invertebrates. The high detection frequency of bifenthrin and overall pyrethroid concentrations, especially for particle-bound residues, suggest that underground urban catch basins constitute an important secondary source for extended and widespread contamination of downstream surface waters by pesticides such as pyrethroids in urban regions.

Contaminants of emerging concerns in recycled water: Fate and risks in agroecosystems.

Recycled water (RW) has been increasingly recognized as a valuable source of water for alleviating the global water crisis. When RW is used for agricultural irrigation, many contaminants of emerging concern (CECs) are introduced into the agroecosystem. The ubiquity of CECs in field soil, combined with the toxic, carcinogenic, or endocrine-disrupting nature of some CECs, raises significant concerns over their potential risks to the environment and human health. Understanding such risks and delineating the fate processes of CECs in the water-soil-plant continuum contributes to the safe reuse of RW in agriculture. This review summarizes recent findings and provides an overview of CECs in the water-soil-plant continuum, including their occurrence in RW and irrigated soil, fate processes in agricultural soil, offsite transport including runoff and leaching, and plant uptake, metabolism, and accumulation. The potential ecological and human health risks of CECs are also discussed. Studies to date have shown limited accumulation of CECs in irrigated soils and plants, which may be attributed to multiple attenuation processes in the rhizosphere and plant, suggesting minimal health risks from RW-fed food crops. However, our collective understanding of CECs is rather limited and knowledge of their offsite movement and plant accumulation is particularly scarce for field conditions. Given a large number of CECs and their occurrence at trace levels, it is urgent to develop strategies to prioritize CECs so that future research efforts are focused on CECs with elevated risks for offsite contamination or plant accumulation. Irrigating specific crops such as feed crops and fruit trees may be a viable option to further minimize potential plant accumulation under field conditions. To promote the beneficial reuse of RW in agriculture, it is essential to understand the human health and ecological risks imposed by CEC mixtures and metabolites.

When vector control and organic farming intersect: Pesticide residues on rice plants from aerial mosquito sprays.

Conflicts often exist between the use of pesticides for public health protection and organic farming. A prominent example is the use of insecticides for mosquito control in rice fields designated for organic farming. Rice fields, with static water and other conducive conditions, are favorable mosquito habitats. Best management practices are urgently needed to ensure the integrity of organic farming while addressing the need for public health protection. In this study, we evaluated aerial ultra-low-volume (ULV) applications of two classes of mosquito adulticides, pyrethrins and organophosphates, and their deposition and residues on rice plants throughout an active growing season in the Sacramento Valley of California. Frequent applications of pyrethrin synergized with piperonyl butoxide (PBO) and rotating applications of synergized pyrethrins and naled, an organophosphate, were carried out on two large blocks of rice fields. Aerial ULV application of either synergized pyrethrins or naled was able to generate uniform droplets above the fields with high efficacy for mosquito control. Rice leaf samples were collected before and after a subset of applications, and rice grains were sampled at harvest. Frequent applications of synergized pyrethrins resulted in some accumulation of the synergist PBO on rice leaves, but pyrethrins and naled dissipated rapidly from the leaves after each application with no noticeable accumulation over repeated applications. At harvest, no detectable residues of the pesticides or PBO were found in the rice grains. The absence of pesticide residues in the rice grains at harvest suggested that the ULV aerial application led to deposition of only very low levels of residues on rice plants during the growing season. When coupled with the short persistence and/or poor mobility of the insecticides, such applications resulted in negligible pesticide residues in rice grains.

Investigating the toxicities of different functionalized polystyrene nanoplastics on Daphnia magna.

Nanoplastics (NPs) spread widely with water and air current, and they can accumulate in aquatic organisms, even penetrating biofilms, which may cause persistent toxicity and potential hazards. This current study aimed to reveal the toxicological mechanism of different functionalized polystyrene (PS) NPs on Daphnia magna (D. magna) by investigating toxicity endpoints in individual level and biochemical level. In this study, acute toxicity, behavioral parameters and biomarker responses of D. magna was measured in the exposure of different functionalized PS NPs (plain PS, PS-p-NH2, PS-n-NH2 and PS-COOH). The results indicated that when exposed to the plain PS, ROS induction would activate MAPKs, thereby causing lethality and adverse behavior effects on D. magna; while the functionalized PS NPs were less toxic than the plain PS, especially for PS-p-NH2 which was severely flocculated after exposure, thus showing no immobilization at the investigated concentrations. Also, the antioxidant system was mainly stimulated due to the direct interaction with the cell surface receptor, which was different from the plain PS. Consequently, this work suggests significant effects of functional groups on NPs for environmental toxicity studies, and provides a better understanding of the toxicological mechanism on the toxicity of PS NPs toward D. magna.

Quantification of the combined toxic effect of polychlorinated biphenyls and nano-sized polystyrene on Daphnia magna.

It has been reported that nanoplastics (NP) could cause serious toxicity and accumulative effects on aquatic organisms as well as interact with organic pollutants and influence potential hazards when exposed to biota. The current study aimed to quantitatively investigate the combined acute toxic effect of polychlorinated biphenyls (PCBs) and nano-sized polystyrene (PS) plastic on aquatic organisms based on analyte speciation. First, the combined acute toxicity of PCB-18 and 100 nm PS to Daphnia magna (D. magna) in water was evaluated. Then, speciation analysis of the exposure system was conducted by measuring the sorption coefficients (logKNP) of PCBs to nano-sized PS (ranging from 5.28 to 6.56), which demonstrated the PS could substantially decrease the free concentrations of PCBs. The results showed that a low concentration of the PS could decrease the toxicity to D. magna., which might be originated from the decreased free concentration of PCB-18. However, when the PS concentration was high enough, an opposite effect was observed because the PS dominated the lethality instead of PCB-18. The current study is helpful to clarify the PCB occurrence in ecosystems and provide an in-depth understanding of the eco-toxicological effects of nanoscale plastics.

Effect of dissolved organic matter on pre-equilibrium passive sampling: A predictive QSAR modeling study.

Pre-equilibrium passive sampling is a simple and promising technique for studying sampling kinetics, which is crucial to determine the distribution, transfer and fate of hydrophobic organic compounds (HOCs) in environmental water and organisms. Environmental water samples contain complex matrices that complicate the traditional calibration process for obtaining the accurate rate constants. This study proposed a QSAR model to predict the sampling rate constants of HOCs (polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and pesticides) in aqueous systems containing complex matrices. A homemade flow-through system was established to simulate an actual aqueous environment containing dissolved organic matter (DOM) i.e. humic acid (HA) and (2-Hydroxypropyl)-ß-cyclodextrin (ß-HPCD)), and to obtain the experimental rate constants. Then, a quantitative structure-activity relationship (QSAR) model using Genetic Algorithm-Multiple Linear Regression (GA-MLR) was found to correlate the experimental rate constants to the system state including physicochemical parameters of the HOCs and DOM which were calculated and selected as descriptors by Density Functional Theory (DFT) and Chem 3D. The experimental results showed that the rate constants significantly increased as the concentration of DOM increased, and the enhancement factors of 70-fold and 34-fold were observed for the HOCs in HA and ß-HPCD, respectively. The established QSAR model was validated as credible (RAdj.2=0.862) and predictable (Q2=0.835) in estimating the rate constants of HOCs for complex aqueous sampling, and a probable mechanism was developed by comparison to the reported theoretical study. MAIN FINDING OF THE WORK: The present study established a QSAR model of passive sampling rate constants and calibrated the effect of DOM on the sampling kinetics.