Concentration Of Diquat Research Articles

Rapid and sensitive quantification of paraquat and diquat in human serum by liquid chromatography/time-of-flight mass spectrometry using atmospheric pressure photoionization

We developed a rapid and sensitive liquid chromatography/time-of-flight mass spectrometry (LC/TOF–MS) method using atmospheric pressure photoionization (APPI) for the determination of paraquat and diquat in human serum. Serum samples were extracted with aqueous formic acid and acetonitrile. After vortexing and centrifugation, the supernatants were filtered with ultrafiltration cartridges followed by APPI-LC/TOF–MS analysis using a hydrophilic interaction chromatography analytical column. The total amount of time required for analyzing serum samples was ≤20 min. Calibration curves using solvent standards were linear in the range of 0.0005–1.25 μg/ml. The intraday recoveries (n = 6) for paraquat and diquat added to human serum at 0.1 μg/ml were 99.0 and 91.9 %, respectively, with relative standard deviations of 5.8 and 6.5 %. The limits of detection calculated at a signal-to-noise ratio of 3 were 0.005 μg/ml for paraquat and 0.006 μg/ml for diquat. This method was applied in the analysis of four autopsy cases involving suspected paraquat intoxications. The concentration of paraquat and diquat in serum ranged from <0.005 to 72 μg/ml.

Studies on Degradation of Diquat Pesticide in Aqueous Solutions Using Electrochemical Method

The C/PbO2 electrode assisted electrochemical removal of diquat dibromide herbicides solutions has been the subject of the present investigation under several operating conditions. The optimum conditions of the treatment process are: current density of 150 mA/cm2, pH 2.2, NaCl concentration 2 g/L, temperature of 10?C and initial diquat concentration of 50 mg/L. The time of electrolysis is 60 min for degradation rate of diquat and chemical oxygen demand (COD) removal is 210 min. The results were obtained by UV-Vis spectrophotometer and the present designed electrode was coincident.

Manejo químico de Eichhornia crassipes e Brachiaria subquadripara com Diquat em condições de reservatório

Este trabalho teve como objetivo avaliar a eficiência do herbicida diquat no controle de plantas de Eichhornia crassipes e Brachiaria subquadripara em condições de reservatório. As parcelas experimentais apresentavam 650 m² e foram delimitadas e posicionadas por redes de pesca nas margens do reservatório de Salto Grande, Americana-SP. Os tratamentos testados foram: herbicida diquat aplicado na formulação Reward, nas doses de 960 g i.a. ha-1 (duas aplicações de 480 g, com intervalo de 15 dias), 960 g i.a. ha-1 (aplicação única), 1.920 g i.a. ha-1 (duas aplicações de 960 g, com intervalo de 15 dias), além de uma testemunha sem aplicação do herbicida. Para monitoramento das concentrações de diquat, foram coletadas amostras de água antes da aplicação do herbicida e 1, 2, 4, 7, 14 e 28 dias após aplicação (DAA) na área experimental e na montante e jusante da barragem. A análise da eficiência do diquat foi realizada através de avaliações visuais de controle no período (1, 2, 4, 7, 14, 21 e 28 DAA do herbicida) e aos dois dias após a segunda aplicação. O herbicida diquat mostrou-se eficiente no controle das plantas de E. crassipes, independentemente da dose e do manejo de aplicação, e seu efeito sobre as plantas de B. subquadripara foi temporário.

Effects of diquat and fomesafen applied alone and in combination with a nonylphenol polyethoxylate adjuvant on Lemna minor in aquatic indoor microcosms

The influence of tank-mix adjuvants on pesticide toxicity remains largely unknown. Agral ® 90, a nonylphenol polyethoxylated tank-mix adjuvant, has been used with diquat (bipyridylium herbicide) and fomesafen (diphenyl-ether herbicide) in aquatic indoor microcosms in order to compare the toxicity of the single compounds and of binary herbicide–adjuvant mixtures to Lemna minor. Twenty-four microcosms were used and treatments were performed with substances alone or with herbicide–adjuvant binary mixtures, at two concentrations levels (44.4 and 222.2 μg/L for the herbicides, and 100 and 500 μg/L for Agral 90). Toxicity was assessed weekly for 1 month through growth measurements, as inferred from the relative frond number (RFN) and relative frond area (RFA). Concentrations of diquat and fomesafen in water and sediments were measured weekly. The herbicides showed very different behaviour in microcosms, with a rapid disappearance of diquat from the aqueous phase whereas fomesafen levels remained almost constant over time. Diquat strongly inhibited the growth of L. minor whereas fomesafen had no effect on plant growth. Presence of the adjuvant only slightly reduced the effect of the lowest concentration of diquat, probably as a result of dispersion of the herbicide at the water surface. It is concluded that tank-mix adjuvant designed to improve herbicide efficiency in the terrestrial environment did not have any effect on aquatic plants when applied to the aquatic environment.

A carbon paste electrode modified with kaolin for the detection of diquat

A carbon paste electrode modified with kaolin was employed for the quantification of diquat from aqueous solutions. The new electrode (K-CPE) revealed interesting electroanalytical detection of diquat based on the adsorption of this herbicide onto kaolin under open circuit conditions. The diquat reduction peaks were observed around − 0.69 V and − 0.97 V respectively for peaks P 1 and P 2 (vs. SCE) in 0.1 mol L − 1 K 2SO 4 using square wave voltammetry. The response depends on the concentration of diquat in the bulk solution as well as the parameters involved in the preconcentration, pH and the measurement steps. The best results were obtained under the following optimized conditions: 5 min accumulation time, 5 mV pulse amplitude, 1 mV s − 1 scan rate in 0.1 mol L − 1 potassium sulfate. Using such parameters a linear dynamic range up 80 mol L − 1 diquat was observed with a detection and quantification limits of 4.21 × 10 − 9 mol L − 1 and 3.55 × 10 − 8 mol L − 1 respectively. The recovery (I%) was obtained by spiking natural water with 2 × 10 − 5 mol L − 1 diquat.

The in vivo gene expression signature of oxidative stress

How higher organisms respond to elevated oxidative stress in vivo is poorly understood. Therefore, we measured oxidative stress parameters and gene expression alterations (Affymetrix arrays) in the liver caused by elevated reactive oxygen species induced in vivo by diquat or by genetic ablation of the major antioxidant enzymes CuZn-superoxide dismutase (Sod1) and glutathione peroxidase-1 (Gpx1). Diquat (50 mg/kg) treatment resulted in a significant increase in oxidative damage within 3-6 h in wild-type mice without any lethality. In contrast, treatment of Sod1(-/-) or Gpx1(-/-) mice with a similar concentration of diquat resulted in a significant increase in oxidative damage within an hour of treatment and was lethal, i.e., these mice are extremely sensitive to the oxidative stress generated by diquat. The expression response to elevated oxidative stress in vivo does not involve an upregulation of classic antioxidant genes, although long-term oxidative stress in Sod1(-/-) mice leads to a significant upregulation of thiol antioxidants (e.g., Mt1, Srxn1, Gclc, Txnrd1), which appears to be mediated by the redox-sensitive transcription factor Nrf2. The main finding of our study is that the common response to elevated oxidative stress with diquat treatment in wild-type, Gpx1(-/-), and Sod1(-/-) mice and in untreated Sod1(-/-) mice is an upregulation of p53 target genes (p21, Gdf15, Plk3, Atf3, Trp53inp1, Ddit4, Gadd45a, Btg2, Ndrg1). A retrospective comparison with previous studies shows that induction of these p53 target genes is a conserved expression response to oxidative stress, in vivo and in vitro, in different species and different cells/organs.

Efeito do período de exposição a concentrações de diquat no controle de plantas de Egeria densa, Egeria najas e Ceratophyllum demersum

O período de permanência do herbicida na água pode ser influenciado pelo fluxo da água nos reservatórios e pela adsorção a partículas de argilas em suspensão, bem como pela degradação luminosa e por microrganismos. Objetivou-se com este trabalho avaliar diferentes períodos de exposição a concentrações do herbicida diquat no controle de Egeria densa, Egeria najas e Ceratophyllum demersum. O delineamento experimental utilizado foi o inteiramente casualizado, com quatro repetições, em esquema fatorial 6 x 5, mais uma testemunha. Foram testados seis períodos de exposição das plantas (30, 60, 120, 240, 480 e 960 minutos) a cinco concentrações do herbicida diquat (0,075; 0,15; 0,3; 0,6; e 1,2 ppm produto comercial Reward 240 g L ¹). As avaliações de controle das plantas daninhas imersas foram visuais e, no final do experimento, foi avaliada a massa seca das plantas, para determinar a porcentagem de redução da biomassa. Observou-se que apenas 30 minutos de exposição das espécies imersas E. densa e C. demersum à concentração de 0,075 ppm foi suficiente para proporcionar redução da massa seca em ambas as espécies. Para controle de E. najas aos 7 DAA houve necessidade de um período maior que 120 minutos de exposição, considerando a mesma concentração do herbicida. Esses resultados evidenciam o potencial de uso do diquat no controle de plantas daninhas aquáticas imersas em locais que apresentam rápida renovação de água.

Documentation of landoltia (Landoltia punctata) resistance to diquat

Landoltia was collected and cultured from a canal in Lake County, Florida, where diquat was used repeatedly during the past 20–30 yr for duckweed control. Recent applications of diquat failed to provide adequate control of duckweed, and a new commercial formulation of diquat was suspected. The new formulation was not the cause of reduced efficacy. Static exposures (48 h) to various concentrations of diquat were used to compare the susceptibility of the Lake County landoltia accession to one never exposed to diquat. These static tests indicated that landoltia, from a population with no prior history of herbicide treatment, was extremely susceptible to diquat. The accession from Lake County, FL had developed resistance to diquat, and was also cross resistant to paraquat. The resistance factor was 50 for diquat and 29 for paraquat. The Lake County accession also exhibited reduced ion leakage after diquat exposure under light and dark conditions. This suggests the resistance mechanism to the bipyridylium herbicides in landoltia is independent of photosynthetic electron transport. This research documents the first aquatic plant species that has developed resistance to the bipyridylium herbicides.

Induction of Phenotypes Resembling CuZn-Superoxide Dismutase Deletion in Wild-Type Yeast Cells: An in Vivo Assay for the Role of Superoxide in the Toxicity of Redox-Cycling Compounds

Yeast (Saccharomyces cerevisiae) lacking the enzyme CuZn-superoxide dismutase (sod1delta) display a large number of dioxygen sensitive phenotypes, such as amino acid auxotrophies, sensitivity to elevated temperatures, and sensitivity to 100% dioxygen, which are attributed to superoxide stress. Such cells are exquisitely sensitive to small amounts of the herbicide paraquat (methyl viologen), which is known to produce high fluxes of superoxide in vivo via a redox-cycling mechanism. We report that dioxygen sensitive phenotypes similar to those seen in sod1delta cells can be induced in wild-type cells by treatment with moderate concentrations of paraquat or diquat, another bipyridyl herbicide, providing strong evidence that the mechanism of toxicity for both of these compounds is attributable to superoxide stress. Certain redox-cycling quinone compounds (e.g., menadione and plumbagin) are also far more toxic toward sod1delta than to wild type. However, treatment of wild-type yeast with menadione or plumbagin did not induce sod1delta-like phenotypes, although toxicity was evident. Thus, their toxicity in wild type cells is predominantly, but not exclusively, due to mechanisms unrelated to superoxide production. Further evidence for a different basis of toxicity toward wild-type yeast in these two classes of redox-cycling compounds includes the observations that (i) growth in low oxygen alleviated the effects of paraquat and diquat but not those of menadione or plumbagin and (ii) activity of the superoxide sensitive enzyme aconitase is affected by very low concentrations of paraquat but only by higher, growth inhibitory concentrations of menadione. These results provide the basis for an easy qualitative assay of the contribution of redox-cycling to the toxicity of a test compound. Using this method, we analyzed the Parkinsonism-inducing compound 1-methyl-4-phenylpyridinium and found that redox cycling and superoxide toxicity are not the predominant factor in its toxic mechanism.

Transgenic Mice Overexpressing Glutathione Peroxidase 4 Are Protected against Oxidative Stress-induced Apoptosis

Glutathione peroxidase 4 (Gpx4) is uniquely involved in the detoxification of oxidative damage to membrane lipids. Our previous studies showed that Gpx4 is essential for mouse survival and that Gpx4 deficiency makes cells vulnerable to oxidative injury. In the present study, we generated two lines of transgenic mice overexpressing Gpx4 (Tg(GPX4) mice) using a genomic clone containing the human GPX4 gene. Both lines of Tg-(GPX4) mice, Tg5 and Tg6, had elevated levels of Gpx4 (mRNA and protein) in all tissues investigated, and overexpression of Gpx4 did not cause alterations in activities of glutathione peroxidase 1, catalase, Cu/Zn superoxide dismutase, and manganese superoxide dismutase. The human GPX4 transgene rescued the lethal phenotype of null mutation of the mouse Gpx4 gene, indicating that the transgene can replace the essential role of mouse Gpx4 in mouse development. Cell death induced by t-butylhydroperoxide and diquat was significantly less in murine embryonic fibroblasts from Tg(GPX4) mice compared with wild type mice. Liver damage and lipid peroxidation induced by diquat were reduced significantly in Tg(GPX4) mice. In addition, diquat-induced apoptosis was decreased in Tg(GPX4) mice, as evidenced by attenuated caspase-3 activation and reduced cytochrome c release from mitochondria. These data demonstrate that Gpx4 plays a role in vivo in the mechanism of apoptosis induced by oxidative stress that most likely occurs through oxidative damage to mitochondrial phospholipids such as cardiolipin.

Carrier-mediated extraction of bipyridilium herbicides across the hydrophobic liquid membrane

Supported liquid membrane (SLM) method for preconcentration and enrichment of the two bipyridilium herbicides, namely diquat and paraquat, from environmental water samples has been developed. The permanently charged cationic herbicides were extracted from a flowing aqueous solution to a stagnant acidic acceptor solution across a liquid membrane containing 40% (v/v) di-(2-ethylhexyl) phosphoric acid dissolved in di- n-hexyl ether. The mass transfer of analytes is driven by the counter-coupled transport of hydrogen ions from the acceptor to the donor phase. The efficiency of the extraction process depends on the donor solution pH, the amount of the mobile carrier added to the liquid membrane and the concentration of the counter ion in the acceptor solution. The applicability of the method for extraction of these quaternary ammonium herbicides from environmental waters was also investigated by spiking analyte sample solutions in river water. With 24 h sample enrichment concentrations of diquat and paraquat down to ca. 10 ng/L could be detected in environmental waters.

Carrier-mediated extraction of bipyridilium herbicides across the hydrophobic liquid membrane

Supported liquid membrane (SLM) method for preconcentration and enrichment of the two bipyridilium herbicides, namely diquat and paraquat, from environmental water samples has been developed. The permanently charged cationic herbicides were extracted from a flowing aqueous solution to a stagnant acidic acceptor solution across a liquid membrane containing 40% (v/v) di-(2-ethylhexyl) phosphoric acid dissolved in di- n -hexyl ether. The mass transfer of analytes is driven by the counter-coupled transport of hydrogen ions from the acceptor to the donor phase. The efficiency of the extraction process depends on the donor solution pH, the amount of the mobile carrier added to the liquid membrane and the concentration of the counter ion in the acceptor solution. The applicability of the method for extraction of these quaternary ammonium herbicides from environmental waters was also investigated by spiking analyte sample solutions in river water. With 24 h sample enrichment concentrations of diquat and paraquat down to ca. 10 ng/L could be detected in environmental waters.

EFFECTS OF DIQUAT, AN AQUATIC HERBICIDE, ON THE DEVELOPMENT OF MALLARD EMBRYOS

Bipyridylium herbicides produce embryotoxic and teratogenic effects in dipteran, amphibian, avian, and mammalian organisms. Diquat dibromide, a bipyridylium compound, is commonly used as an aquatic herbicide. Mallard (Anas platyrhynchos) eggs were exposed to diquat by immersing the eggs for 10 s in solutions of 0.88, 3.5, 7, 14, or 56 g/L on either d 4 or 21 of incubation. Application of diquat on d 4 yielded an estimated LC50 of 19.5 g/L through 18 d of incubation, and 9.6 g/L through hatching. Body and organ weights, and bone lengths of hatchlings did not differ between control and treatment groups with the exception of a slight increase in brain weight in the 14 g/L group. Malformations in diquat-treated embryos included defects of the brain, eye, bill, limb, and pelvis; skeletal scoliosis; and incomplete ossification. Subcutaneous edema was also present. Significant manifestations of oxidative stress were apparent in hatchlings and included increased hepatic thiobarbituric acid-reactive substances (TBARS) (lipid peroxidation) and decreased brain reduced glutathione (GSH). Brain protein-bound sulfhydryls (PBSH) increased. Diquat applied on d 21 of incubation yielded an estimated LC50 of 12.6 g/L through hatching. Exposure at this late stage of development did not produce deformities. Body and organ weights and, bone lengths of hatchlings did not differ between control and treatment groups. Significant manifestations of oxidative stress in hatchlings included decreased brain GSH, increased oxidized glutathione (GSSG), and ratio of GSSG to GSH. This study suggests that concentrations of diquat commonly used for aquatic weed control, when based upon the dilution effect of average water depth of the application area, would probably have little impact on mallard embryos. However, concentrations applied above ground to weeds and cattails along ditches could adversely affect the survival and development of mallard embryos, and presumably other avian species nesting in such habitats.

A new diquat derivative appropriate for colourimetric measurements of biological materials in the presence of paraquat.

A new colourimetric method is described for the quantification of diquat using a yellow-coloured derivative produced by heating diquat in alkaline solution at 80 degrees C. The absorption maximum of the yellow derivative is 420 nm and the molar absorption coefficient is 2.76 x 10(4) (0.15 in 1 microgram diquat/ml with 1 cm light path). The absorption at 420 nm shows a linear concentration dependence in the range 0.1-10 micrograms/ml and fading of the colour is about 5% after 1 h. Under the same conditions, paraquat does not produce any coloured products. The concentration of diquat in the solution containing both diquat and paraquat can be determined by the absorption of diquat derivative at 420 nm without interference from paraquat. By adding sodium dithionite to the solution the concentration of paraquat can be determined by the absorption of paraquat radicals at 600 nm without interference from diquat, because the yellow derivative does not react with dithionite. This yellow diquat derivative can be extracted completely with cyclohexanol by saturating the solution with Na2SO4. The absorption maximum in cyclohexanol shifts to 440 nm with the same molar absorbance and the same half-band width as in water. Fading of the colour is less than 5% after 24 h in cyclohexanol. Perchloric acid (3%) and trichloroacetic acid (4.5%) which are often used for deproteinization of tissue homogenates, do not inhibit production of the coloured derivative at pH 13.5 or extraction of the derivative with cyclohexanol. This method is suitable for a quick determination of small amounts of diquat in tissues, since the extraction with cyclohexanol not only concentrates the derivative rapidly but also quite efficiently eliminates the coloured substances in tissue homogenates. The detection limit of diquat is 0.02 microgram/ml for blood and 0.05 microgram/g for liver when 1 ml or 1 g is used for analysis. In three human cases of fatal intoxication, both paraquat and diquat were quantified using 50 microliters of serum. In non-toxic dosing of diquat to rats for 14 days, the diquat level was highest in the spleen followed by the kidneys.

Sensitive determination of diquat by a kinetic method using the stopped-flow mixing technique.

A simple, sensitive, selective, fast and inexpensive assay for the determination of diquat is proposed. The method is based on the reduction of the herbicide to a strongly fluorescent monocation radical with sodium dithionite. The initial rate of this reaction is directly proportional to the diquat concentration. The stopped-flow mixing technique was used because the kinetic data can be obtained in only 7 s, meaning that the method can be automated. The calibration graph is linear over the range 5-500 ng ml-1 and the precision (RSD) is close to 1.2%. The applicability of the method was demonstrated by determining the herbicide in different kinds of samples.

Simple method for analysis of diquat in biological fluids and tissues by high-performance liquid chromatography

A simple HPLC method has been described to quantify diquat in biological fluids and tissues. This method permits separation and quantification of diquat from blood, bile, urine, liver and kidney. It does not require special pretreatment of the samples prior to analysis, nor a specially prepared analytical column. Various concentrations of diquat were added (10–300 nmol/ml or g) to fluids or tissues. Analysis of blank samples revealed no substrates that interfere with diquat elution. Excellent recovery (95–105%) was obtained. Diquat (120 μmol/kg, i.v.) was injected to rats and quantified in bile, blood and liver. Concentration of diquat was higher in blood and bile than liver. Therefore, this method is applicable for quantification of diquat in toxicological samples, and may be used to determine structurally similar compounds such as paraquat.

Disposition and toxicokinetics of diquat in channel catfish

The disposition of the aquatic herbicide diquat was studied in channel catfish ( Ictalurus punctatus) after water exposure to 14C-diquat dibromide concentrations of 5 and 20 μg/ml for up to 6 days. An apparent steady-state plasma concentration of 0.6% of the exposure water concentration was achieved after 24 h, and steady-state tissue levels were reached by 72 h. The highest steady-state concentration of diquat occurred in the trunk kidney, which was about 100 times that observed in plasma. Diquat concentrations in white muscle were low and similar to plasma levels of diquat. Autoradiographs of sagittal sections of a catfish exposed to 14C-diquat dibromide also indicated that the highest concentration of residue present in the animal was located in the trunk kidney and that lower concentrations were associated with the liver and gills. The majority of liver residue, and especially that in the bile, was unidentified metabolites. After intravascular administration of 1 mg/kg, toxicokinetic analysis of the plasma concentration-time profile of diquat using a two-compartment model provided the following values: steady-state volume of distribution (V ss) = 2920 ± 740 ml kg −1; total body clearance (Cl b) = 87.8 ± 27 ml h −1 kg −1 and elimination halflife (t 1 2 ,β ) = 35.8 ± 8.9 h .

The Toxicity of Diquat, Endothall, and Fluridone to the Early Life Stages of Fish

ABSTRACT While most aquatic herbicides have undergone some toxicity testing for effects on non-target aquatic organisms, little of this testing has been conducted on early life stages of gamefish found in lakes undergoing treatment. Commercial formulations of diquat, endothall, and fluridone were selected for acute toxicity testing using very early life stages of walleye (Stizostedion vitreum), largemouth bass (Micropterus salmoides), and smallmouth bass (Micropterus dolomieu). In addition, the rates of diquat photodegradation and uptake by sediment were determined. These results were used to predict diquat concentrations in lakes of various depths. The results of the toxicity tests were compared to the predicted concentrations. Diquat, with 96-h LCSOs of 0.74–4.9 mg/L, was more toxic to these early life stages than endothall or fluridone, with 96-h LC50s of 16–130 mg/L and 1.8–13 mg/L respectively. The LC50s for endothall and fluridone were at least one order of magnitude greater than the labeled application concentrations. As the LC50s for diquat were very close to the predicted concentration, the safety margin for the use of diquat appears to be very small.

Evidence for redox cycling of diquat in rat small intestine

It has previously been established that acute diquat (1,1′-ethylene, 2,2′-bipyridilium) toxicity in the rat is associated with stimulation of net fluid secretion into the gastrointestinal tract. We have examined the possibility that the mechanism of diquat toxicity in the small intestine involves redox cycling of the bipyridyl leading to a disturbance of biochemical function and oxidative stress. Experiments performed in vitro showed that diquat (10 μM to 1 mM) produced an increase in activity of the pentose phosphate pathway in rat small intestinal tissue slices, suggesting that there was oxidation of NADPH even at concentrations of diquat which do not cause intestinal fluid secretion in anaesthetized rats. When the effect of diquat on pentose phosphate activity was measured in rats in situ at a dose which causes maximal fluid secretion [50 mM diquat dibromide (DQBr 2)], production of 14CO 2 from [1- 14C]-glucose increased by 278±28% (N = 4) within 1 hr of exposure to diquat. Under these same conditions, the tissue content of NADPH in the proximal small intestine was significantly depleted, though there was no corresponding increase in NADP + concentration. Diquat had no effect on tissue concentrations of either the reduced or oxidized forms of NAD. It is likely that NADPH oxidation at low diquat concentrations can be adequately compensated for by mechanisms within the tissue which protect against oxidative stress. However, the data also suggest that diquat-induced fluid secretion in the rat small intestine is associated with redox cycling of bipyridyl leading to depletion of NADPH.

Different distribution of paraquat and diquat in human poisoning cases after ingestion of a combined herbicide.

This report describes a slight difference in the rate of decrease of serum paraquat and diquat concentrations in eight human cases of poisoning by the herbicide PreegloxL (containing paraquatCl2, 5% and diquatBr2, 7%) and the distribution of each in three autopsied cases. There was no variation between the serum concentrations of paraquat and diquat within 24 h after ingestion, but paraquat remained at a slightly higher concentration than diquat after more than 24 h. The decrease of urinary paraquat and diquat concentrations was almost the same during the 24-h determination period. In three autopsied cases, diquat concentrations in the tissues were relatively lower than those of paraquat, except in bile. Paraquat and diquat were unevenly distributed in various tissues and fluids, but the distribution patterns of each in any particular tissues were quite similar. As no difference was observed in the decrease of urinary paraquat and diquat, the much higher concentration of diquat in bile indicates that bile may be one of the effective factors in lowering the concentration of diquat in serum and in tissues of the human body long after ingestion.