Elevated water temperature reduces the acute toxicity of the widely used herbicide diuron to a green alga, Pseudokirchneriella subcapitata

In the actual environment, temperatures fluctuate drastically through season or global warming and are thought to affects risk of pollutants for aquatic biota; however, there is no report about the effect of water temperature on toxicity of widely used herbicide diuron to fresh water microalgae. The present research investigated inhibitory effect of diuron on growth and photosynthetic activity of a green alga Pseudokirchneriella subcapitata at five different temperatures (10, 15, 20, 25, and 30 °C) for 144 h of exposure. As a result, effective diuron concentrations at which a 50 % decrease in algal growth occurred was increased with increasing water temperature ranging from 9.2 to 20.1 μg L^–1 for 72 h and 9.4–28.5 μg L^–1 for 144 h. The photochemical efficiency of photosystem II (F _v/F _m ratio) was significantly reduced at all temperatures by diuron exposure at 32 μg L^–1 after 72 h. Inhibition rates was significantly increased with decreased water temperature (P?<?0.01). Intracellular H₂O₂ levels as an indicator of oxidative stress were also decreased with increasing temperature in both control and diuron treatment groups and were about 2.5 times higher in diuron treatment groups than that of controls (P?<?0.01). Our results suggest water temperatures may affect the toxicokinetics of diuron in freshwater and should therefore be considered in environmental risk assessment.     

Phytotoxicity of atrazine, isoproturon, and diuron to submersed macrophytes in outdoor mesocosms

The submersed macrophytes Elodea canadensis, Myriophyllum spicatum and Potamogeton lucens were constantly exposed over a five-week period to environmentally relevant concentrations of atrazine, isoproturon, diuron, and their mixture in outdoor mesocosms. Effects were evaluated investigating photosynthetic efficiency (PE) of the three macrophytes and growth of M. spicatum and E. canadensis. Adverse effects on PE were observed on days 2 and 5 after application. M. spicatum was found to be the more sensitive macrophyte. E. canadensis and P. lucens were less sensitive to atrazine, diuron and the mixture and insensitive to isoproturon. PE of M. spicatum was similarly affected by the single herbicides and the mixture demonstrating concentration addition. Growth of E. canadensis and M. spicatum was not reduced indicating that herbicide exposure did not impair plant development. Although PE measurements turned out to be a sensitive method to monitor PSII herbicides, plant growth remains the more relevant ecological endpoint in risk assessment.     

Respiration induced by substrate and bacteria diversity after application of diuron,hexazinone, and sulfometuron-methyl alone and in mixture

Abstract

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 ¹⁴C-glucose solution was applied. The released ¹⁴CO₂ 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 ¹⁴CO₂ evolution. Diuron showed a greater ¹⁴CO₂ 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.     

The veterinary drug ivermectin influences immune response in the yellow dung fly (Scathophaga stercoraria)

Phenoloxidase (PO) is a key enzyme involved in the immune response of insects. We show that egg-to-adult exposure to residues of 0.001, but not 0.0005 mg kg⁻¹ ivermectin elevated PO activity in yellow dung flies (Scathophaga stercoraria) developing in cattle dung. Fly fat content was unaffected by the treatments. Therefore, the response of PO was a direct effect of ivermectin and not an indirect one caused by an alteration in body ‘condition’. This supports the non-intuitive conclusion that flies surviving exposure to faecal residues may have enhanced immune function. To our knowledge, this is the first study to assess the effects on PO activity of insecticidal residues in livestock dung. The non-target effects of such residues are of wide interest, given the global use of veterinary products.     

Phytotoxicity of diuron alone and in combination with copper or folpet on duckweed (Lemna minor)

The photosystem II-herbicide diuron is widely used for weed control in Champagne's vineyards. Its important use and its relative persistence make it of particular interest for ecotoxicological studies. Toxicity of diuron was assessed on Lemna minor L., a representative aquatic macrophyte regularly used for toxicological studies. Toxicity assessments were based on inhibition of growth and total chlorophyll content of L. minor cultures after 7 days. Growth was inhibited and IC(50) and IC(90) were, respectively, 25 and 60 microg l(-1), but chlorophyll content of L. minor increased in response to the herbicide. When diuron was combined with copper, growth inhibition of L. minor depended on the concentrations of both chemicals. For some concentrations, combination of these chemicals resulted in a slight (but non-significant) antagonism. Additivity was observed for all other mixtures. When diuron was combined with folpet, growth and chlorophyll content of L. minor only depended on the concentration of the herbicide. Diuron was also found to prevent the copper-induced decrease of chlorophyll content when it was combined with this metal. A multifactorial model was found more appropriate to characterize interactions between pesticides than Abott's model.     

Bioaccumulation and metabolisation of (14)C-pyrene by the Pacific oyster Crassostrea gigas exposed via seawater

The first objective of this study was to determine the bioaccumulation kinetics of pyrene in the soft tissues of Crassostrea gigas (mantle, muscle, gills, digestive gland, and the remaining soft tissues). As bivalves can biotransform hydrocarbons in more polar compounds (metabolites) that are more easily excreted, the second objective was to investigate the oyster capacity to metabolize pyrene into its metabolite, the 1-hydroxypyrene. To these ends, oysters were exposed 24 h to waterborne ¹⁴C-pyrene then placed in depuration conditions for 15 d. Oysters efficiently bioaccumulated pyrene in their soft tissues and equilibrium was reached within the exposure time. The metabolite1-hydroxypyrene was also detected in oyster tissues but represented only 4-14% of the parent pyrene. At the end of the exposure period, the gills and the mantle showed the highest pyrene proportion of total soft tissue content, i.e. 47% and 26%, respectively. After 15 d of depuration, the mantle contained 32% and 30% of the remaining pyrene and 1-hydroxypyrene, respectively. As C. gigas did not display a high capacity for metabolizing pyrene, it can be considered as a good bioindicator species to survey and monitor pyrene contamination in the coastal marine environment.     

Effects of low concentrations of the phenylurea herbicide diuron on biofilm algae and bacteria

A system of recirculating channels was used in this study to examine the long-term effects (29 d) of environmentally realistic concentrations of the herbicide diuron (from 0.07 to 7 μg L⁻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.     

Influence of organic amendments on diuron leaching through an acidic and a calcareous vineyard soil using undisturbed lysimeters

The influence of different organic amendments on diuron leaching was studied through undisturbed vineyard soil columns. Two composts (A and D), the second at two stages of maturity, and two soils (VR and Bj) were sampled. After 1 year, the amount of residues (diuron + metabolites) in the leachates of the VR soil (0.19-0.71%) was lower than in the Bj soil (4.27-8.23%), which could be explained by stronger diuron adsorption on VR. An increase in the amount of diuron leached through the amended soil columns, compared to the blank, was observed for the Bj soil only. This result may be explained by the formation of mobile complexes between diuron and water-extractable organic matter (WEOM) through the Bj soil, or by competition between diuron and WEOM for the adsorption sites in the soil. For both soils, the nature of the composts and their degree of maturity did not significantly influence diuron leaching.     

Determination of the microscopic rate constants for the hydrolysis of diuron in soil/water mixture

A kinetic equation for the analysis of the degradation reaction of xenobiotic molecules in the soil/water mixture has been derived. By means of this equation we have evaluated the microscopic rate constant for the abiotic hydrolysis of the herbicide diuron in the water phase of a soil/water mixture assuming that the reaction occurs only in the water phase and that diuron is reversibly adsorbed by the soil with a higher rate. The soil catalytic capacity on the hydrolysis of diuron was evaluated.     

Leaching of oryzalin and diuron through undisturbed vineyard soil columns under outdoor conditions

Field studies monitoring herbicide pollution in the vineyards of Burgundy (France) have revealed that drinking water reservoirs are contaminated with several pre-emergence herbicides. An assessment of the leaching of two such herbicides, diuron and oryzalin, was therefore performed using lysimeters, under outdoor conditions, from May 2001 to May 2002. Four vineyard soils from Vosne-Romanée (Burgundy) were chosen along a topolithosequence: a rendosol and three calcosols. After 673 mm of rainfall, greater amounts of diuron than oryzalin were measured in percolates: respectively 0.10-0.84% and 0.02-0.43% of applied herbicide, depending on soils. Measurements for diuron metabolites detected greater amounts of DCPMU than DCPU in the percolates: respectively 0.05-0.13% and 0-0.04% of the applied diuron. At the end of the monitoring period, more residues of diuron than oryzalin were recovered in the soil profiles: respectively 4.6-9% and 1.4-4.4%. The oryzalin residues were found mainly in the upper 10 cm of soil columns, whereas diuron residues were present in the whole core. The mobility of both oryzalin and diuron seems fairly well-related to soil organic carbon content; the mobility of diuron is also related to soil texture (sand and coarse material contents). Under such experimental conditions, this study confirms that diuron leaching, and therefore potential groundwater contamination, is greater than that of oryzalin.     

Responses of Hyalella azteca and phytoplankton to a simulated agricultural runoff event in a managed backwater wetland

We assessed the aqueous toxicity mitigation capacity of a hydrologically managed floodplain wetland following a synthetic runoff event amended with a mixture of sediments, nutrients (nitrogen and phosphorus), and pesticides (atrazine, S-metolachlor, and permethrin) using 48-h Hyalella azteca survival and phytoplankton pigment, chlorophyll a. The runoff event simulated a 1 h, 1.27 cm rainfall event from a 16 ha agricultural field. Water (1 L) was collected every 30 min within the first 4 h, every 4 h until 48 h, and on days 5, 7, 14, 21, and 28 post-amendment at distances of 0, 10, 40, 300 and 500 m from the amendment point for chlorophyll a, suspended sediment, nutrient, and pesticide analyses. H. azteca 48-h laboratory survival was assessed in water collected at each site at 0, 4, 24, 48 h, 5 d and 7 d. Greatest sediment, nutrient, and pesticide concentrations occurred within 3 h of amendment at 0 m, 10 m, 40 m, and 300 m downstream. Sediments and nutrients showed little variation at 500 m whereas pesticides peaked within 48 h but at <15% of upstream peak concentrations. After 28 d, all mixture components were near or below pre-amendment concentrations. H. azteca survival significantly decreased within 48 h of amendment up to 300 m in association with permethrin concentrations. Chlorophyll a decreased within the first 24 h of amendment up to 40 m primarily in conjunction with herbicide concentrations. Variations in chlorophyll a at 300 and 500 m were associated with nutrients. Managed floodplain wetlands can rapidly and effectively trap and process agricultural runoff during moderate rainfall events, mitigating impacts to aquatic invertebrates and algae in receiving aquatic systems.     

Sorption, degradation, and leaching of tebuthiuron and diuron in soil columns

A study in small outdoor lysimeters was carried out to determine the leaching of the herbicides tebuthiuron and diuron in different soil types, using undisturbed soil columns. Soil sorption and degradation for both herbicides were also studied in the laboratory. The multi-layered AF (Attenuation Factor) model was evaluated for predicting the herbicides leaching in undisturbed soil columns. Tebuthiuron leached in greater amounts than diuron in both soils. Sorption was well represented by linear and Freundlich equations, however parameters from the linear equations were used in the AF model. In general, both herbicides presented very low sorption, with diuron presenting lower values of sorption coefficient than tebuthiuron in the two soils. Chromatographic data indicated rapid late degradation of diuron and tebuthiuron in both soil types at two different depths. Simple exponential equation was not able to represent degradation, thus a bi-exponential equation was used, and some model adjusting was needed. Average measured amounts of each herbicide were compared with amounts predicted by the multi-layered-soil AF model. The AF model was able to predict leaching amounts in the sandy soil, especially for diuron, however it did not perform well in the clayey soil.     

Volatilization of polycyclic aromatic hydrocarbons from coal-tar-sealed pavement

The effects of the herbicide atrazine on the gill of the freshwater fish Prochilodus lineatus were evaluated after exposure of fish to 2, 10 and 25 μg L⁻¹ atrazine during 48 h (acute exposure) and 14 d (subchronic exposure). Ions and osmolality were measured in plasma and gill samples were taken to determine the Na⁺/K⁺-ATPase (NKA) and carbonic anhydrase (CA) activities and for morphological analysis. Plasma osmolality and Na⁺ and Cl⁻ ions changed depending on atrazine concentration, but atrazine exposure had no effect on the Na⁺/Cl⁻ ratio. NKA activity did not change after atrazine exposure, but CA activity decreased in fish exposed to 25 μg L⁻¹ for 14 d. Gill MRC density decreased after acute exposure but did not change in fish exposed to the subchronic treatment. The MRC density at the epithelial surface increased in fish exposed to 25 μg L⁻¹, and the MRC fractional area (MRCFA) increased in fish exposed to 10 μg L⁻¹. The changes in MRCs provide evidence of morphological adjustments to maintain ionic homeostasis in spite of the inhibition of CA activity at the highest atrazine concentration.     

Sorption and desorption kinetics of diuron,fluometuron, prometryn and pyrithiobac sodium in soils

Abstract

The sorption and desorption characteristics of four herbicides (diuron, fluometuron, prometryn and pyrithiobac‐sodium) in three different cotton growing soils of Australia was investigated. Kinetics and equilibrium sorption and desorption isotherms were determined using the batch equilibrium technique. Sorption was rapid (> 80% in 2 h) and sorption equilibrium was achieved within a short period of time (ca 4 h) for all herbicides. Sorption isotherms of the four herbicides were described by Freundlich equation with an r² value > 0.98. The herbicide sorption as measured by the distribution coefficient (K_d) values ranged from 3.24 to 5.71 L/kg for diuron, 0.44 to 1.13 L/kg for fluometuron, 1.78 to 6.04 L/kg for prometryn and 0.22 to 0.59 L/kg for pyrithiobac‐sodium. Sorption of herbicides was higher in the Moree soil than in Narrabri and Wee Waa soils. When the K_d values were normalised to organic carbon content of the soils (K_oC), it suggested that the affinity of the herbicides to the organic carbon increased in the order: pyrithiobac‐sodium < fluometuron < prometryn < diuron. The desorption isotherms were also adequately described by the Freundlich equation. For desorption, all herbicides exhibited hysteresis and the hysteresis was stronger for highly sorbed herbicides (diuron and prometryn) than the weakly sorbed herbicides (fluometuron and pyrithiobac‐sodium). Hysteresis was also quantified as the percentage of sorbed herbicides which is not released during the desorption step ω = [n_ad / n_de ‐1] x 100). Soil type and initial concentration had significant effect on ω. The effect of sorption and desorption properties of these four herbicides on the off‐site transport to contaminate surface and groundwater are also discussed in this paper.     

Assessing the genotoxic potentials of arsenic in tilapia (Oreochromis mossambicus) using alkaline comet assay and micronucleus test

This experiment was conducted to study the genotoxic potentials of sodium arsenite (NaAsO₂) in freshwater fish Oreochromis mossambicus by using alkaline comet assay and micronucleus (MN) test. Fish were exposed to three different concentrations (3 ppm, 28 ppm and 56 ppm) of arsenic and gill, liver and blood tissue samples were collected after 48 h, 96 h and 192 h of exposure. Arsenic exposure induced DNA damage in all tissues examined in a concentration dependent manner. A significant (p < 0.05) increase in the comet tail DNA (%) of the exposed fish liver, gill, and blood was observed after 48 h and 96 h of exposure, but a decline in DNA damage was recorded in all the tissues at all the three concentrations studied after 192 h of exposure. Liver tissue exhibited significantly (p < 0.05) higher DNA damage at all the concentrations examined, followed by gill and blood. Higher liver tail DNA (51.38 ± 0.21%) refers that it is more prone to injury to arsenic toxicity than the gill and blood. In blood samples arsenic induced micronucleus formation in a concentration dependent manner and highest (5.8 ± 0.46%) value was recorded in 56 ppm after 96 h of exposure, whereas, it was decreased after 192 h of exposure at all the three concentrations of NaAsO₂ examined which refers to the DNA repairing ability of fish to arsenic toxicity. The results of this study depict the genotoxic potentials of arsenic to fish which in turns provide insight on advanced study in aquatic toxicology.     

Isolation, characterization and diuron transformation capacities of a bacterial strain Arthrobacter sp. N2

A bacterial strain able to transform diuron was isolated from a soil by enrichment procedures. Strain isolation was realized by plating on minimal-agarose medium spread with this herbicide and selecting the colonies surrounded by a clear thin halo. One strain was characterized and identified as an Arthrobacter sp. It metabolized diuron and the final transformation product, 3,4-dichloroaniline, was produced in stoichiometric amounts. The transformation of diuron at different concentrations was more efficient in the presence of alternative sources of carbon and nitrogen. The bacterial activity was also evaluated in soil microcosms with a consequent disappearance of diuron and concomitant appearance of 3,4-dichloroaniline, of which the concentration decreased thereafter. Bacterial cells inoculated in the microcosms survived as viable but eventually nonculturable cells.     

Short and long-term effects of clofibric acid and diclofenac on certain biochemical and ionoregulatory responses in an Indian major carp, Cirrhinus mrigala

Extensive use of pharmaceuticals in human and veterinary medicine and aquaculture practices pose a serious threat to aquatic organisms. In the present investigation, Cirrhinus mrigala an Indian major carp was exposed to different concentrations of clofibric acid (CA) and diclofenac (DCF) and certain biochemical and ionoregulatory responses were assessed under short and long term exposures. During short-term (96 h) exposure period, plasma glucose and sodium (Na⁺) levels were increased at all concentrations (1, 10 and 100 μg L⁻¹) of CA and DCF treated fish. Plasma protein and chloride (Cl⁻) levels were found to be decreased at all concentrations of CA and DCF exposed fish comparatively to control groups. Meanwhile an increase in plasma potassium (K⁺) level was noted in fish exposed to CA treatments alone and in DCF treatments it was decreased. In long-term exposure (35 d), plasma Na⁺ and Cl⁻ levels were found to be significantly increased at all concentration of CA and DCF. However, a biphasic trend was observed in plasma glucose, protein and K⁺ levels. In both the treatments, a significant (P < 0.01 and P < 0.05) changes were observed in all parameters measured in fish exposed to different concentrations of CA and DCF. The results of the present investigation indicate that both the drugs caused significant changes in biochemical and ionoregulatory responses of fish at all concentrations. The alterations of these parameters can be useful in monitoring of pharmaceutical residues present in aquatic environment.     

Exploitation of subabul stem lignin as a matrix in controlled release agrochemical nanoformulations: a case study with herbicide diuron

The utilization of nanomaterials in the domain of agriculture is at an inception, especially in the development of controlled release agrochemical nanoformulations. The present study demonstrated the potential of subabul stem lignin as a matrix material in agrochemical formulations using nanotechnology. In this study, “nanoprecipitation” method was employed and “optimized” to fabricate a stable herbicide, “diuron nanoformulation” (DNF). “Optimized DNF” (ODNF) has 5.17?±?0.49 % diuron loading efficiency (DLE) and 74.3?±?4 % encapsulation efficiency (EE). The size of nanoparticles in ODNF was 166?±?68 nm as revealed by FESEM/TEM studies. Physicochemical characterization of ODNF by UV, FT-IR, and DSC studies revealed the successful loading of diuron within the lignin matrix. The ODNF exhibited nonlinear biphasic release profile for diuron. Further, the bioefficacy of diuron released from ODNF was tested using canola (Brassica rapa). B. rapa seedlings grown in the soil supplemented with ODNF showed early signs of leaf chlorosis and mortality when compared with seedlings grown in the presence of commercial diuron formulation (CDF) or bulk diuron (BD), respectively. This study not only revealed the exploitation of subabul stem lignin as a “matrix” in the controlled release nanoformulation of diuron but also opened up new avenues for utilizing it as matrix for several other agrochemicals associated with the growth and development of the plant.     

Cytogenetic status of human lymphocytes after exposure to low concentrations of p,p'-DDT, and its metabolites (p,p'-DDE, and p,p'-DDD) in vitro

Despite that the use of DDT has been restricted for more than 40 years to malaria affected areas, low doses of this pesticide and its metabolites DDE and DDD can be found in the environment around the world. Although it has been shown that these pollutants induce cell and DNA damage, the mechanisms of their cytogenotoxic activity remains largely unknown. This study looks into their possible genotoxic effects, at doses that can be found in body fluids, on human lymphocytes using the cytokinesis-block micronucleus assay and the comet assay. After exposure for 1, 6, and 24 h compounds p,p′-DDT (0.1 μg mL⁻¹), p,p′-DDE (4.1 μg mL⁻¹), and p,p′-DDD (3.9 μg mL⁻¹) showed increase in DNA damage. The most significant results were observed at exposure period of 24 h where number of micronucleated cells increased from control 2.5 ± 0.71 to 23.5 ± 3.54, 13.5 ± 0.71, and 16.5 ± 6.36 for DDT, DDE, and DDD, respectively. Similar effect was observed using comet test where the percentage of DNA in comets tail increased from control 1.81 ± 0.16 to 17.24 ± 0.55, 11.21 ± 0.56 and 9.28 ± 0.50 for each compound, respectively. At the same time Fpg-comet assay failed to report induction of oxidative DNA damage of these pollutants. Additionally, the type of cell death was determined using diffusion assay and necrosis dominated. Our findings suggest that even at low concentrations, these pesticides could induce cytogenetic damage to human peripheral blood lymphocytes and in that manner have the impact on human health as well.     

Sorption and desorption kinetics of diuron, fluometuron, prometryn and pyrithiobac sodium in soils

The sorption and desorption characteristics of four herbicides (diuron, fluometuron, prometryn and pyrithiobac-sodium) in three different cotton growing soils of Australia was investigated. Kinetics and equilibrium sorption and desorption isotherms were determined using the batch equilibrium technique. Sorption was rapid (> 80% in 2 h) and sorption equilibrium was achieved within a short period of time (ca 4 h) for all herbicides. Sorption isotherms of the four herbicides were described by Freundlich equation with an r2 value > 0.98. The herbicide sorption as measured by the distribution coefficient (Kd) values ranged from 3.24 to 5.71 L/kg for diuron, 0.44 to 1.13 L/kg for fluometuron, 1.78 to 6.04 L/kg for prometryn and 0.22 to 0.59 L/kg for pyrithiobac-sodium. Sorption of herbicides was higher in the Moree soil than in Narrabri and Wee Waa soils. When the Kd values were normalised to organic carbon content of the soils (Koc), it suggested that the affinity of the herbicides to the organic carbon increased in the order: pyrithiobac-sodium < fluometuron < prometryn < or = diuron. The desorption isotherms were also adequately described by the Freundlich equation. For desorption, all herbicides exhibited hysteresis and the hysteresis was stronger for highly sorbed herbicides (diuron and prometryn) than the weakly sorbed herbicides (fluometuron and pyrithiobac-sodium). Hysteresis was also quantified as the percentage of sorbed herbicides which is not released during the desorption step (omega = [nad/nde - 1] x 100). Soil type and initial concentration had significant effect on omega. The effect of sorption and desorption properties of these four herbicides on the off-site transport to contaminate surface and groundwater are also discussed in this paper.