Degradation of four pesticides in five urban landscape soils: human and environmental health risk assessment.

Pesticides are the most cost-effective means of pest control; however, the serious concern is about the non-target effects due to their extensive and intensive use in both agricultural and non-agricultural settings. The degradation rate constant (k) and half-life (DT50) of four commonly used pesticides, glyphosate, 2,4-D, chlorothalonil and dimethoate were determined in five Australian urban landscape soils, with varying physicochemical characteristics, to assess their environmental and human health risks. The k values (day-1) for the selected pesticides were inversely proportional to those of organic carbon (OC), silt, clay and Fe and Al oxides, and directly proportional to pH and sand content in soils. In contrast, the calculated values of DT50 (days) of all the four pesticides in five soils positively correlated with OC, clay, silt and oxides of Fe and Al, whereas soil pH and sand content exhibited a negative correlation. The calculated values of environmental indices, GUS and LIX, for the selected pesticides indicate their potential portability into water bodies, affecting non-target organisms as well as food safety. The evaluation for human non-cancer risk of these pesticides, based on the calculated values of hazard quotient (HQ) and hazard index (HI), suggested that exposure of adults and children to soils, contaminated with 50% of initially applied concentrations, through ingestion, dermal and inhalation pathways might cause negligible to zero non-carcinogenic risks. The present data might help the stakeholders in applying recommended doses of pesticides in urban landscapes and regulatory bodies concerned in monitoring the overall environmental quality and implementing safeguard policies. Our study also clearly demonstrates the need for developing improved formulations and spraying technologies for pesticides to minimize human and environmental health risks.

Toxicity assessment of historical aqueous film-forming foams (AFFFs) using cell-based assays.

Aqueous film-forming foam (AFFF) has historically contained high concentrations of long-chain per-and polyfluoroalkyl substances (PFAS), which have been linked with adverse health outcomes. However, the toxicity of historical AFFFs remains largely unknown, presenting uncertainties in their risk assessment. This study assessed the toxicity of historical AFFFs by exposing human liver cells (HepG2) to various dilutions of 3M Light Water AFFF or Ansulite AFFF (0.001%, 0.002%, 0.005%, 0.009%, 0.019%, 0.038%, 0.075%, 0.15%, and 0.3%) for 24 h. The effects of the two AFFF formulations on the cell viability, intracellular reactive oxygen species (ROS) production, Nrf2-ARE activity, and DNA damage were assessed by CellTiter 96® Aqueous One Solution Cell Proliferation Assay (MTS kit), dichlorofluorescein diacetate assay, luciferase assay, and alkaline Comet assay, respectively. The results revealed that the two brands of AFFFs tested were toxic to HepG2 cells at dilutions lower than the recommended 3% application formulation. Specifically, exposure to 3M Light Water AFFF or Ansulite AFFF induced a dilution-dependent decrease in cell viability, increased intracellular ROS production, and increased Nrf2-ARE activity. However, except for the highest concentration (lowest dilution) of 3M Light Water AFFF tested (0.038%.), both 3M Light Water AFFF and Ansulite AFFF did not significantly induce cellular DNA damage. Overall, 3M Light Water AFFF was more toxic than Ansulite AFFF. The findings from this study provided valuable in vitro toxicity data that may better inform the health risk assessment of these historical AFFFs.

Behavior and fate of fungicide chlorothalonil in urban landscape soils and associated environmental concern.

This novel study investigated the behavior and fate of chlorothalonil in terms of kinetics, sorption‒desorption and leaching potential in urban landscape soils using batch experiments. The pseudo-second-order model well described the sorption kinetics of chlorothalonil in urban soils. Consequently, chlorothalonil was partitioned into heterogeneous surfaces of soil following the Freundlich isotherm model. According to PCA, soil organic matter (OM), silt, clay, and oxides of Al and Fe exhibited a significant positive correlation (P < 0.05) with chlorothalonil Kd (P < 0.05), while sand content and soil pH showed a negative correlation at P < 0.05. In soils, decreased sorption of chlorothalonil was also due to the presence of undecomposed or partly decomposed OM, whereas increased sorption could be attributed to the combined effect of OM with C = O and C-H groups, silt, clay, Al and Fe oxides and hydrophobicity of the fungicide. Also, HI, GUS, LIX and Kd of four among nine urban soils indicated that chlorothalonil has a great potential for leaching into the groundwater from the soil surface, posing an unintended threat to non-target biota and food safety. Therefore, utmost care must be taken while applying chlorothalonil in urban landscapes, particularly on impervious surfaces, to minimize the impact on the ecosystem.

Glyphosate use in urban landscape soils: Fate, distribution, and potential human and environmental health risks.

This novel study investigated the fate and distribution in soils, and potential exposure risk of glyphosate, an extensively used herbicide in urban landscapes. The rate-determining step of glyphosate sorption in urban soils involved chemisorption processes through exchange or sharing of electrons that followed the pseudo-second-order kinetics model. As evidenced by the Freundlich isotherm model, glyphosate gets partitioned into heterogeneous surfaces of soil organic matter (OM) and clay minerals, and then diffused into soil micropores. The principal component analysis revealed that soil OM (R2 = 0.873), oxides of Al (R2 = 0.361) and Fe (R2 = 0.126), and contents of clay (R2 = 0.061) and silt (R2 = 0.432) were positively correlated with the distribution coefficient (Kd) of glyphosate, while alkaline pH (R2 = -0.389) and sand content (R2 = -0.343) negatively correlated with the Kd values. Well-decomposed soil OM, consisting of C-H and CO functional groups, enhanced glyphosate sorption, whereas partially decomposed/undecomposed OM facilitated desorption process. Desorption of glyphosate was favoured in seven of nine selected soils due to adverse hysteresis effects (HI = 0.74-1.0). The higher values of leachability index (0.31-1.0) and groundwater ubiquity score (1.60-3.44) calculated for the urban soils indicated the great leaching potential of glyphosate from soil surface to waterbodies. Use of glyphosate on impermeable surfaces might directly contaminate water sources and affect potability of water, non-target biota, and food safety. The calculated values of cancer risk (10-8‒10-12) and hazard quotient (1.47 × 10-6‒4.12 × 10-6) suggested that the human exposure to glyphosate-contaminated soils through dermal, ingestion and inhalation pathways might cause negligible or no carcinogenic and non-carcinogenic risks to humans. Therefore, glyphosate should be applied judiciously at recommended concentrations in the urban landscapes, mainly on impervious surfaces, to minimize its health impacts in humans and environment.

Sorption-desorption of dimethoate in urban soils and potential environmental impacts.

The environmental fate and impact of dimethoate application in the urban environment were assessed in nine selected soils. The pseudo-second-order kinetics model described the kinetics of dimethoate sorption very well in the urban soils exhibiting two distinct phases, an initial partitioning into clay surfaces and soil organic matter, and eventual diffusion into soil micropores. Dimethoate sorption in the urban soils followed the Freundlich model with an R2 value of 0.94-0.99, suggesting a multi-layered sorption on the heterogeneous surfaces. Sorption of dimethoate in the soils was influenced by clay, silt, organic matter, carboxyl and alkyl groups, and Al and Fe oxides. The undecomposed or incompletely decomposed organic matter present in the soils greatly reduced the sorption and enhanced desorption. The calculated lower values for Freundlich constant (KF) indicate the high mobility of dimethoate in the selected soils. Also, the values of groundwater ubiquity score (GUS), leachability index (LIX), hysteresis index (HI), and coefficient of distribution (Kd) for dimethoate in the soils clearly suggest that the insecticide is prone to leaching out significantly from the soil surface to groundwater. Moreover, the surface runoff from impervious places in the urban environment can be considered as a direct source of groundwater contamination, thereby affecting the quality of potable water besides posing a threat to non-target organisms of ecological importance and food safety. Thus, the present novel study suggests that the application of dimethoate in the urban environment having impervious surfaces must be judicious in order to minimize the potential human and ecological health risks.

Movement and Fate of 2,4-D in Urban Soils: A Potential Environmental Health Concern.

The fate and movement of 2,4-dichlorophenoxyacetic acid (2,4-D), in terms of sorption-desorption and leaching potential, were evaluated in urban soils following the batch experimental method. The sorption kinetics of 2,4-D in soils followed both "fast" and "slow" sorption processes that could be well described by a pseudo-second-order kinetics model, suggesting that 2,4-D was partitioned into soil organic matter and clay surfaces, and eventually diffused into soil micropores. The sorption isotherms were linear, following both Langmuir and Freundlich models. Partially decomposed or undecomposed organic matter present in urban soils decreased sorption and increased desorption of 2,4-D. Also, sorption of 2,4-D increased with an increase in the contents of clay and Al and Fe oxides, whereas sand and alkaline pH increased the desorption process. The lower calculated K d values suggest that 2,4-D is highly mobile in urban soils than in agricultural soils. The calculated values of groundwater ubiquity score, leachability index, and hysteresis index indicated that the herbicide is highly prone to leach out from surface soil to groundwater which might affect the quality of potable water. The present study clearly suggests that 2,4-D must be judiciously applied in the urban areas in order to minimize the potential health and environmental risks.

Controversies over human health and ecological impacts of glyphosate: Is it to be banned in modern agriculture?

Glyphosate, introduced by Monsanto Company under the commercial name Roundup in 1974, became the extensively used herbicide worldwide in the last few decades. Glyphosate has excellent properties of fast sorption in soil, biodegradation and less toxicity to nontarget organisms. However, glyphosate has been reported to increase the risk of cancer, endocrine-disruption, celiac disease, autism, effect on erythrocytes, leaky-gut syndrome, etc. The reclassification of glyphosate in 2015 as 'probably carcinogenic' under Group 2A by the International Agency for Research on Cancer has been broadly circulated by anti-chemical and environmental advocacy groups claiming for restricted use or ban of glyphosate. In contrast, some comprehensive epidemiological studies involving farmers with long-time exposure to glyphosate in USA and elsewhere coupled with available toxicological data showed no correlation with any kind of carcinogenic or genotoxic threat to humans. Moreover, several investigations confirmed that the surfactant, polyethoxylated tallow amine (POEA), contained in the formulations of glyphosate like Roundup, is responsible for the established adverse impacts on human and ecological health. Subsequent to the evolution of genetically modified glyphosate-resistant crops and the extensive use of glyphosate over the last 45 years, about 38 weed species developed resistance to this herbicide. Consequently, its use in the recent years has been either restricted or banned in 20 countries. This critical review on glyphosate provides an overview of its behaviour, fate, detrimental impacts on ecological and human health, and the development of resistance in weeds and pathogens. Thus, the ultimate objective is to help the authorities and agencies concerned in resolving the existing controversies and in providing the necessary regulations for safer use of the herbicide. In our opinion, glyphosate can be judiciously used in agriculture with the inclusion of safer surfactants in commercial formulations sine POEA, which is toxic by itself is likely to increase the toxicity of glyphosate.

Pesticides in the urban environment: A potential threat that knocks at the door.

Pesticides play a pivotal role in controlling pests and disease infestations not only in urban agriculture but also in non-agricultural settings. Several pesticides like herbicides, insecticides, fungicides, rodenticides, etc. are applied unintentionally at higher concentrations even in small urban areas such as lawns, gardens and impermeable surfaces. Consequent to their indiscriminate use, both extensively and intensively, in the urban areas, contamination of pesticides poses a serious threat to the environment, living organisms and food safety. Although the fate and ecological effects of pesticides and their residues have been thoroughly understood in agricultural soils, information available in the literature on the impact of these contaminants in the urban environment is very limited and fragmentary. In fact, the fate and behaviour of pesticide residues in the urban environment are distinct from those in other ecosystems since the soils in urban areas greatly vary in their physico-chemical properties. Development of sustainable and eco-friendly approaches for remediation of even urban soils contaminated with pesticides is therefore greatly warranted. Thus, the present critical review is the first single source that provides updated knowledge on the sources, nature and extent of pesticide pollution in the urban environment, and the ecological and human health effects of pesticides and their residues. The potential of nano-encapsulation of pesticides for their application in urban settings has also been discussed.