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While diuron residues are being detected more frequently in agricultural soils, there is limited information available regarding their potential phytotoxicity to non-target grain crops. This study aims to determine robust phytotoxicity thresholds for three common, but contrasting, crop species (canola, chickpea, and wheat) exposed to a range of diuron concentrations and to determine how loamy sand soil can change the toxicity thresholds relative to an inert sand. The log-logistic non-linear regression model proved most effective in determining toxicity thresholds by analysing crop responses to diuron. Canola was the most sensitive to diuron in sand followed by wheat and chickpea. Diuron exhibits higher phytotoxicity in sand compared to loamy sand, with ED 50 values (which is the dose at which diuron causes a 50% decrease in plant growth) of 0.03 mg kg -1 and 0.07 mg kg -1 for canola shoot biomass inhibition and 0.01 mg kg -1 and 0.06 mg kg -1 for root dry weight reduction, respectively. The ED 50 values for wheat shoot biomass (0.11 and 0.24 mg kg -1 ) in sand and loamy sand, respectively, and the ED 50 values for root growth inhibition are 0.14 mg kg -1 in sand and 0.19 mg kg -1 in loamy sand. These values were lower than label concentrations and previously estimated average and maximum diuron residue loads (0.17 and 0.29 mg kg -1 ) in Western Australia paddocks. The larger ED 50 values of diuron in the loamy sand can be attributed to higher soil organic matter and cation exchange capacity that decreased bio-available diuron levels. Average diuron residue loads in Western Australia crop fields exceed the ED 50 value emphasizes the need for careful planning of crop rotations to avoid crop phytotoxicity from soil-borne diuron residues. Further study is needed to determine the effect of a wider range of soil properties such as pH, clay content, and soil organic matter on the phytotoxicity risk of diuron to rotational crops.

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.

Freshwater biofilms have been increasingly used during the last decade in ecotoxicology due to their ecological relevance to assess the effect(s) of environmental stress at the community level. Despite growing knowledge about the effect of various stressors on the structure and the function of these microbial communities, a strong research effort is still required to better understand their response to chemical stress and the influence of environmental stressors in this response. To tackle this challenge, untargeted metabolomics is an approach of choice because of its capacity to give an integrative picture of the exposure to multiple stress and associated effect as well as identifying the molecular pathways involved in these responses. In this context, the present study aimed to explore the use of an untargeted metabolomics approach to unravel at the molecular/biochemical level the response of the whole biofilm to chemical stress and the influence of various environmental factors in this response. To this end, archived high-resolution mass spectrometry data from previous experiments at our laboratory on the effect of the model photosynthesis inhibitor diuron on freshwater biofilm were investigated by using innovative solutions for OMICs data (e.g., DRomics) and more usual chemometric approaches (multivariate and univariate statistical analyses). The results showed a faster (1 min) and more sensitive response of the metabolome to diuron than usual functional descriptors, including photosynthesis. Also, the metabolomics response to diuron resulted from metabolites following various trends (increasing, decreasing, U/bell shape) along increasing concentration and time. This metabolomics response was influenced by the temperature, photoperiod, and flow. A focus on a plant-specific omega-3 (eicosapentaenoic acid) playing a key role in the trophic chain highlighted the potential relevance of metabolomics approach to establish the link between molecular alteration and ecosystem structure/functioning impairment but also how complex is the response and the influence of all the tested factors on this response at the metabolomics level. Altogether, our results underline that more fundamental researches are needed to decipher the metabolomics response of freshwater biofilm to chemical stress and its link with physiological, structural, and functional responses toward the unraveling of adverse outcome pathways (AOP) for key ecosystem functions (e.g., primary production).

Tropical seagrasses are at their highest risk of exposure to photosystem II (PSII) herbicides when elevated rainfall and runoff from farms transports these toxicants into coastal habitats during summer, coinciding with periods of elevated temperature. PSII herbicides, such as diuron, can increase the sensitivity of corals to thermal stress, but little is known of the potential for herbicides to impact the thermal optima of tropical seagrass. Here we employed a well-plate approach to experimentally assess the effects of diuron on the photosynthetic performance of Halophila ovalis leaves across a 25 °C temperature range (36 combinations of these stressors across 15–40 °C). The thermal optimum for photosynthetic efficiency (▵ ) in H. ovalis was 31 °C while lower and higher temperatures reduced ▵ as did all elevated concentrations of diuron. There were significant interactions between the effects of temperature and diuron, with a majority of the combined stresses causing sub-additive (antagonistic) effects. However, both stressors caused negative responses and the sum of the responses was greater than that caused by temperature or diuron alone. These results indicate that improving water quality (reducing herbicide in runoff) is likely to maximise seagrass health during extreme temperature events that will become more common as the climate changes.

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.

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.

Urban agriculture is crucial to local populations, but the risk of it contaminating water has rarely been documented. The aim of this study was to assess pesticide contamination of surface waters from the Méfou watershed (Yaoundé, Cameroon) by 32 selected herbicides, fungicides, and insecticides (mainly polar) according to their local application, using both grab sampling and polar organic compounds integrative samplers (POCIS). Three sampling campaigns were conducted in the March/April and October/November 2015 and June/July 2016 rainy seasons in urban and peri-urban areas. The majority of the targeted compounds were detected. The quantification frequencies of eight pesticides were more than 20% with both POCIS and grab sampling, and that of diuron and atrazine reached 100%. Spatial differences in contamination were evidenced with higher contamination in urban than peri-urban rivers. In particular, diuron was identified as an urban contaminant of concern because its concentrations frequently exceeded the European water quality guideline of 0.200 μg/L in freshwater and may thus represent an ecological risk due to a risk quotient > 1 for algae observed in 94% of grab samples. This study raises concerns about the impacts of urban agriculture on the quality of water resources and to a larger extent on the health of the inhabitants of cities in developing countries. Graphical abstract

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 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.

The phenylurea herbicides are persistent in soil and water, making necessary the de-velopment of techniques for their removal from the environment. To identify new options in this regard, bacterial strains were isolated from a soil historically managed with pesticides. Ochrobactrum anthropi CD3 showed the ability to remove completely herbicides such as diuron, linuron, chlorotoluron and fluometuron from aqueous solution, and up to 89% of isoproturon. In the case of diuron and linuron, their main metabolite, 3,4-dichloroaniline (3,4-DCA), which has a higher toxicity than the parent compounds, was formed, but remained in solution without further degradation. O. anthropi CD3 was also tested for bioremediation of two different agricultural soils artificially contaminated with diuron, employing bioremediation techniques: (i) biostimulation, using a nutrient solution (NS), (ii) bioaugmentation, using O. anthropi CD3, and iii) bioavailability enhancement using 2-hydroxypropyl-β-cyclodextrin (HPBCD). When bioaugmentation and HPBCD were jointly applied, 50% of the diuron initially added to the soil was biodegraded in a range from 4.7 to 0.7 d. Also, 3,4-DCA was degraded in soil after the strain was inoculated. At the end of the soil biodegradation assay an ecotoxicity test confirmed that after inoculating O. anthropi CD3 the toxicity was drastically reduced.