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Diuron, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, is a worldwide used herbicide whose biotransformation gives rise to the metabolites, 3-(3,4-dichlorophenyl)-1-methylurea (DCPMU) and 3,4-dichloroaniline (DCA). Previous studies indicate that diuron and/or its metabolites are toxic to the bladder urothelium of the Wistar rats where, under certain conditions of exposure, they may induce successively urothelial cell degeneration, necrosis, hyperplasia and eventually tumors. The hypothesis was raised that the molecular initiating event (MIE) of this Adverse Outcome Pathway is the mitochondrial toxicity of those compounds. Therefore, this study aimed to investigate in vitro the metabolic alterations resulting from urothelial mitochondria isolated from male Wistar rats exposure to diuron, DCPMU and DCA at 10 and 100 µM. A non-targeted metabolomic analysis using mass spectrometry showed discriminative clustering among groups and alterations in the intensity abundance of membrane-associated molecules phosphatidylcholine, phosphatidylinositol and phosphatidylserine, in addition to methylhexanoyl-CoA and, particularly for diuron 100 µM, dehydro-L-gulonate, all of them involved in critical mitochondrial metabolism. Collectively, these data indicate the mitochondrial dysfunction as an MIE that triggers cellular damage and death observed in previous studies. [ABSTRACT FROM AUTHOR]

Cadmium (Cd) is one of the most toxic heavy metals for plants and humans. Reactive oxygen species (ROS) are some of the primary signaling molecules produced after Cd treatment in plants but the contribution of different organelles and specific cell types, together with the impact of light is unknown. We used Arabidopsis lines expressing GRX1-roGFP2 (glutaredoxin1-roGFP) targeted to different cell compartments and analysed changes in redox state over 24 h light/dark cycle in Cd-treated leaf discs. We imaged redox state changes in peroxisomes and chloroplasts in leaf tissue. Chloroplasts and peroxisomes were the most affected organelles in the dark and blocking the photosynthetic electron transport chain (pETC) by DCMU (3-(3,4-dichlorophenyl)-1,1-dimethylurea) promotes higher Cd-dependent oxidation in all organelles. Peroxisomes underwent the most rapid changes in redox state in response to Cd and DCMU and silencing chloroplastic NTRC (NADPH thioredoxin reductase C) considerably increases peroxisome oxidation. Total NAD(P)H and cytosolic NADH decreased during exposure to Cd, while Ca +2 content in chloroplasts and cytosol increased in the dark period. Our results demonstrate a Cd-, time- and light-dependent increase of oxidation of all organelles analysed, that could be in part triggered by disturbances in pETC and photorespiration, the decrease of NAD(P)H availability, and differential antioxidants expression at subcellular level., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Luisa M. Sandalio reports financial support was provided by Spanish Scientific Research Council. Maria C. Romero-Puertas reports financial support was provided by Ministry of Science, and Innovation and Universities. Luisa M. Sandalio reports financial support was provided by Junta de Andalucía Consejería de Educación. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Microalgal growth-based tests are international standards for ecotoxicity assessment; however, their long exposure times, large sample volumes, and reliance on a single growth-endpoint make them inadequate for rapid toxicity screening. Here, we aimed to develop a rapid and simple ecotoxicological test using the fast-growing green alga Mychonastes afer, with multiple endpoints-growth, lipid content, and photosynthesis. We exposed M. afer to two metals-silver and copper-and two herbicides-atrazine and diuron-for 24 h and identified the most sensitive and reliable endpoints for each toxicant: the maximum electron transport rate (ETR max ) for Ag, Cu and atrazine, and the lipid content for diuron. Lipid content was found to be both a sensitive and reliable biomarker, meeting the effluent limit guidelines in both the Republic of Korea and the USA. The sensitivity of M. afer to Ag and atrazine also closely matched the HC 5 values derived from the species sensitivity distribution approach, confirming its reliability for setting regulatory concentrations of these contaminants. Our calculated predicted no-effect concentration (PNEC) values were similar to established European Union PNECs for Ag, Cu, atrazine, and diuron, underlining the utility of these biological endpoints for ecological risk assessment and regulatory decision making. This method required lower sample volume (2 mL vs 100 mL) and exposure time (24 h vs 72-120 h) than conventional green algal tests, and eliminated the need for labour-intensive cell counting, expensive equipment, and chlorophyll fluorescence measurement expertise. Overall, this M. afer test can be a valuable tool for the rapid screening of wastewater for metals and herbicides, contributing to environmental protection and management practices., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

Diuron (N-(3,4-dichlorophenyl)-N,N‑dimethylurea, DCMU), a ureic herbicide, is extensively used in agriculture to boost crop productivity; however, its extensive application culminates in notable environmental pollution, especially in aquatic habitats. Therefore, the present study investigated the effect of diuron on the dinoflagellate Alexandrium pacificum, which is known to induce harmful algal blooms (HAB), and its potential to biodegrade DCMU. Following a four-day DCMU exposure, our results revealed that A. pacificum proficiently assimilated DCMU at concentrations of 0.05 mg/L and 0.1 mg/L in seawater, attaining a complete reduction (100 % efficiency) after 96 h for both concentrations. Moreover, evaluations of paralytic shellfish toxins content indicated that cells subjected to higher DCMU concentrations (0.1 mg/L) exhibited reductions of 73.4 %, 86.7 %, and 75 % in GTX1, GTX4, and NEO, respectively. Exposure to DCMU led to a notable decrease in A. pacificum's photosynthetic efficacy, accompanied by increased levels of reactive oxygen species (ROS) and suppressed cell growth, with a growth inhibition rate of 41.1 % at 72 h. Proteomic investigations pinpointed the diminished expression levels of specific proteins like SxtV and SxtW, linked to paralytic shellfish toxins (PSTs) synthesis, as well as key proteins associated with Photosystem II, namely PsbA, PsbD, PsbO, and PsbU. Conversely, proteins central to the cysteine biosynthesis pathways exhibited enhanced expression. In summary, our results preliminarily resolved the molecular mechanisms underlying the response of A. pacificum to DCMU and revealed that DCMU affected the synthesis of PSTs. Meanwhile, our data suggested that A. pacificum has great potential in scavenging DCMU., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Diuron is a globally used herbicide for weed control but has anti-androgenic effects on androgens (testosterone and androstenedione), antagonist effects on thyroid hormone signaling, and haematological effects due to their biotransformation in fish. Endocrine-disrupting biomarkers such as thyroid hormones, sex hormones, and haematological indices of Clarias gariepinus sub-adults exposed to sub-lethal diuron concentrations were studied over a 28-day period. C. gariepinus (n = 200) sub-adults were exposed to sub-lethal concentrations (0.00, 0.09, 0.18, 0.26, and 0.35 mg/L) of diuron. Changes in the hormonal and haematological profiles of the exposed fish were concentration and exposure duration-dependent. The thyroxine (T4), tri-iodothyronine (T3), and 17β-estradiol (E2) profiles decreased with an increase in concentration and exposure duration. The haemoglobin, pack cell volume, red blood cell, white blood cell, mean cell volume, and mean corpuscular haemoglobin cell decreased, while the mean corpuscular haemoglobin increased with an increase in concentration and exposure duration. Diuron induced stress and altered the physiological mechanisms of fish, and its application in farmlands should be regulated so as to enable a sustainable aquatic eco-system and fishery resources., Competing Interests: Declaration of competing interest The authors declare that they have no competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

The rise in the utilization of pesticides within industrial and agricultural practices has been linked to the occurrence of these substances in aquatic environments. The objective of this work was to evaluate the uptake and adverse impacts of Diuron (Di) and Triclosan (TCS) on the mussel species Mytilus galloprovincialis. To accomplish this, the accumulation and toxicity of these pesticides were gauged following a brief period of exposure spanning 14 days, during which the mussels were subjected to two concentrations (50 and 100 μg/L) of each substance that are ecologically relevant. Chemical analysis of Di and TCS within gills and digestive gland showed that these pesticides could be accumulated in mussel's tissues. In addition, Di and TCS are preferably accumulated in digestive gland. Measured biomarkers included physiological parameters (filtration FC and respiration RC capacity), antioxidant enzyme activities (superoxide dismutase and catalase), oxidative damage indicator (Malondialdheyde concentration) and neurotoxicity level (acetylcholinesterase activity) were evaluated in gills and digestive glands. Both pesticides were capable of altering the physiology of this species by reducing the FC and RC in concentration and chemical dependent manner. Both pesticides induced also an oxidative imbalance causing oxidative stress. The high considered concentration exceeded the antioxidant defense capacity of the mussel and lead to membrane lipid peroxidation that resulted in cell damage. Finally, the two pesticides tested were capable of interacting with the neuromuscular barrier leading to neurotoxicity in mussel's tissues by inhibiting acetylcholinesterase. The ecotoxicological effect depended on the concentration and the chemical nature of the contaminant. Obtained results revealed also that the Di may exert toxic effects on M. galloprovincialis even at relatively low concentrations compared to TCS. In conclusion, this study presents innovative insights into the possible risks posed by Diuron (Di) and Triclosan (TCS) to the marine ecosystem. Moreover, it contributes essential data to the toxicological database necessary for developing proactive environmental protection measures., Competing Interests: Declaration of Competing Interest The authors declare no competing interests., (Copyright © 2023. Published by Elsevier Inc.)

In the environment, or during mammalian metabolism, the diuron herbicide (3-(3,4-dichlorophenyl)-1,1-dimethylurea) is transformed mainly into 3-(3,4-dichlorophenyl)-1-methylurea (DCPMU) and 3,4-dichloroaniline (DCA). Previous research suggests that such substances are toxic to the urothelium of Wistar rats where, under specific exposure conditions, they may induce urothelial cell degeneration, necrosis, hyperplasia, and eventually tumors. However, the intimate mechanisms of action associated with such chemical toxicity are not fully understood. In this context, the purpose of the current in vitro study was to analyze the underlying mechanisms involved in the urothelial toxicity of those chemicals, addressing cell death and the possible role of mitochondrial dysfunction. Thus, human 1T1 urothelial cells were exposed to six different concentrations of diuron, DCA, and DCPMU, ranging from 0.5 to 500 µM. The results showed that tested chemicals induced oxidative stress and mitochondrial damage, cell cycle instability, and cell death, which were more expressive at the higher concentrations of the metabolites. These data corroborate previous studies from this laboratory and, collectively, suggest mitochondrial dysfunction as an initiating event triggering urothelial cell degeneration and death.

The endophytic bacteria live in close nuptial relationship with the host plant. The stress experienced by the plant is expected to be transferred to the endophytes. Thus, plants thriving at polluted sites are likely to harbor pollutant-degrading endophytes. The present study reports the isolation of phenylurea herbicides assimilating Bacillus sps. from Parthenium weed growing at diuron-contaminated site. The isolated endophytes exhibited plant growth–promoting (PGP) activities. Among five isolated diuron-degrading endophytes, the most efficient isolate Bacillus licheniformis strain SDS12 degraded 85.60 ± 1.36% of 50 ppm diuron to benign form via formation of degradation intermediate 3, 4-dichloroaniline (3,4-DCA). Cell-free supernatant (CFS) obtained after diuron degradation by strain SDS12 supported algal growth comparable with the pond water. The chlorophyll content and photosynthetic efficiency of green algae decreased significantly in the presence of diuron-contaminated water; however, no such change was observed in CFS of strain SDS12, thus, suggesting that strain SDS12 can be applied in aquatic bodies for degrading diuron and reducing diuron toxicity for primary producers. Further, the use of PGP and diuron-degrading bacteria in agriculture fields will not only help in remediating the soil but also support plant growth. [ABSTRACT FROM AUTHOR]

Organotin-based (OTs: TBT and TPT) antifouling paints have been banned worldwide, but recent inputs have been detected in tropical coastal areas. However, there is a lack of studies evaluating the toxicity of both legacy and their substitute antifouling booster biocides (e.g., Irgarol and diuron) on neotropical species. Therefore, the acute toxicity of four antifouling biocides (TBT, TPT, Irgarol, and diuron) was investigated using the marine planktonic organisms Acartia tonsa and Mysidopsis juniae, the estuarine tanaid Monokalliapseudes schubarti (water exposure), and the burrowing amphipod Tiburonella viscana (spiked sediment exposure). Results confirmed the high toxicity of the OTs, especially to planktonic species, being about two orders of magnitude higher than Irgarol and diuron. Toxic effects of antifouling compounds were observed at levels currently found in tropical coastal zones, representing a threat to planktonic and benthic invertebrates. Furthermore, deterministic PNEC marine sediment values suggest that environmental hazards in tropical regions may be higher due to the higher sensitivity of tropical organisms. Since regulations on antifouling biocides are still restricted to a few countries, more ecotoxicological studies are needed to derivate environmental quality standards based on realistic scenarios. The present study brings essential contributions regarding the ecological risks of these substances in tropical and subtropical zones., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Runoff losses of herbicides have rarely been compared simultaneously under the same conditions. Our aim was to directly compare herbicide runoff losses, normalised for the amount present (relative runoff loads) and in absolute terms. Toxicity and runoff concentrations were combined to provide a risk ranking relative to diuron. Four rainfall simulation trials were conducted in sugarcane in the Great Barrier Reef catchment. Herbicides studied were older PSII residuals (atrazine, ametryn, diuron, hexazinone), alternative residuals (isoxaflutole, imazapic, metribuzin, metolachlor, pendimethalin) and knockdown herbicides (glyphosate, 2,4-D, fluroxypyr) and the tracer bromide (Br). Simulations were conducted two days after spraying, before differences due to half-lives were apparent. Two trials had bare soil and two had sugarcane trash. Herbicide runoff losses and concentrations were closely related to the amount applied, runoff amounts and partitioning coefficients. Relative runoff losses and absolute losses were similar for most older and alternative residual herbicides, 2,4-D and Br. Glyphosate and pendimethalin relative runoff losses were low, due to greater sorption. Isoxaflutole, imazapic, and fluroxypyr are applied at much lower rates and runoff losses were low. Herbicides were lost in the dissolved phase, except pendimethalin. There was a large range in toxicity relative to diuron. There is a range of herbicide choices posing less offsite risk than diuron and ametryn, which have high application rates and high toxicity. Herbicide choice should consider application rate, runoff losses, sorption, and toxicity., Competing Interests: Declaration of competing interest This work was supported by Australian and Queensland Governments' Paddock to Reef Integrated Monitoring, Modelling and Reporting Program, Australian Government's Reef Rescue Research and Development Program, Queensland Government's Reef Water Quality R&D Science Program, and Sugar Research Australia Ltd. and USQ (Project NCA011). Sediment partitioning was funded by Reef Rescue R&D Project RRRD038. The author has no competing interests., (Crown Copyright © 2022. Published by Elsevier B.V. All rights reserved.)

This study provides a comprehensive compilation of published toxicological and environmental data further used to assess the ecological risks of six antifouling biocides, including tributyltin (TBT), Irgarol 1051, Diuron, Chlorothalonil, 4,5-Dichloro-N-octyl-3(2H)-isothiazolone (DCOIT), and Dichlofluanid. The standard maximum concentration and standard continuous concentration of antifouling biocides were derived by the species susceptibility distribution method. Following that, the ecological risk assessment of antifouling biocides in the aquatic environment was conducted using the hazard quotient, margin of safety, joint probability curve, and Monte Carlo random sampling method. The following is a concise list of the antifouling biocide dangers associated with acute and chronic risks: Irgarol 1051 > TBT > Diuron > DCOIT > Chlorothalonil > Dichlofluanid. It is strongly advised that systematic and ongoing monitoring of these biocides in coastal areas take place, as well as the creation of acceptable and efficient environmental protection measures, to safeguard the coastal environment's services and functions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

The presence and toxicity of waterborne diuron in aquatic environments pose a severe threat to non-target organisms. However, the chronic impact of diuron in marine fish has been poorly investigated. In this study, we report the chronic effects (30 and 60 days) of environmentally relevant concentrations of diuron (0.1, 1, and 10 μg L -1 ) on economically important marine fish, red seabream (Pagrus major), and black rockfish (Sebastes schlegelii) by evaluating several parameters, including hormone levels, immunity, hepatic function, and antioxidant defense. Significant decreases in 17β-estradiol and 11-ketotestosterone levels and gonadosomatic index were observed on day 60 in fish exposed to 10 μg L -1 diuron. Parameters of immunity, such as alternative complement activity, lysozyme activity, and total immunoglobulin levels, were significantly lowered by 60-day exposure to 10 μg L -1 diuron in both fish. Significant decreases in the hepatic enzyme activities of alanine transaminase and aspartate transaminase were observed with an induction of cortisol on day 60 in fish exposed to 10 μg L- 1 diuron. Intracellular malondialdehyde and glutathione levels were significantly increased by 10 μg L- 1 diuron at day 60 with an increase in the enzymatic activities of catalase and superoxide dismutase. Overall, black rockfish were more sensitive to diuron than red seabream. These results suggest that consistent exposure to environmentally relevant concentrations of diuron is detrimental to the reproduction, immunity, and health of marine fish., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Seaweeds are some of the principal primary producers of marine environments, and they are important ecological elements of coastal ecosystems. The effects of harmful chemicals on seaweeds may adversely affect coastal ecosystems, hence we aimed to develop a new phytotoxicity test using the gametophytes of a common temperate kelp species, Undaria pinnatifida (KU-1630), for the widely used antifouling chemical substances Cybutryne, Diuron, Cu 2+ , and Zn 2+ . Toxicity to gametophytes of U. pinnatifida was assessed by comparing the relative growth rate (RGR) at the logarithmic growth phase. Fragmentation method, initial algal biomass, photon irradiance, and adhesive period were investigated for developing optimal test conditions. Cybutryne exposure tests were performed with seven replicates and control, the RGR ranging from 0.17 to 0.19, while mean 7-day EC 50 and no observed effect concentration (NOEC) were 5.1 μg/L and 1.8 μg/L, respectively. The 7-day EC 50 for other antifoulants was 14 μg/L for Diuron, 17 μg/L for Cu 2+ , and 1500 μg/L for Zn 2+ . This test method demonstrated high sensitivity and reproducibility, and it may be added to the routine methods used for toxicity evaluation of hazardous chemicals., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Microplastics are considered as the emerging pollutants, which not only directly affect aquatic organisms, but also causes combined pollution by adsorbing other pollutants. Diuron, as one of the most widely used herbicides, is frequently monitored in the aquatic environment for its adverse effects on aquatic organisms. However, little is known about the combined toxicity of microplastics and diuron to aquatic organisms, especially diatoms. In this study, freshwater diatom (Cyclotella meneghiniana) and marine diatom (Skeletonema costatum) were selected to study the individual and combined toxicity of microplastics (polystyrene, 0.6- 1.0 μm) and diuron. Experimental concentrations of microplastics and diuron were set at 50 mg/L and 100 μg/L, respectively, which have been shown to significantly inhibit the growth of aquatic organisms. Results suggested that both single microplastics and single diuron significantly inhibited the growth of the two diatoms, while significant SOD and MDA increase were only found in single diuron exposure. For diatoms exposed to individual microplastics, the microplastic particles adsorbed inside Cyclotella sp. and those aggregated around Skeletonema sp. were the major factor inhibiting the growth of diatom, respectively. According to the independent action model, the combined toxicity for both diatoms were all antagonistic. The adsorption behavior of microplastics to diuron alleviated the intracellular damage to diatoms caused by diuron, and the oxidative stress induced by diuron mitigated the physical damage to diatoms caused by microplastics. Collectively, our findings suggest that the co-existence of microplastics and diuron may affect their respective toxicity to diatoms. The mechanism of this "cross-phenomenon" between microplastics and diuron and their combined toxicity to different aquatic organisms need to be further studied., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

The toxicity of diuron herbicide and its metabolites has been extensively investigated; however, their precise toxic mechanisms have yet to be fully appreciated. In this context, we evaluated the toxic mechanism of diuron, 3,4-dichloroaniline (DCA) and 3-(3,4-dichlorophenyl)-1-methylurea (DCPMU), using Caenorhabditis elegans (C. elegans) in the L1 larval stage. For this purpose, worms were acutely exposed to the test chemicals with a preliminary concentration range of 0.5 to 500 μM and first analyzed for lethality (%). Next, the highest concentration (500 μM) was considered for survival (%), reactive oxygen and nitrogen species (RONS), glutathione (GSH) and ATP levels, autophagy index, behavior, and dopaminergic neurodegeneration parameters. Interestingly, increased lethality (%) was found for all chemicals at the higher concentrations tested (100 and 500 μM), with significant differences at 500 μM DCA (p < 0.05). A decrease in the median survival was observed mainly for DCA. Although no changes were observed in RONS production, GSH levels were significantly increased upon diuron and DCA treatment, likely reflecting an attempt to restore the redox status. Moreover, diuron and its metabolites impaired ATP levels, suggesting an alteration in mitochondrial function. The latter may trigger autophagy as an adaptive survival mechanism, but this was not observed in C. elegans. Dopaminergic neurotoxicity was observed upon treatment with all the tested chemicals, but only diuron induced alterations in the worms' locomotor behavior. Combined, these results indicate that exposure to high concentrations of diuron and its metabolites elicit distinct adverse outcomes in C. elegans, and DCA in particular, plays an important role in the overall toxicity observed in this experimental model., (© 2022. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Atrazine and diuron are among the most widely used antifoulant biocides in the world. Due to their persistence in the environment, they can induce adverse effects on non-targeted organisms. In this study, we investigated the chronic in vivo toxicity of atrazine and diuron with further assessments on oxidative stress responses (e.g., oxidative stress, antioxidant) and multixenobiotic resistance (MXR) function in the rotifer Brachionus koreanus, a non-targeted microzooplanktonic grazer at the primary level of the marine food chain. Although similar oxidative response was shown by both biocides, diuron induced stronger retardation on reproduction and population growth rates of B. koreanus while moderate effects were observed by atrazine. This higher toxicity of diuron was shown to be associated with its stronger inhibition of MXR conferred by P-glycoprotein and multidrug resistance proteins which play as a first line of defense by transporting various toxicants out of a cell. Our study provides new insight into non-targeted effects of biocides on marine zooplankton and mechanisms beyond their different degrees of toxicity., (Copyright © 2022. Published by Elsevier Inc.)

Coastal ecosystems such as those in the Great Barrier Reef (GBR) lagoon, are exposed to stressors in flood plumes including low light (caused by increased turbidity) and agricultural pesticides. Photosystem II (PSII)-inhibiting herbicides are the most frequently detected pesticides in the GBR lagoon, but it is not clear how their toxicity to phototrophic species depends on light availability. This study investigated the individual and combined effects of PSII-inhibiting herbicide, diuron, and reduced light intensity (as a proxy for increased turbidity) on the marine diatom, Phaeodactylum tricornutum. Effective quantum yield (EQY) and cell density were measured to calculate responses relative to the controls over 72-h, in tests with varying stressor intensities. Individually, diuron concentrations (0.1-3 μg l -1 ) were not high enough to significantly reduce growth (cell density), but led to decreased EQY; while, low light generally led to increased EQY, but only reduced growth at the lowest tested light intensity (5 μmol photons m -2 s -1 ) after 48-hours. P. tricornutum was less affected by diuron when combined with low light scenarios, with increased EQY (up to 163% of the controls) that was likely due to increased electron transport per photon, despite lesser available photons at this low light intensity. In contrast, growth was completely inhibited relative to the controls when algae were simultaneously exposed to the highest stressor levels (3 μg l -1 diuron and 5 μmol photons m -2 s -1 ). This study highlights the importance of measuring more than one biological response variable to capture the combined effects of multiple stressors. Management of water quality stressors should consider combined impacts rather than just the impacts of individual stressors alone. Reducing suspended sediment and diuron concentrations in marine waters can decrease harmful effects and bring synergistic benefits to water quality., (Copyright © 2022 The Authors. Published by Elsevier Inc. All rights reserved.)

Abstract: A system of recirculating channels was used in this study to examine the long-term effects (29d) of environmentally realistic concentrations of the herbicide diuron (from 0.07 to 7μgL−1) on biofilm communities. The autotrophic activity of biofilms was affected by this herbicide, as reflected by a marked decrease in the photosynthetic efficiency. Diuron exposure also increased chlorophyll-a content and reduced the biovolume of diatom taxa at low concentrations. The effects on bacteria were also remarkable. Bacterial abundance was reduced after a week of exposure to the herbicide at a range of concentrations. Effects were on the number of live bacteria and on the increase in the leucine-aminopeptidase activity. It is suggested that inputs of herbicides to the river ecosystem at low concentrations may cause a chain of effects in the biofilm, which include inhibitory effects on algae but also indirect effects on the relationships between biofilm components. [Copyright &y& Elsevier]

Effect-directed analysis (EDA) aims at identifying the compound(s) responsible for toxicity in a complex environmental sample where several dozens of contaminants can be present. In this study, we used an environmental mixture extracted from the Polar Organic Chemical Integrative Sampler (POCIS) previously immersed downstream a landfill (River Ponteils, South West France), to perform an EDA approach using a microalgal bioassay based on the photosynthetic capacities of diatom (Nitzschia palea) cultures. Adverse effects on photosynthetic capacities were recorded when algae were exposed to the entire POCIS extract (> 85% inhibition at the highest concentration tested). This result was coherent with the detection of diuron and isoproturon, which were the 2 most concentrated herbicides in the extract. However, the EDA process did not allow pointing out the specific compound(s) responsible for the observed toxicity but rather suggested that multiple compounds were involved in the overall toxicity and caused mixture effects., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The widespread agricultural use of the phenylurea herbicide Diuron (DCMU) requires the investigation of ecotoxicological risk in freshwater and soil ecosystems in light of potential effects on non-target primary producers and a heavier effect on higher trophic levels. We used microalgae-based fluorimetric bioassays for studying the interferences on the photosynthesis of a freshwater and soil model green microalga ( Chlamydomonas reinhardtii ) induced by environmentally relevant concentrations of the herbicide DCMU. Measurements of steady-state chlorophyll a (Chl-a) fluorescence emission spectra were performed; as well, the kinetics of the Chl-a fluorescence transient were recorded. Percentage indexes of interference on photosynthesis were calculated after comparison of steady-state and kinetic Chl-a fluorescence measurements of DCMU-exposed and control C. reinhardtii cell suspensions. The results obtained after 30 min exposure to the herbicide DCMU confirmed a significant inhibitory effect of DCMU 2 μg/L, and no significant differences between %ι values for DCMU 0.2 μg/L and 0.02 μg/L exposures. Positive %ε values from kinetic measurements of the Chl-a fluorescence transient confirmed the same interfering effect of 2 μg/L DCMU on PSII photochemistry in the exposed C. reinhardtii cell suspensions. Negative values of %ε observed for 0.2 and 0.02 μg/L DCMU exposures could be attributable to a presumptive 'stimulatory-like' effect in the photochemistry of photosynthesis. Short-term exposure to sub-μg/L DCMU concentration (≤0.2 μg/L) affects the photosynthetic process of the model microalga C. reinhardtii . Similar environmental exposures could affect natural communities of unicellular autotrophs, with hardly predictable cascading secondary effects on higher trophic levels.

Coastal marine systems are the most sensitive zones to emerging pollutants. The present study aims to investigate the effect of Diuron on the meiofaunal assemblages, collected from the Bizerte channel (Tunisia). Microcosm experiments were set up using four increasing Diuron concentrations [D1 (10 ng g -1 dry weight (DW)), D2 (50 ng g -1 DW), D3 (250 ng g -1 DW) and (1250 ng g -1 DW)] compared to non-contaminated sediments (controls) and all plots were incubated for 30 days. Our results show that Diuron-supplemented sediments provoked the significant decrease of meiofaunal abundance as well as a change in nematodes' diversity and structure composition. All univariate indices, as well as the cumulative k-dominance, were lower in the Diuron than the control plot. Additionally, the ordination of treatments according to the two-dimensional nMDS plots analysis showed a clear structural separation of the Diuron treated replicates from the controls based on the functional groups lists. These current data emphasize the utility of the use of biological traits in the detection of disturbances in the aquatic biotope., (Copyright © 2021. Published by Elsevier Ltd.)

This study aimed to identify the toxicity effect of Diuron on Tegillarca granosa by determining accumulation in the soft tissues and alteration on the gill tissue structure. Wild stocks T. granosa were grouped to identify the initial Diuron concentration and 48-h exposure in different concentrations (0, 1, 2, 3, and 4 mg·L -1 ). The Diuron in tissue was extracted using an established procedure and identified using High-Performance Liquid Chromatography (HPLC). Gills were analysed for histopathological study; tissue structure was classified and scored using a developed scoring system. Diuron concentration in the soft tissue of exposed T. granosa was in the range 1.27-8.09 mg·kg -1 , w/w and not proportionately increase along with the exposure concentration. The mean index values of the gill histopathology ranged from 5.25-7.67 and classified as moderate to severe. Gills characteristics and T. granosa protective behaviour potentially limit Diuron accumulation in the soft tissue., (Copyright © 2021. Published by Elsevier Ltd.)

One of the most important anthropogenic impacts on freshwater aquatic ecosystems close to intensive agriculture areas is the cumulative increase in herbicide concentrations. The threat is especially relevant for phytoplankton organisms because they have the same physiological targets as the plants for which herbicides have been designed. This led us to explore the evolutionary response of three phytoplanktonic species to increasing concentrations of two herbicides and its consequences in terms of growth and photosynthesis performance. Specifically, we used an experimental ratchet protocol to investigate the differential evolution and the limit of resistance of a cyanobacterium (Microcystis aeruginosa) and two chlorophyceans (Chlamydomonas reinhardtii and Dictyosphaerium chlorelloides) to two herbicides in worldwide use: glyphosate and diuron. Initially, the growth rate of M. aeruginosa and D. chlorelloides was completely inhibited when they were exposed to a dose of 0.23 ppm diuron or 40 ppm glyphosate, whereas a higher concentration of both herbicides (0.46 ppm diuron or 90 ppm glyphosate) was necessary to abolish C. reinhardtii growth. However, after running a ratchet protocol, the resistance of the three species to both herbicides increased by an adaptation process. M. aeruginosa and D. chlorelloides were able to grow at 1.84 ppm diuron and 80 ppm glyphosate and C. reinhardtii proliferated at twice these concentrations. Herbicide-resistant strains showed lower growth rates than their wild-type counterparts in the absence of herbicides, as well as changes on morphology and differences on photosynthetic pigment content. Besides, herbicide-resistant cells generally showed a lower photosynthetic performance than wild-type strains in the three species. These results indicate that the introduction of both herbicides in freshwater ecosystems could produce a diminution of primary production due to the selection of herbicide-resistant mutants, that would exhibit lower photosynthetic performance than wild-type populations., (Copyright © 2021. Published by Elsevier B.V.)

River biofilm communities are the first ones to be exposed to all toxic discharges received via run off from agricultural fields. Hence, changes in river biofilm community structure and growth pattern are considered as indicator of overall health of lotic ecosystem. Toxicants have effect on biofilm biomass, photosynthetic efficiency and chlorophyll a concentrations. Mathematical models may be applied to estimate the overall vigor of riverine ecosystems considering biofilms as indicators. Herein, previous empirical data of Ricart et al. (2009) on long term effects of environmentally relevant concentrations of diuron on biofilm communities of the River Llobregat, Spain was considered as our model inputs. Our objective is to understand the influence of diuron, chlorophyll a concentrations and photosynthetic efficiency on biovolume using a statistical model. The non-linear relationships between biovolume (dependent variable) and diuron, chlorophyll a concentrations and photosynthetic efficiency (independent variables) were represented by constructing three separate basis functions based on day 8 empirical data. Biovolume, due to nonlinear influence as yielded by the basis functions were used in a multiple linear regression model to estimate the net biovolume. Model validation was done based on day 29 empirical data. The experimentally determined biovolume and our model estimated biovolume showed similar trends. Also, diuron and photosynthetic efficiency had significant (p < 0.05) influence on biovolume. Since, the predominance of diatoms as biofilms within periphytic layers is very common in lotic systems, estimation of changes in diatom biovolume will be significant to assess the effect of herbicides. Diatom biovolume of any day (for example day 22) mentioned in the experimental study may be determined by this model, without the requirement of tedious manual biovolume calculation. Our model will be useful in numerous other studies undertaken on the toxic effect of pollutants on biofilms to quickly and accurately estimate the biofilm biovolume., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The effects of herbicide diuron on photosynthesis and vertical migration of intertidal microphytobenthos (MPB) assemblages were investigated using chlorophyll fluorometry. The results shown diuron ≤ 60 μg L -1 had no obvious effect on MPB vertical migration during 24 h indicated by consistent rhythm. Low concentration of 10 μg L -1 diuron had no significant influence on MPB photosynthesis throughout, however, high concentrations of 40, 50, and 60 μg L -1 had significant impacts exhibited by decreased parameters of maximum relative electron transport rate (rETR max ), maximal PS II quantum yield (F v /F m ) and non-photochemical quenching (NPQ). For middle concentrations of 20 and 30 μg L -1 , above decreased 3 parameters recovered sooner or later after 2 h or 16.5 h. Comparatively, rETR max , F v /F m and NPQ are concentration dependent and more sensitive than other parameters in assessing diuron toxicity. This study revealed the potential of using MPB assemblages and chlorophyll fluorometry for rapid assessing diuron toxicity in coastal sediments., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Although booster biocides (Irgarol, diuron, chlorothalonil, dichlofluanid, and DCOIT) have been detected in sediments along the Brazilian coastal areas, the risk associated to their occurrence and levels is still unknown. Thus, the ecological risk of booster biocides to sediment-dwelling organisms from the Brazilian coast was assessed using a risk characterization approach through the Risk Quotient (Measured environmental concentration (MEC)/Predicted no effect concentrations (PNECs)). Sedimentary PNECs for Irgarol, diuron, chlorothalonil and DCOIT were derived based on published ecotoxicological data from both freshwater and marine studies, while a NORMAN methodology was used to derived it for dichlofluanid. Results showed that DCOIT, diuron, Irgarol, chlorothalonil, and dichlofluanid can pose high risk on 47%, 35%, 15%, 1% and 1%, respectively, of the 113 Brazilian sites appraised. Considering the trend of expansion of navigation/maritime activities, DCOIT may worsen its impact over the coastal areas of Brazil, especially ports, but also ship/boatyards, marinas, and maritime traffic zones. The present study is an important contribution to support advance on policy formulation concerning booster biocides worldwide, particularly considering the lack of regulation on the use of antifouling biocides in Brazil., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The Great Barrier Reef (GBR) is threatened by climate change and local pressures, including contaminants in nearshore habitats. This study investigated the combined effects of a GBR-relevant contaminant, the herbicide diuron, under current and two future climate scenarios on the coral Acropora millepora. All physiological responses tested (effective quantum yield (ΔF/Fm'), photosynthesis, calcification rate) were negatively affected with increasing concentrations of diuron. Interactive effects between diuron and climate were observed for all responses; however, climate had no significant effect on ΔF/Fm' or calcification rates. Photosynthesis was negatively affected as the climate scenarios were adjusted from ambient (28.1 °C, pCO 2  = 397 ppm) to RCP8.5 2050 (29.1 °C, pCO 2  = 680 ppm) and 2100 (30.2 °C, pCO 2  = 858 ppm) with EC50 values declining from 19.4 to 10.6 and 2.6 μg L -1 diuron in turn. These results highlight the likelihood that water quality guideline values may need to be adjusted as the climate changes., (Crown Copyright © 2021. Published by Elsevier Ltd. All rights reserved.)

Diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] is a substituted urea herbicide, carcinogenic for the rat urinary bladder. It has been hypothesized that Diuron cytotoxicity, resulting in regenerative proliferation, leads to urothelial hyperplasia and, finally, to bladder tumors, but molecular mechanisms of carcinogenesis have not still fully investigated. Here, we report the results of a study aimed at verifying the involvement of BAG3, an intracellular protein expressed in several tumors, in the Diuron-induced carcinogenesis. For this purpose, we analyzed the effect of Diuron on human primary urothelial cells and on human dermal fibroblasts. We found that while high concentrations of Diuron have a cytotoxic effect in human primary urothelial cells, in the same cells, noncytotoxic concentrations of the herbicide induce BAG3 expression. These findings show that BAG3 is a molecular target of Diuron and unravel the possible involvement of BAG3 protein in bladder carcinogenesis induced by the herbicide. In addition, these results suggest that BAG3 might be a potential early biomarker of damage induced by chronic exposure to Diuron., (© 2020 Wiley Periodicals LLC.)

Recently, research has contributed to better knowledge on the occurrence of pesticides in coastal water by identifying frequently detected substances, their concentration range and their acute and chronic toxicity for organisms. Pesticide pollution is of particular concern in France due to important agricultural activities and presence of several exoreic catchment areas that vehicle pesticides up to coastal waters, impacting non-target marine species. Several ecotoxicology questions remain to be addressed concerning the long-term effects of chronic pesticide exposure and the mechanisms involved in adaptation to chemical stress. In the present study, we brought new insights on the genetic and epigenetic effects of the herbicide diuron in oyster genitors. During gametogenesis, we exposed Crassostrea gigas to environmentally realistic herbicide concentrations (0.2-0.3 μg L -1 during two 7-day periods at half-course and end of gametogenesis). Diuron exposure was shown to decrease global DNA methylation and total methyltransferase activity in whole oyster tissue; this is consistent with the previous observation of a significant decrease in DNMT1 gene expression. Diuron effect seemed to be tissue-specific; hypermethylation was detected in the digestive gland, whereas diuron exposure had no effect on gill and gonad tissue. The genotoxicity of diuron was confirmed by the detection of one adduct in gonad DNA. By using in vitro approaches and human DNMT1 (DNMT1 has not been purified yet in bivalves), the presence of DNA lesions (adduct, 8-oxodGuo) was shown to interfere with DNMT1 activity, indicating a complex interaction between DNA damage and DNA methylation. Based on our results, we propose mechanisms to explain the effect of diuron exposure on DNA methylation, a widespread epigenetic mark.

The combined algae test is a 96-well plate-based algal toxicity assay with the green algae Raphidocelis subcapitata that combines inhibition of 24-h population growth rate with inhibition of photosynthesis detected after 2 and 24 h with pulse-amplitude modulated (PAM) fluorometry using a Maxi-Imaging PAM. The combined algae test has been in use for more than a decade but has had limitations due to incompatibilities of the measurements of the 2 biological endpoints on the same microtiter plates. These limitations could be overcome by increasing growth rates and doubling times on black, clear-bottom 96-well plates by application of dichromatic red/blue light-emitting diode illumination. Different robotic dosing approaches and additional data evaluation methods helped to further expand the applicability domain of the assay. The combined algae test differentiates between nonspecifically acting compounds and photosynthesis inhibitors, such as photosystem II (PSII) herbicides. The PSII herbicides acted immediately on photosynthesis and showed growth rate inhibition at higher concentrations. If growth was a similar or more sensitive endpoint than photosynthesis inhibition, this was an indication that the tested chemical acted nonspecifically or that a mixture or a water sample was dominated by chemicals other than PSII herbicides acting on algal growth. We fingerprinted the effects of 45 chemicals on photosynthesis inhibition and growth rate and related the effects of the single compounds to designed mixtures of these chemicals detected in water samples and to the effects directly measured in water samples. Most of the observed effects in the water samples could be explained by known photosystem II inhibitors such as triazines and phenylurea herbicides. The improved setup of the combined algae test gave results consistent with those of the previous method but has lower costs, higher throughput, and higher precision. Environ Toxicol Chem 2020;39:2496-2508. © 2020 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC., (2020 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.)

Examination of the impact of Diuron contamination on blood cockles (Tegillarca granosa) was conducted by combining field screening at three sampling events and a toxicity test. Diuron was extracted using the liquid-liquid extraction (LLE) technique and analyzed using HPLC-UV. The median lethal concentration (LC 50 ) of Diuron on T. granosa was tested under a 72-h exposure. Diuron in water samples ranged from not detected (ND) to 3910 ppb, which was the highest concentration detected in samples after the irrigation water was discharged from the paddy plantation. Diuron was not detected in sediment samples. Mortality of T. granosa ranged from 4.74 to 38.33% with the highest percentages recorded after the release of the irrigation water. The LC 50 value of Diuron was 1.84 ppm. This study suggests that irrigation water from paddy plantation that drifts to coastal areas containing Diuron harms T. granosa at the study area., (Copyright © 2020 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Conventional photosystem II (PSII) herbicides applied in agriculture can pose significant environmental risks to aquatic environments. In response to the frequent detection of these herbicides in the Great Barrier Reef (GBR) catchment area, transitions towards 'alternative' herbicides are now widely supported. However, water quality guideline values (WQGVs) for alternative herbicides are lacking and their potential ecological impacts on tropical marine species are generally unknown. To improve our understanding of the risks posed by some of these alternative herbicides on marine species under tropical conditions, we tested the effects of four herbicides on the widely distributed diatom Chaetoceros muelleri. The PSII herbicides diuron, propazine, and tebuthiuron induced substantial reductions in both 24 h effective quantum yields (ΔF/F m ') and 3-day specific growth rates (SGR). The effect concentrations, which reduced ΔF/F m ' by 50% (EC 50 ), ranged from 4.25 µg L -1 diuron to 48.6 µg L -1 propazine, while the EC 50 s for SGR were on average threefold higher, ranging from 12.4 µg L -1 diuron to 187 µg L -1 tebuthiuron. Our results clearly demonstrated that inhibition of ΔF/F m ' in PSII is directly linked to reduced growth (R 2  = 0.95) in this species, further supporting application of ΔF/F m ' inhibition as a valid bioindicator of ecological relevance for PSII herbicides that could contribute to deriving future WQGVs. In contrast, SGR and ΔF/F m ' of C. muelleri were nonresponsive to the non-PSII herbicide haloxyfop at the highest concentration tested (4570 µg L -1 ), suggesting haloxyfop does not pose a risk to C. muelleri. The toxicity thresholds (e.g. no effect concentrations; NECs) identified in this study will contribute to the derivation of high-reliability marine WQGVs for some alternative herbicides detected in GBR waters and support future assessments of the cumulative risks of complex herbicide mixtures commonly detected in coastal waters.

The main organochlorinated compounds used on agricultural crops are often recalcitrant, affecting nontarget organisms and contaminating rivers or groundwater. Diuron (N-(3,4-dichlorophenyl)-N',N'-dimethylurea) is a chlorinated herbicide widely used in sugarcane plantations. Here, we evaluated the ability of 13 basidiomycete strains of growing in a contaminated culture medium and degrading the xenobiotic. Dissipation rates in culture medium with initial 25 mg/L of diuron ranged from 7.3 to 96.8%, being Pluteus cubensis SXS 320 the most efficient strain, leaving no detectable residues after diuron metabolism. Pycnoporus sanguineus MCA 16 removed 56% of diuron after 40 days of cultivation, producing three metabolites more polar than parental herbicide, two of them identified as being DCPU and DCPMU. Despite of the strong inductive effect of diuron upon laccase synthesis and secretion, the application of crude enzymatic extracts of P. sanguineus did not catalyzed the breakdown of the herbicide in vitro, indicating that diuron biodegradation was not related to this oxidative enzyme., Competing Interests: The author(s) declare(s) that there is no conflict of interest regarding the publication of this paper., (Copyright © 2020 Caroline Henn et al.)

The toxicity of the insecticide carbofuran and herbicide diuron (individually and in mixture) to the invertebrates Paramecium caudatum and Ceriodaphnia silvestrii was evaluated. Acute and chronic toxicity tests were carried out with the diuron and carbofuran active ingredients and their commercial products, Diuron Nortox® 500 SC and Furadan® 350 SC, respectively. Individual toxicity tests showed that C. silvestrii was more sensitive to both carbofuran and diuron than P. caudatum. In single exposures, both pesticides caused adverse effects to C. silvestrii in environmentally relevant concentrations (48 h EC 50  = 0.001 mg L -1 and 8 d LOEC = 0.00038 mg L -1 for formulated carbofuran; 8 d LOEC < 0.05 mg L -1 for formulated diuron). For P. caudatum, carbofuran and diuron in single exposures were only slightly toxic (24 h IC 50  = 5.1 mg L -1 and 6.9 mg L -1 for formulated carbofuran and diuron, respectively). Acute and chronic exposures to diuron and carbofuran mixtures caused significant deviations of the toxicity predicted by the Concentration Addition and Independent Action reference models for both test species. For the protozoan P. caudatum, a dose-dependent deviation was verified for mortality, with synergism caused mainly by carbofuran and antagonism caused mainly by diuron. For protozoan population growth, however, an antagonistic deviation was observed when the active ingredient mixtures were tested. In the case of C. silvestrii, antagonism at low concentrations and synergism at high concentrations were revealed after acute exposure to active ingredient mixtures, whereas for reproduction an antagonistic deviation was found. Commercial formulation mixtures presented significantly higher toxicity than the active ingredient mixtures. Our results showed that carbofuran and diuron interact and cause different toxic responses than those predicted by the individually tested compounds. Their mixture toxicity should therefore be considered in risk assessments as these pesticides are likely to be present simultaneously in edge-of-field waterbodies., Competing Interests: Declaration of competing interest The authors declare that they have no conflict of interest., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Diuron, a highly used herbicide worldwide, is metabolized into several toxic metabolites. DCA (3,4-dichloroaniline), DCPU [3-(3, 4-dichlorophenyl)urea] and DCPMU [3-(3,4-dichlorophenyl)-1-methyl urea] reduced viability of human placental choriocarcinoma BeWo, human breast adenocarcinoma MCF-7 and human colon adenocarcinoma Caco-2 cells as judged by the MTT assay, where color formation is dependent on functional mitochondria in viable cells. Based on the IC 50 values in BeWo cells the order of cytotoxicity was DCA > DCPU > diuron > DCPMU, and in Caco-2 cells DCPMU > DCPU > DCA, diuron. In MCF-7 cells, only DCPU had an IC 50 within the range of the concentrations used. In the PI-digitonin viability assay, only the highest concentration (200 μM) of DCPU caused a statistically significant decrease in viability in any cell line. There was no correlation between cytotoxicity and ROS production. This indicates that diuron metabolites are toxic in cells of human origin with mitochondria as the target, but ROS not the likely mechanism., Competing Interests: Declaration of Competing Interest The authors declare that there are no conflicts of interest., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Biocides of antifouling agents can cause problems in marine ecosystems by damaging to non-target algal species. Aquatic bioassays are important means of assessing the quality of water containing mixtures of contaminants and of providing a safety standard for water management in an ecological context. In this study, a rapid, sensitive and inexpensive test method was developed using free-living male and female gametophytes of the brown macroalga Undaria pinnatifida. A conventional fluorometer was employed to evaluate the acute (48 h) toxic effects of six antifouling biocides: 4,5-Dichloro-2-octyl-isothiazolone (DCOIT), diuron, irgarol, medetomidine, tolylfluanid, zinc pyrithione (ZnPT). The decreasing toxicity in male and female gametophytes as estimated by EC 50 (effective concentration at which 50% inhibition occurs) values was: diuron (0.037 and 0.128 mg l -1 , respectively) > irgarol (0.096 and 0.172 mg l -1 , respectively) > tolylfluanid (0.238 and 1.028 mg l -1 , respectively) > DCOIT (1.015 and 0.890 mg l -1 , respectively) > medetomidine (12.032 and 12.763 mg l -1 , respectively). For ZnPT, 50% fluorescence inhibition of U. pinnatifida gametophytes occurred at concentrations above 0.4 mg l -1 . The Undaria method is rapid, simple, practical, and cost-effective for the detection of photosynthesis-inhibiting biocides, thus making a useful tool for testing the toxicity of antifouling agents in marine environments.

Variations of temperature and photoperiod throughout different seasons can affect aquatic communities such as biofilms. Biofilms, generally present at the base of trophic chains in freshwaters, are also subject to organic contamination, and are especially affected by herbicides. Many studies have investigated the effect and interactions of herbicides and environmental factors on biofilms, but never with a toxicokinetic point of view. The objective of this study was to assess structural and functional changes in biofilms exposed to diuron, and to link them with contaminant accumulation, under the influence of temperature and light variations. To this aim, biofilms were exposed to all possible combinations of three concentrations (0, 5 and 50 µg L -1 ) of diuron, two temperatures (10 and 26 °C), and two light/dark photoperiods (16/8, 10/14), for durations of 0, 1 and 3 days. Diuron accumulation in biofilms was quantified and structural descriptors (protein and polysaccharide contents, dry weight) and functional endpoints (photosynthetic and enzymatic activities) were analyzed. The results obtained mainly highlighted the influence of temperature on diuron bioaccumulation and the associated toxic impact on biofilms. Bioaccumulation in biofilms exposed during three days at 10 °C, at the highest diuron concentration, was in average 1.4 times higher than bioaccumulation on biofilms exposed to 26 °C. Accordingly, the photosynthetic yield was more inhibited at lower than at higher temperatures. Temperature was also the highest impacting factor for metabolism regulation; for example, at 26 °C after three days of exposure, polysaccharide production was boosted under both photoperiods tested.

Pesticides are the chemicals of increased concern regarding their adverse environmental effects. In particular, the reports on their joint toxicity effects are scarce in the literature. Therefore, this paper describes the experiments on toxicities of four pesticides: alachlor, chlorfenvinphos, diuron, and isoproturon, toward Vibrio fischeri. In particular, the joint toxicity effects for all possible binary combinations of the pesticides were analyzed. The analysis included the application of concentration addition and independent action models at two toxicity levels: EC 10 and EC 50 . The analysis revealed additive behavior between all pesticide pairs. The only exception was isoproturon and chlorfenvinphos whose combination resulted in synergistic toxic activity. The original form of the logistic function was given preference over the linearized form in describing the response-dose relationships of investigated pesticides., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The sediments of water bodies are not only pollutants sink but also sources of pollution. The assessment for the whole-sediment toxicity is still challenging research. Although the application of immobilized algal bead could overcome the practical difficulties in sediment toxicity assay, the weak growth and reduced sensitivity of algae inside the bead restricted its application. In this study, a sediment toxicity test was developed using immobilized sediment and Chlorella vulgaris. The immobilized sediment was prepared by mixing 2 g freeze-dried sediment and 15-mL 3% (w/v) alginate and hardened in a 4% (w/v) CaCl 2 solution. Based on a C. vulgaris growth inhibition test and using the immobilized sediment, the median effective concentration value (EC 50 ) of the spiked Cu and diuron was 506.23 and 2.37 mg/kg respectively, lower than that of using immobilized algae (719.62 and 3.12 mg/kg respectively). The Cu and diuron concentrations in the corresponding overlying water from the spiked immobilized and free sediment showed that sediment pollutants' diffusion capacity was not decreased after immobilization. By using the immobilized sediment in algae toxicity bioassay, the changes in the sediment toxicity of a polluted river before and after dredging was evaluated. The C. vulgaris growth inhibition in sediment A decreased from 81.94% to 8.43%; sediment B remained unchanged; sediment C stimulated the growth of C. vulgaris before dredging (-15.56%), but inhibited the algae growth after dredging (26.88%), and sediment D decreased growth inhibition from 32.66% to -12.60%., (Copyright © 2019 Elsevier Inc. All rights reserved.)

The aim of the present review was to give an overview of the current state of science concerning herbicide exposure and toxicity to aquatic primary producers. To this end we assessed the open literature, revealing the widespread presence of (mixtures of) herbicides, inevitably leading to the exposure of non-target primary producers. Yet, herbicide concentrations show strong temporal and spatial variations. Concerning herbicide toxicity, it was concluded that the most sensitive as well as the least sensitive species differed per herbicide and that the observed effect concentrations for some herbicides were rather independent from the exposure time. More extensive ecotoxicity testing is required, especially considering macrophytes and marine herbicide toxicity. Hence, it was concluded that the largest knowledge gap concerns the effects of sediment-associated herbicides on primary producers in the marine/estuarine environment. Generally, there is no actual risk of waterborne herbicides to aquatic primary producers. Still, median concentrations of atrazine and especially of diuron measured in China, the USA and Europe represented moderate risks for primary producers. Maximum concentrations due to misuse and accidents may even cause the exceedance of almost 60% of the effect concentrations plotted in SSDs. Using bioassays to determine the effect of contaminated water and sediment and to identify the herbicides of concern is a promising addition to chemical analysis, especially for the photosynthesis-inhibiting herbicides using photosynthesis as endpoint in the bioassays. This review concluded that to come to a reliable herbicide hazard and risk assessment, an extensive catch-up must be made concerning macrophytes, the marine environment and especially sediment as overlooked and understudied environmental compartments.

Fatty acids (FA) are crucial for the maintenance of membrane fluidity and play a central role in metabolic energy storage. Polyunsaturated fatty acids play an essential ecological role since they are key parameters in the nutritional value of algae. Pesticide impacts on fatty acid profiles have been documented in marine microalgae, but remain understudied in freshwater diatoms. The aims of this study were to: 1) investigate the impact of diuron and S-metolachlor on "classical descriptors" (photosynthesis, growth rate, pigment contents, and on the expression levels of target genes in freshwater diatoms), 2) examine the impact of these pesticides on diatom fatty acid profiles and finally, 3) compare fatty acid profiles and "classical descriptor" responses in order to evaluate their complementarity and ecological role. To address this issue, the model freshwater diatom Gomphonema gracile was exposed during seven days to diuron and S-metolachlor at 10 μg.L -1 . G. gracile was mostly composed of the following fatty acids: 20:5n3; 16:1; 16:0; 16:3n4; 14:0 and 20:4n6 and highly unsaturated fatty acids were overall the best represented fatty acid class. S-metolachlor decreased the growth rate and chlorophyll a content of G. gracile and induced the expression of cox1, nad5, d1 and cat genes, while no significant impacts were observed on photosynthesis and carotenoid content. In a more global way, S-metolachlor did not impact the fatty acid profiles of G. gracile. Diuron inhibited photosynthesis, growth rate, chlorophyll a content and induced cat and d1 gene expressions but no significant effect was observed on carotenoid content. Diuron decreased the percentage of highly unsaturated fatty acids but increased the percentage of monounsaturated fatty acids. These results demonstrated that fatty acids responded to diuron conversely to pigment content, suggesting that fatty acids can inform on energy content variation in diatoms subjected to herbicide stress., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The use of alternative biocides has increased due to their economic and ecological relevance. Although data regarding the toxicity of commercial alternative biocides in marine organisms are accumulating, little is known about their toxic pathways or mechanisms. To compare the toxic effects of commercial alternative biocides on non-target pelagic fish (flounder) embryos, we investigated the adverse effects of developmental malformation and transcriptional changes. Three biocides including Diuron, Irgarol 1051 ® and Sea-Nine 211 ® produced a largely overlapping suite of developmental malformations, including tail-fin fold defects and dorsal body axis curvature. In our test, the potencies of these biocides were ranked in the following order with respect to malformation and mortalities: Sea-Nine 211 ®  > Irgarol 1051 ®  > Diuron. Consistent with the toxicity rankings, the expression of genes related to heart formation was greater in embryonic flounder exposed to Sea-Nine 211 ® than in those exposed to Irgarol 1051 ® or Diuron, while expression of genes related to fin malformation was greater in the Irgarol 1051 ® exposure group. In analyses of differential gene expression (DEG) profiles (fold change of genes with a cutoff P < 0.05) by high-throughput sequencing (RNA-seq), genes associated with nervous system development, transmembrane transport activity, and muscle cell development were significantly changed commonly. Embryos exposed to Diuron showed changes related to cellular protein localization, whereas genes associated with immune system processes were up-regulated significantly in embryos exposed to Irgarol 1051 ® . Genes related to actin filament organization and embryonic morphogenesis were up-regulated in embryos exposed to Sea-Nine 211 ® . Overall, our study provides a better understanding of the overlapping and unique developmental toxic effects of three commercial booster biocides through transcriptomic analyses in a non-target species, embryonic flounder., (Copyright © 2019. Published by Elsevier Inc.)

Diuron is an herbicide, which is used to control a wide variety of annual and perennial broadleaf, grassy weeds, and mosses. However, the toxicity of diuron in HepG2 cells and zebrafish embryos was unclear. In this study, HpeG2 cells and zebrafish embryos were exposed to different concentrations of diuron for 24 h and 48 h, respectively. Results reveal the diuron caused cytotoxicity and the generation of reactive oxygen species (ROS) in the treated HepG2 cells. The effects of diuron on the expression of catalase and superoxide dismutase (SOD1 and SOD2), an antioxidant enzyme, were investigated. Results showed that only SOD1 was significantly induced after treated diuron 48 h, but the expression of catalase and SOD2 was unaffected. Additionally, the cytotoxicity of diuron was not attenuated in cells pretreated with of N-acetyl-cysteine (NAC), a well-known antioxidant, indicating that oxidative stress could not contribute to cellular death in the treated HepG2 cells. In zebrafish embryos, results from proteomic analysis show that 332 differentially upregulated proteins and 199 down-regulated proteins were detected in the treated embryos (P < 0.05). In addition to the up-regulated antioxidant proteins (prdx3, cat, prdx4, txnrd1, prdx1, sod1, prdx2, and sod2), some decreased proteins were related to cytoskeleton formation, tight junction, and gap junction, which could be related to the malformation of the treated zebrafish embryos. In summary, diuron caused cytotoxicity in HepG2 cells, and the mechanisms of toxicity in zebrafish were addressed using the proteomic analysis., (Copyright © 2019 Elsevier Inc. All rights reserved.)

This study was aimed to develop an objective way of quantifying the reproductive status of the green macroalga, Ulva pertusa using a vital stain and programmed automated analysis (by Image J program). The EC 50 values (with 95% CI), the concentrations of toxicants inducing a reduction of 50% in sporulation after 96 h exposure, from the newly developed method were similar to those obtained by the conventional method: 0.651 (0.598-0.705) mg l -1 for Cd, 0.144 (0.110-0.162) mg l -1 for Cu, 0.180 (0.165-0.195) mg l -1 for atrazine, 0.076 (0.049-0.094) mg l -1 for diuron and 30.6 (26.5-34.4) ml l -1 for DMSO, respectively. When the EC 50 values from this study were compared to that those from literatures, the sensitivity for some toxicants was similar or higher than that of U. fasciata (1.930 mg l -1 for germination for Cd), U. armoricana (0.250 mg l -1 for Fv/Fm for Cu), U. reticulata (0.126-1.585 mg l -1 for growth for Cu), and U. intestinalis (0.650 mg l -1 for Fv/Fm for atrazine). The subjective views of the experimental performers can be eliminated using the newly developed method. The Ulva method gave consistent responses to Cu and Cd of internationally allowable ranges for effluents, implying that the method is a useful tool for monitoring industrial wastewaters containing these metals., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The photosynthetic machinery of the cyanobacterium Synechocystis sp. PCC 6803 resides in flattened membrane sheets called thylakoids, situated in the peripheral part of the cellular cytoplasm. Under photosynthetic conditions these thylakoid membranes undergo various dynamical processes that could be coupled to their energetic functions. Using Neutron Spin Echo Spectroscopy (NSE), we have investigated the undulation dynamics of Synechocystis sp. PCC 6803 thylakoids under normal photosynthetic conditions and under chemical treatment with DCMU (3-(3,4-dichlorophenyl)-1,1-dimethylurea), an herbicide that disrupts photosynthetic electron transfer. Our measurements show that DCMU treatment has a similar effect as dark conditions, with differences in the undulation modes of the untreated cells compared to the chemically inhibited cells. We found that the disrupted membranes are 1.5-fold more rigid than the native membranes during the dark cycle, while in light they relax approximately 1.7-fold faster than native and they are 1.87-fold more flexible. The strength of the herbicide disruption effect is characterized further by the damping frequency of the relaxation mode and the decay rate of the local shape fluctuations. In the dark, local thicknesses and shape fluctuations relax twice as fast in native membranes, at 17% smaller mode amplitude, while in light the decay rate of local fluctuations is 1.2-fold faster in inhibited membranes than in native membranes, at 56% higher amplitude. The disrupted electron transfer chain and the decreased proton motive force within the lumenal space partially explain the variations observed in the mechanical properties of the Synechocystis membranes, and further support the hypothesis that the photosynthetic process is tied to thylakoid rigidity in this type of cyanobacterial cell.

Biofilms are considered as good bioindicators of contamination by means of their capacity to react quickly to xenobiotics exposure, and their pivotal role in sustaining the aquatic trophic web. The exchanges of dissolved substances between water column and biofilm can be modulated by flow velocity. This study deals with toxicokinetic (transfer mechanisms) and toxicodynamic (effects) modelling of pesticides under two contrasted flow conditions. Diuron was used to run a 2-h kinetic study on mature biofilms in river channels. Two flow conditions were considered (⋘1 cm·s -1 : lentic environments such as ponds, 2 cm·s -1 : lotic environments such as watercourses). Three concentrations were tested in order to estimate contamination levels in biofilms: 0, 5 (environmentally relevant concentration) and 50 (to determine the concentration effect) μg·L -1 . The effect of the above-mentioned factors was also assessed on biofilms photosynthesis inhibition. For successive sampling times between 0 and 2 h, the raw biofilms and EPS tightly bound to cells plus microorganisms (T-EPS-M), were physically separated and analysed for diuron accumulation and structural and functional microbial descriptors. Diuron amounts accumulated in biofilm increased with increasing diuron exposure. Biofilms accumulated higher amounts of diuron at the lower flow velocity compared to high flow for raw biofilms, while accumulation in the T-EPS-M fraction was similar between flow conditions. Consequently, both flow velocity and diuron exposure had an influence on diuron bioaccumulation and distribution. Photosynthesis inhibition over time was directly linked to the exposure concentration of diuron recorded in the T-EPS-M fraction. These results suggest that flow causes a loss of organic matter in biofilms, decreasing the total accumulation of diuron, especially within diffusible EPS. As pesticide distribution in biofilm is a major factor in the onset of toxicity, the novel fractioning method presented here will improve further toxicokinetic and toxicodynamic studies dealing with biofilms exposed to organic toxicants., (Copyright © 2018 Elsevier B.V. All rights reserved.)

After application, herbicides often reach the soil and affect non-target soil microorganisms, decreasing their population, diversity or affecting metabolic activity. Therefore, laboratory studies were performed to evaluate the effects of diuron, hexazinone and sulfometuron-methyl alone and mixed upon carbon transformation by soil microorganisms in clayey and sandy soils and the effect on bacterial diversity and structure. Control treatment without herbicide application was also performed. Sub-samples from the control and herbicide treatments (10 g - in triplicate) were collected before herbicide application and 7, 14, 28 and 42 days after treatment (DAT), then 1 mL of 14 C-glucose solution was applied. The released 14 CO 2 was trapped in 2 M NaOH solution and the radioactivity was analyzed by liquid scintillation counting (LSC), 12 h after glucose application. The effect of herbicides on bacterial diversity was evaluated by T-RFLP. The experiment was conducted in a complete randomized design. Hexazinone did not affect 14 CO 2 evolution. Diuron showed a greater 14 CO 2 evolution in sandy and clayey soil, while sulfometuron-methyl led to an increase in sandy soil, at 42 DAT. A greater evolution of carbon was observed in the treatment with herbicide mixture in sandy soil, compared with the same treatment in clayey soil or control. However, the herbicide mixture application did not affect the soil biological activity measured by the respiration rate induced by substrate. On the other hand, the herbicide mixtures affected the bacterial diversity in both soils, being the strongest effect to diuron and sulfometuron-methyl in clayey soil and hexazinone in sandy soil.

A critical need exists to develop rapid, in situ, and real-time tools to monitor the impact of pollution discharge toxicity on aquatic ecosystems. The present paper deals with the development of a novel, simple-to-use, low-cost, portable, and user-friendly algal biosensor. In this study, a complete and autonomous portable fluorimeter was developed to assess the A-chlorophyll fluorescence of microalgae, inserted by capillarity into low-cost and disposable xurography-based microfluidic chips. Three microalgae populations were used to develop the biosensor: Chlorella vulgaris, Pseudokirchneriella subcapitata, and Chlamydomonas reinhardtii. Biosensor feasibility and sensitivity parameters, such as algal concentration and light intensity, were optimized beforehand to calibrate the biosensor sensitivity with Diuron, a pesticide known to be very toxic for microalgae. Finally, the biosensor was employed in 10 aqueous urban polluted samples (7 urban wet-weather discharges and 3 wastewater) in order to prove its reliability, reproducibility, and performance in the detection of toxic discharges in the field., (Copyright © 2018 Elsevier B.V. All rights reserved.)

As compared to their temperate counterparts, few toxicity tests have been conducted so far into the evaluation of the sensitivity of indigenous tropical species to pesticides. Especially mixture toxicity assessments appear to be scarce. To contribute to increase our knowledge in this arena, we evaluated the acute toxicity of diuron and carbofuran and their mixtures to the neotropical oligochaetes Allonais inaequalis and Dero furcatus, and the ostracod Strandesia trispinosa. Tests were performed with both the pure active ingredients, as well as their formulated products. The toxicity of the latter to the three test organisms was generally greater than that of the pure active ingredients, although absolute differences were rather small. The sensitivity of the indigenous species was slightly greater than temperate test species from the same taxonomic groups. The concentration addition conceptual model best described the results of the mixture toxicity data. Derived deviations of this model appeared to be dependent on the test organism and as to whether the pesticides were applied as active ingredients or their commercial products. Reported field concentrations of the two pesticides indicate risks to freshwater biota, especially if they are both present. The test species used in the present study are concluded to be suitable candidates as surrogate test organisms in local pesticide risk evaluations.

Seagrass meadows suffered large-scale declines in the past century. The 'wasting disease', pathognomonically associated with Labyrinthula zosterae, reduced populations of Zostera marina on both sides of the North Atlantic in, and since, the 1930s, coinciding with intensive agricultural use of artificial fertilizers and herbicides. This study tests the long-standing hypothesis that nutrient enrichment and a herbicide increases vulnerability to pathogens. Z. marina shoots from the Thames Estuary grown in elevated nitrate concentrations had significantly higher rates of infection by L. zosterae than controls, but not by Aplanochytrium sp., another slime-mould like protist. Z. marina shoots grown in 2μg·l -1 Diuron solutions and infected separately by L. zosterae and Aplanochytrium sp. had significantly higher wasting indices than controls. The results identified Aplanochytrium sp. as another opportunistic pathogen causing a seagrass wasting-type disease and support the hypothesis that pollution by herbicides and nitrate increases the susceptibility of Z. marina to infections., (Copyright © 2017 Elsevier Ltd. All rights reserved.)