The negative influence of agrochemicals (pesticides: insecticide, fungicide, and herbicide) on biodiversity is a major ecological concern. In recent decades, many insect species are reported to have rapidly declined worldwide, and pesticides, including neonicotinoids and fipronil, are suspected to be partially responsible. In Japan, application of systemic insecticides to nursery boxes in rice paddies is considered to have caused rapid declines in Sympetrum (Odonata: Libellulidae) and other dragonfly and damselfly populations since the 1990s. In addition to the direct lethal effects of pesticides, agrochemicals indirectly affect Odonata populations through reductions in macrophytes, which provide a habitat, and prey organisms. Due to technical restrictions, most previous studies first selected target chemicals and then analyzed their influence on focal organisms at various levels, from the laboratory to the field. However, in natural and agricultural environments, various chemicals co-occur and can act synergistically. Under such circumstances, targeted analyses might lead to spurious correlations between a target chemical and the abundance of organisms. To address such problems, in this study we adopted a novel technique, “Comprehensive Target Analysis with an Automated Identification and Quantification System (CTA-AIQS)” to detect wide range of agrochemicals in water environment. The relationships between a wide range of pesticides and lentic Odonata communities were surveyed in agricultural and non-agricultural areas in Saga Plain, Kyushu, Japan. We detected significant negative relationships between several insecticides, i.e., acephate, clothianidin, dinotefuran, flubendiamide, pymetrozine, and thiametoxam (marginal for benthic odonates) and the abundance of lentic Epiprocta and benthic Odonates. In contrast, the herbicides we detected were not significantly related to the abundance of aquatic macrophytes, suggesting a lower impact of herbicides on aquatic vegetation at the field level. These results highlight the need for further assessments of the influence of non-neonicotinoid insecticides on aquatic organisms.

The widespread use of nano-enabled agrochemicals in agriculture for remediating soil and improving nutrient use efficiency of organic and chemical fertilizers is increasing continuously with limited understanding on their potential risks. Recent studies suggested that nanoparticles (NPs) are harmful to soil organisms and their stimulated nutrient cycling in agriculture. However, their toxic effects under natural input farming systems are just at its infancy. Here, we aimed to examine the harmful effects of nano-agrochemical zinc oxide (ZnONPs) to poultry (PM) and farmyard manure (FYM) C and N cycling in soil-plant systems. These manures enhanced microbial counts, CO₂ emission, N mineralization, spinach yield and N recovery than control (unfertilized). Soil applied ZnONPs increased labile Zn in microbial biomass, conferring its consumption and thereby reduced the colony-forming bacterial and fungal units. Such effects resulted in decreasing CO₂ emitted from PM and FYM by 39 and 43%, respectively. Further, mineralization of organic N was reduced from FYM by 32%, and PM by 26%. This process has considerably decreased the soil mineral N content from both manure types and thereby spinach yield and plant N recoveries. In the ZnONPs amended soil, only about 23% of the applied total N from FYM and 31% from PM was ended up in plants, whereas the respective fractions in the absence of ZnONPs were 33 and 53%. Hence, toxicity of ZnONPs should be taken into account when recommending its use in agriculture for enhancing nutrient utilization efficiency of fertilizers or soil remediation purposes.

Strobilurins are popular fungicides used in agriculture on a global scale. Due to their widespread use as agrochemicals, they can enter aquatic environments at concentrations that can elicit adverse effects in organisms. This review synthesizes the current state of knowledge regarding the toxic effects of strobilurin fungicides on aquatic species, including algal species, Daphnia magna, and fish species, to determine risk to aquatic organisms and ecosystems. Data show that the toxicities of strobilurins vary widely across aquatic species. Strobilurins bind cytochrome bc1 in mitochondrial complex III in fungi, and as such, research in aquatic species has focused on mitochondria-related endpoints following exposures to strobilurins. In fish, studies into the activities of mitochondrial complexes and the expression of genes involved in the electron transfer chain have been conducted, converging on the theme that mitochondrial complexes and their enzymes are impaired by strobilurins. In general, the order of toxicity of strobilurins for fish species are pyraoxystrobin > pyraclostrobin ≈ trifloxystrobin > picoxystrobin > kresoxim-methyl > fluoxastrobin > azoxystrobin. In addition to mitochondrial toxicity, studies also report genotoxicity, immunotoxicity, cardiotoxicity, neurotoxicity, and endocrine disruption, and each of these events can potentially impact whole organism-level processes such as development, reproduction, and behavior. Screening data from the US Environmental Protection Agency ToxCast database supports the hypothesis that these fungicides may act as endocrine disruptors, and high throughput data suggest estrogen receptor alpha and thyroid hormone receptor beta can be activated by some strobilurins. It is recommended that studies investigate the potential for endocrine disruption by strobilurins more thoroughly in aquatic species. Based on molecular, physiological, and developmental outcomes, a proposed adverse outcome pathway is presented with complex III inhibition in the electron transfer chain as a molecular initiating event. This review comprehensively addresses sub-lethal toxicity mechanisms of strobilurin fungicides, important as the detection of strobilurins in aquatic environments suggests exposure risks in wildlife.

South Africa is the largest agrochemical user in sub-Saharan Africa, with over 3000 registered pesticide products. Although they reduce crop losses, these chemicals reach non-target aquatic environments via leaching, spray drift or run-off. In this review, attention is paid to legacy and current-use pesticides reported in literature for the freshwater environment of South Africa and to the extent these are linked to endocrine disruption. Although banned, residues of many legacy organochlorine pesticides (endosulfan and dichlorodiphenyltrichloroethane (DDT)) are still detected in South African watercourses and wildlife. Several current-use pesticides (triazine herbicides, glyphosate-based herbicides, 2,4-dichlorophenoxyacetic acid (2,4-D) and chlorpyrifos) have also been reported. Agrochemicals can interfere with normal hormone function of non-target organism leading to various endocrine disrupting (ED) effects: intersex, reduced spermatogenesis, asymmetric urogenital papillae, testicular lesions and infertile eggs. Although studies investigating the occurrence of agrochemicals and/or ED effects in freshwater aquatic environments in South Africa have increased, few studies determined both the levels of agricultural pesticides present and associated ED effects. The majority of studies conducted are either laboratory-based employing in vitro or in vivo bioassays to determine ED effects of agrochemicals or studies that investigate environmental concentrations of pesticides. However, a combined approach of bioassays and chemical screening will provide a more comprehensive overview of agrochemical pollution of water systems in South Africa and the risks associated with long-term chronic exposure.

Growing applications of nanoagrichemicals have resulted in their increasing accumulation in agricultural soils, which could modify soil properties and affect soil health. A greenhouse pot trial was conducted to determine the effects of three metallic nanoagrichemicals on several fundamental chemical properties of a rice paddy soil, including zinc oxide nanoparticles (ZnO NPs) and copper oxide nanoparticles (CuO NPs) at 100 mg/kg, and silicon oxide nanoparticles (SiO₂ NPs) at 500 mg/kg, as well as their bulk and ionic counterparts. The investigated soil amendments displayed significant and distinctive impact on the examined soil chemical properties relevant to agricultural production, including soil pH, redox potential, soil organic carbon (SOC), cation exchange capacity (CEC), and plant available As. For example, all amendments increased the bulk soil pH at day 47 to some extent, but the increase was substantially higher for SiO₃²⁻ (37.7%) than other amendments (5.8%–13.7%). Soil Eh was elevated markedly at day 47 after the addition of soil amendments in both the bulk soil (45.9%–74.4%) and rice rhizosphere soil (20.3%–68.9%). CuO NPs and Cu²⁺ generally exhibited greater impact on soil chemical properties than other agrichemicals. Significantly different responses to soil amendments were observed between bulk and rhizosphere soils, suggesting the essential role of plants in affecting soil properties and their responses to environmental disturbance. Overall, our results confirmed that the tested amendments could have remarkable impacts on the fundamental chemical properties of rice paddy soils.

Aquatic pollution from emerging organic contaminants (EOCs) is of key environmental importance in India and globally, particularly due to concerns of antimicrobial resistance, ecotoxicity and drinking water supply vulnerability. Here, using a broad screening approach, we characterize the composition and distribution of EOCs in groundwater in the Gangetic Plain around Patna (Bihar), as an exemplar of a rapidly developing urban area in northern India. A total of 73 EOCs were detected in 51 samples, typically at ng.L⁻¹ to low μg.L⁻¹ concentrations, relating to medical and veterinary, agrochemical, industrial and lifestyle usage. Concentrations were often dominated by the lifestyle chemical and artificial sweetener sucralose. Seventeen identified EOCs are flagged as priority compounds by the European Commission, World Health Organisation and/or World Organisation for Animal Health: namely, herbicides diuron and atrazine; insecticides imidacloprid, thiamethoxam, clothianidin and acetamiprid; the surfactant perfluorooctane sulfonate (and related perfluorobutane sulfonate, perfluorohexane sulfonate, perfluorooctanoic acid and perfluoropentane sulfonate); and medical/veterinary compounds sulfamethoxazole, sulfanilamide, dapson, sulfathiazole, sulfamethazine and diclofenac. The spatial distribution of EOCs varies widely, with concentrations declining with depth, consistent with a strong dominant vertical flow control. Groundwater EOC concentrations in Patna were found to peak within ∼10 km distance from the River Ganges, indicating mainly urban inputs with some local pollution hotspots. A heterogeneous relationship between EOCs and population density likely reflects confounding factors including varying input types and controls (e.g. spatial, temporal), wastewater treatment infrastructure and groundwater abstraction. Strong seasonal agreement in EOC concentrations was observed. Co-existence of limited transformation products with associated parent compounds indicate active microbial degradation processes. This study characterizes key controls on the distribution of groundwater EOCs across the urban to rural transition near Patna, as a rapidly developing Indian city, and contributes to the wider understanding of the vulnerability of shallow groundwater to surface-derived contamination in similar environments.

As agriculture expands to provide food and wellbeing to the world’s growing population, there is a simultaneous increasing concern about the use of agrochemicals, which can harm non-target organisms, mainly in the aquatic environment. The fungicide Mancozeb (MZ) has been used on a large-scale and is a potent inducer of oxidative stress. Therefore, there is an urgent need for the development of more sensitive biomarkers designed to earlier biomonitoring of this compound. Here we tested the hypothesis that behavioral changes induced by sublethal MZ concentrations would occur first as compared to biochemical oxidative stress markers. Embryos at 4 h post-fertilization (hpf) were exposed to Mancozeb at 5, 10 and 20 μg/L. Controls were kept in embryo water only. Behavioral and biochemical parameters were evaluated at 24, 28, 72, and 168 hpf after MZ exposure. The results showed that MZ significantly altered spontaneous movement, escape responses, swimming capacity, and exploratory behavior at all exposure times. However, changes in ROS steady-stead levels and the activity of antioxidant enzymes were observable only at 72 and 168 hpf. In conclusion, behavioral changes occurred earlier than biochemical alterations in zebrafish embryos exposed to MZ, highlighting the potential of behavioral biomarkers as sensitive tools for biomonitoring programs.

The transport of trace metals in river–lake systems can potentially increase or decrease primary productivity in some basins and subsequently affect the carbon cycle of watersheds. In this study, we investigated a variety of trace metal concentrations and transport flux in the Poyang Lake basin during four seasons. Results show that the Gan River transports 78% of selenium (Se) and 42% of lead (Pb) into Poyang Lake each year, resulting in heavy metal pollution dominated by Pb and Se in 30%–75% of its water. Although toxic heavy metals, such as Pb, chromium (Cr), and copper (Cu), inhibit phytoplankton growth and decrease its gross primary productivity (GPP), excessive Se could effectually promote productivity. However, the negative effect of Pb on GPP is more significant than the positive effect of Se on GPP; hence, their interaction effectuates a decrease in total primary productivity. Additionally, under high nutrients level, the synergistic effect of heavy metals and nutrients will reduce GPP. Agricultural fertilizer is likely the source of both Pb, Cu, Se and N. Gan River contributes 35%–80% of the heavy metal inputs to Poyang Lake. It is therefore necessary to improve the ecological environment of phytoplankton and promote productivity in the Poyang Lake basin by reducing the application of agricultural chemical fertilizers to control pollution. Our results indicate that the role of certain, less studied trace elements (e.g., Pb, Cr, Cu, and Se) in regulating primary productivity of watershed ecosystems is more important than previously thought. This study also discusses potential impacting mechanisms associated with these metals on phytoplankton, whose biological functions need to be verified in future experiments.

The exposure to endocrine-disrupting compounds (EDCs), such as glyphosate-based herbicides (GBHs), during early life might alter female fertility. The aim of the present study was to evaluate the effects of neonatal exposure to a GBH on sheep uterine development. To achieve this, Friesian ewe lambs were exposed to GBH (2 mg/kg of body weight/day; n = 12) or vehicle (controls; n = 10) through s.c. injections, from postnatal day (PND) 1 to PND14; on PND45, the uteri were obtained to evaluate histomorphological and molecular parameters. Morphological parameters were determined by picrosirius-hematoxylin staining. Protein expression of Ki67 (as a cell proliferation marker), p27, and molecules involved in uterine organogenetic differentiation was measured by immunohistochemistry. We also determined the mRNA expression of the IGF molecular pathway by RT-PCR. Although histomorphology was not modified, the uteri of GBH-exposed ewe lambs showed lower cell proliferation, together with higher p27 protein expression. In addition, the uteri of GBH-exposed ewe lambs showed increased gene expression of insulin-like growth factor binding protein 3 (IGFBP-3), decreased expression of ERα in the luminal (LE) and glandular (GE) epithelia and in the subepithelial stroma (SS), and lower PR expression in the LE but higher in the GE and SS. In addition, GBH treatment decreased the uterine expression of Wnt5a in the GE, of Wnt7a in the SS, of β-catenin in the LE and GE, of Hoxa10 in the SS, and of Foxa2 in the GE as compared with controls. In conclusion, neonatal exposure to GBH decreased cell proliferation and altered the expression of molecules that control proliferation and development in the uterus. All these changes might have adverse consequences on uterine differentiation and functionality, affecting the female reproductive health of sheep. GBH may be responsible for uterine subfertility, acting as an EDC.

Despite the efforts of the European Commission to implement measures that offset the detrimental effects of agricultural intensification, farmland bird populations continue to decline. Pesticide use has been pointed out as a major cause of decline, with growing concern about those agro-chemicals that act as endocrine disruptors. We report here on the effects of flutriafol, a ubiquitous systemic fungicide used for cereal seed treatment, on the physiology and reproduction of a declining gamebird. Captive red-legged partridges (Alectoris rufa; n = 11–13 pairs per treatment) were fed wheat treated with 0%, 20% or 100% of the flutriafol application rate during 25 days in late winter. We studied treatment effects on the reproductive performance, carotenoid-based coloration and cellular immune responsiveness of adult partridges, and their relationship with changes in oxidative stress biomarkers and plasma biochemistry. We also studied the effect of parental exposure on egg antioxidant content and on the survival, growth and cellular immune response of offspring. Exposed partridges experienced physiological effects (reduced levels of cholesterol and triglycerides), phenotypical effects (a reduction in the carotenoid-based pigmentation of their eye rings), and most importantly, severe adverse effects on reproduction: a reduced clutch size and fertile egg ratio, and an overall offspring production reduced by more than 50%. No effects on body condition or cellular immune response of either exposed adult or their surviving offspring were observed. These results, together with previous data on field exposure in wild partridges, demonstrate that seed treatment with flutriafol represents a risk for granivorous birds; they also highlight a need to improve the current regulation system used for foreseeing and preventing negative impacts of Plant Protection Products on wildlife.