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Biomedical subjects

D G Crosby

Publications and source records attributed to D G Crosby.

At least 19 recordsLinked to original sources

Fate and kinetics of carfentrazone-ethyl herbicide in California, USA, flooded rice fields.

Little is known of the environmental fate of the aryltriazolinone herbicide carfentrazone-ethyl (compound I). Rice field applications of Shark 40D commercial formulation to duplicate 5.7 m2 rings (119 g a.i./ha) and 464 m2 commercial basins (224 g a.i./ha) produced pseudo-first-order half-lives (t1/2) of 6.5 to 11.1 h in water and 37.9 to 174 h in sediment. The rapid dissipation from water was due to its hydrolysis to the chloropropionic acid (compound II), which further degraded to its propionic, cinnamic, and benzoic acids. Compound I degraded similarly in soil, but propionic and cinnamic acid levels were higher. Compound I was only weakly adsorbed, but lateral movement of compound II through soil occurred. Laboratory hydrolysis produced quantitative yields of compound II, t1/2 values of 131 h at pH 7 and 3.36 h at pH 9, and slow dissipation at pH 5 (43% at 830 h). Ultraviolet (UV) irradiation of compound I in pH 7 buffer gave dissipation rates similar to those in dark controls (t1/2 113 h vs 128 h), while compound II was comparatively stable to photolysis (t1/2 765 h) and also did not volatilize from water. Ester hydrolysis followed by off-site movement of the acid (compound II) account for the dissipation of compound I.

Agriculture↗

Abiotic processes influencing fipronil and desthiofipronil dissipation in California, USA, rice fields.

Fipronil insecticide dissipated in California rice fields, producing half-lives of 10.5 to 125 h in water and 44.5 to 533 h in soil, depending on the formulation applied and the resulting differences in water solubility. The major degradation products were desthiofipronil in water and fipronil-sulfide in soil, while the sulfone and amide were less abundant. Fipronil was photolyzed rapidly to desthiofipronil in deionized water in the laboratory (t1/2 = 7.97-9.42 h) and even faster in the presence of H2O2 (t1/2 = 0.874-4.51 h). Fipronil was also hydrolyzed to amide in base (t1/2 = 542 h at pH 9) and volatilized slowly from water (H = 6.60 x 10(-6) m3.atm/mol), properties not explaining its rapid field water dissipation. Desthiofipronil was more stable than fipronil to direct photolysis (t1/2 = 120-149 h), was indirectly photolyzed in the presence of H2O2 (t1/2 = 0.853-3.76 h), and was nonvolatile from water. The desthiofipronil observed in field water was formed photochemically from fipronil, accumulated due to slower photolysis and lack of volatility from water, but eventually dissipated.

California↗

Optimized procedures for analyzing primary alkylamines in wines by pentafluorobenzaldehyde derivatization and GC-MS.

Biogenic primary alkylamines in wines are toxicologically significant and affect sensory properties. An optimized method for analysis in wines involving derivatization with pentafluorobenzaldehyde (PFB) to corresponding pentafluorobenzylimines, liquid-liquid extraction, and gas chromatography with mass selective detection is presented. Reaction parameters including pH, temperature, time, and derivatizing agent and amine concentration were varied in simulated wine solution (15% ethanol) to determine effect on reaction efficiency. Optimal reaction efficiency was characterized (pH 12, 24 degrees C, 30 min, and 10 mg/mL PFB), and parameters were used for the analysis of 10 biogenic alkylamines in 12 California wines. Alkylamine concentration in wines ranged from 0.048 to 91 mg/L. Amine recoveries from wines at five fortification levels (0.1-85 mg/L) were generally 81-100%.

Amines↗

Elucidation of fipronil photodegradation pathways.

The phenylpyrazole insecticide fipronil (I) photolyzes to its desthio product (II) in aqueous solution. However, the necessity of an intervening oxidation to a sulfone intermediate (III) has not been resolved, and the photodegradation products of II have not been identified. Using GC-MS, HPLC-UV/vis, electrospray MS, (19)F NMR, and GC-TSD, our objective was to characterize the photodegradation pathways of I, which would clarify the role of III, identify products of II, and explain unbalanced mass accounts in previous studies. Findings showed that II is formed directly and photochemically from I, confirmed by the greater stability of III (t(1/2) 112 h), and that successive oxidations of I to III and then a sulfonate (IV) comprise a second pathway. Compound II underwent photodechlorination, substitution of chlorine by trifluoromethyl, and pyrazole ring cleavage. This work is significant to understanding the photochemistry of novel phenylpyrazole pesticides in the environment.

Gas Chromatography-Mass Spectrometry↗

Environmental fate of rice pesticides in California.

Each of the pesticides reviewed is reported to dissipate from field water after application. Carbofuran is hydrolyzed rapidly under the alkaline conditions usually found in the rice field environment, and its hydrolysis products are also degraded rapidly. The longest half-life reported (18-26 d) was in water that overlaid soil treated with Furadan granular formulation. Generally, carbofuran dissipation ranged from 36 hr to 3 d. Under field application, bensulfuron methyl showed a half-life of 1-3 d, but others have recovered all of the "dissipated" herbicide in the soil compartment. MCPA applied to rice fields is reportedly degraded by the joint action of sunlight and microbial action with a half-life of 3-5 d. Methyl parathion showed a maximum half-life of 9-17 d in a model aquatic ecosystem, but other reports found more rapid dissipation. The half-life of molinate has been observed by numerous researchers to be less than 5 d, with volatility the major route of loss. A half-life as short as 5-7 d has been reported for thiobencarb applied to rice fields, but others report much longer periods; volatility again is expected to be a significant route of loss. Microbial degradation takes place with each of the subject pesticides. Numerous authors have reported enhanced degradation of carbofuran under conditions of repeated application, and this probably holds true for the others. A specialized segment of the microbial population (Pseudomonas spp.) is purported to carry out most of the degradation but is inefficient at degrading the hydrolysis product, carbofuran phenol. Biodegradation of bensulfuron methyl has been observed with actinomycetes, fungi, and bacteria, and takes place primarily by oxidation and hydrolysis. Methyl parathion is biodegraded primarily by nitro reduction to aminomethyl parathion. A fungus, an actinomycete, and a bacterium were shown to biodegrade molinate, primarily by oxidation at the sulfur atom and the azepine ring. Thiobencarb is biodegraded in anaerobic sediments at a slow rate; the dechlorinated thiobencarb was shown to cause dwarfing of rice in some fields. Otherwise, its aerobic biodegradation is rapid and follows the same routes as with molinate. Carbofuran is a systemic insecticide that is rapidly absorbed and translocated to aerial parts of the plant. Carbofuran is metabolized in rice plants to the corresponding phenol, which is irreversibly bound into the plant, as well as to 3-hydroxycarbofuran and other minor components; it is depurated through leaf exudate, from which it volatilizes. Rice plants were observed to take up more bensulfuron methyl through shoots than roots and to metabolize it to the 4-hydroxy analog. The half-life of methyl parathion in Hydrilla verticulla, an aquatic macrophyte, was 1 wk, but little has been reported on methyl parathion in plants. Barnyardgrass was found to absorb greater amounts of molinate than did rice, and it produced larger proportions of basic metabolites, which may form the basis for its selective toxicity. Thiobencarb has been shown to be rapidly absorbed, translocated, and metabolized in rice plants, barnyardgrass, and the broadleaved wild amaranth, smartweed, and lambsquarters. Translocation was more rapid and extensive in barnyardgrass than in rice, and most of the 14C radiolabel was recovered as metabolites. Its terminal metabolite, chlorobenzoic acid, was taken up into lignin-like plant constituents. It is apparent that information on plant uptake and biodegradation is limited--none exists for woody species--but the fact that some species appear resistant to the herbicides suggests that biodegradative ability is general. (ABSTRACT TRUNCATED)

2-Methyl-4-chlorophenoxyacetic Acid↗

Disposition and biotransformation of pentachlorophenol in the red abalone (Haliotis rufescens).

1. The disposition and biotransformation of pentachlorophenol (PCP) in the red abalone (Haliotis rufescens) have been determined. 2. In a flow-through system, three abalones were exposed to 1.2 mg/l of [U-14C]PCP for 5 h to determine bioconcentration and tissue distribution. Retained residues were quantified from radioactivity, while excreted residues were identified and quantified by h.p.l.c. and determination of radioactivity. 3. The 5-h total concentration factor ranged from 16.0 to 21.5; individual tissue concentrations ranged from 133.4 nmol/g in gill to 17.5 nmol/g in gonad. Due to its large size, the foot muscle received the largest amount of total retained residue (47.4%). 4. During a 13-h recovery period the abalones depurated 72.2% of retained residues; however, residue concentration in gonad increased over 100%. PCP was primarily excreted unchanged (89.3%), but small amounts of pentachloro-beta-D-glucoside (7.9%), pentachloroanisole (1.3%), pentachlorophenylsulphate (0.9%), and tetrachloro-p-hydroquinone (0.6%) were also formed.

Animals↗

Sublethal effects of pentachlorophenol in the abalone (Haliotis rufescens) as measured by in vivo 31P NMR spectroscopy.

The sublethal biochemical effects of pentachlorophenol (PCP) were investigated in live, intact red abalones (Haliotis rufescens), using a flow-through exposure system, by in vivo 31P NMR spectroscopy. Based on rangefinding tests (6-hr LC50 = 1.6 mg/L; 6-hr no-observable-effect-level (NOEL) = 0.8 mg/L), three abalones were separately exposed to a sublethal concentration (1.2 mg/L) for 5 hr, followed by a 13 hr recovery period. Effects in foot muscle included both a decrease in phosphoarginine and an increase in inorganic monophosphate concentrations ([PA] and [Pi], respectively); both foot muscle concentrations of adenosine triphosphate [ATP] and intracellular pH (pHi) also declined. Parallel in vitro experiments revealed that concentrations of glycerol 3-phosphate, lactate, citrate, succinate, malate, and alanine (Ala) all increased, while those of glyceraldehyde 3-phosphate and glutamine (Gln) remained stable. Also, these effects were not evident until 2 hr into exposure, possibly the time required for PCP to attain an effective concentration in foot muscle. During recovery, while Pi declined to pre-exposure levels, [PA] completely recovered in only one individual. Also, realkalinization of pHi was similar to recovery of [Pi], and ATP returned to near-initial levels, as did glycerol 3-phosphate, lactate, succinate, malate, and Ala; glyceraldehyde 3-phosphate, citrate, and Gln levels declined. Recovery responses corresponded to the time for PCP clearance from foot muscle. The effects of PCP were similar to those of hypoxia, fatigue, hypersalinity, and arginine kinase inhibitors, and so sublethal PCP concentrations may also inhibit electron transport and arginine kinase as well as uncouple mitochondrial oxidative phosphorylation in intact molluscs. Thus, the effects of pollutants on key biochemical processes may now be measured in intact aquatic organisms as they occur, improving our ability to accurately assess the environmental effects of pollutants in the laboratory.

Animals↗

Comparative biotransformation of molinate (Ordram) in the white sturgeon (Acipenser transmontanus) and common carp (Cyprinus carpio).

1. Juvenile white sturgeon (Acipenser transmontanus) and common carp (Cyprinus carpio) were exposed to 100 micrograms/l [ring-14C]molinate in a flow-through metabolism system. Exposure was in three phases: acclimation (2 h), uptake (24 h), and depuration (24 h). 2. Excreted metabolites were collected on a macroreticular resin, and retained metabolites were extracted from homogenized fish tissue. Identification and quantification was by h.p.l.c. cochromatography (gradient conditions) and determination of 14C, and confirmation was by t.l.c. 3. 14C depuration (elimination) by common carp (77.8%) was significantly slower than that by white sturgeon (96.0%, P less than 0.01) or that previously reported for striped bass (90.5%, P less than 0.01). Differences in bioconcentration were not significant (P less than 0.05). 4. Common carp and white sturgeon oxidized molinate to form several products and hydrolysed, or conjugated with glutathione (GSH), the sulphoxide or sulphone; both fish also formed a D-glucuronic acid conjugate. 5. Common carp were significantly less capable of molinate sulphoxidation and GSH conjugation than either white sturgeon (P less than 0.01) or striped bass (P less than 0.05). 6. The higher toxicity of molinate in common carp may be due to greater bioconcentration, slower depuration, and less efficient metabolic deactivation.

Animals↗

Comparative metabolism of nitroaromatic compounds in freshwater, brackish water and marine decapod crustaceans.

1. The metabolic pathways of p-nitroanisole, 4-nitro-m-cresol and methyl parathion in Malaysian prawns (Macrobrachium rosenbergii), ridgeback prawns (Sicyonia ingentis) and crayfish (Procambarus clarkii) were compared. 2. The Malaysian prawns and ridgeback prawns were shown to O-demethylate 29% and 11%, respectively, of an accumulated level of p-nitroanisole, while crayfish were able to O-demethylate 98% of the accumulated level of nitroanisole. 4-Nitro-m-cresol oxidation was not detected in either prawn species. In contrast, 5-hydroxy-2-nitrobenzaldehyde was the major metabolite formed from nitrocresol metabolism by crayfish. 3. Both prawn species readily dearylated methyl parathion to form p-nitrophenol and p-nitrophenyl conjugates. Crayfish displayed a similar trend in methyl parathion metabolism. 4. Nitroreduction was observed in the metabolism of 4-nitro-m-cresol by ridgeback prawns, which excreted 4-nitroso-m-cresol as a minor product. Reduction products were not observed in the metabolism of the three substrates by Malaysian prawns or crayfish. 5. Conjugation was overall the dominant detoxication pathway observed in the decapods. Malaysian prawns conjugated p-nitrophenol and 4-nitro-m-cresol to form the corresponding beta-D-glucosides and sulphate monoesters. Ridgeback prawns formed beta-D-glucosides in small quantities, preferring conjugation of p-nitrophenol and 4-nitro-m-cresol to form sulphates and unknown conjugates through a unique conjugation pathway. Crayfish conjugated the phenolic substrates to form exclusively the beta-glucosides. 6. The unknown conjugates formed by ridgeback prawns had chromatographic properties similar to the corresponding beta-D-glucosides but were refractory to the deconjugation by alpha- or beta-glucosidase, beta-galactosidase, aryl sulphatase and beta-glucuronidase. Phenolic conjugation ability appeared to follow the order of ridgeback prawns greater than Malaysian prawns greater than crayfish.

Adsorption↗

Pesticide photoproducts: generation and significance.

As with the parent pesticide, the significance of a pesticide photoproduct depends on its concentration in a given environmental compartment, its toxicity, and exposure of the organism or ecosystem of interest. This requires an understanding of the production and environmental chemistry of each photoproduct as well as its toxicity. While these data are generally available for the parent pesticide, they are rarely determined in detail for the photoproducts. Although the environmental photochemistry of each pesticide is different, some generalizations can be made. Photochemical oxidations, reductions, hydrolytic reactions, and isomerizations often generate products identical to those of metabolic and nonbiological transformations. The chemistry and environmental stability of each individual photoproduct can be substantially different from those of the original pesticide and other products. With several notable exceptions, however, photoproducts are generally less stable to environmental forces and less toxic than the parent pesticide, at least to the target organism. A most significant exception is the P = S to P = O conversion in the organophosphorus insecticides. This sunlight promoted reaction is important in treated fields and has been implicated as a cause of injury to farmworkers.

Air Pollutants↗

Comparison of the disposition of several nitrogen-containing compounds in the sea urchin and other marine invertebrates.

1. The disposition of an aromatic amine and three aromatic nitro compounds was investigated in the sea urchin, Strongylocentrotus purpuratus. 2. The sea urchin rapidly eliminated injected compounds. The elimination rate constants decreased in the order p-toluidine greater than p-nitroanisole = p-nitrophenol greater than p-nitrotoluene. The fraction of total injected compound eliminated in 8 h was lowest for p-nitrophenol less than p-toluidine less than p-nitrotoluene less than p-nitroanisole. 3. Biotransformation for the sea urchin was primarily reduction of the nitro group followed by acetylation of the amine. 4. Other animals, starfish (Pisaster ochraceus), sea cucumber (Cucumaria miniata), gum boot chiton (Cryptochiton stelleri) and mussels (Mytilus californianus), injected with p-nitroanisole exhibited a trend toward oxidative biotransformation. 5. Elimination of parent compound was the major pathway for reducing body burden of xenobiotics for the invertebrates studied. 6. p-Toluidine oxidizes during analysis and was thus not suitable for studying biotransformation.

Amines↗

Photodecomposition of DDA.

The photodecomposition of aqueous solutions of 2,2-bis (p-chlorophenyl) acetic acid (DDA) was slow in sunlight and rapid in the laboratory, producing p,p'-dichlorobenzophenone (DCB), p-chlorobenzaldehyde, p-chlorophenol, and several unidentified polar products. p,p'-Dichlorobenzilic acid, and p,p'-dichlorobenzhydrol gave rise to the same photoproducts, while bis-(p-chlorophenyl) methane (DDM) and chlorogenzilate were converted only to DCB. DCB and p-chlorogenzaldehyde proved to be resistant to photodegradation but gradually produced p-chlorobenzoic acid which, in turn, formed p-hydroxybenzoic and benzoic acids, probably the last environmentally detectable links in the long chain of DDT degradation to CO2 and water. High pressure liquid chromatography (HPLC) proved to be ideal for separating and quantitating the parent compounds and their photoproducts directly from the aqueous photolysates or from methanol solutions of the isolates and standards.

Chromatography, Gas↗

Environmental degradation of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD).

Herbicide formulations containing known amounts of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and exposed to natural sunlight on leaves, soil, or glass plates lost most or all of the TCDD during a single day, due principally to photochemical dechlorination. Despite the known persistence of pure TCDD, it is not stable as a contaminant in thin herbicide films exposed to outdoor light.

Dioxins↗

Airborne and surface residues of parathion and its conversion products in a treated plum orchard environment.

Airborne pesticide residues were collected both within and downwind from a parathion-treated plum orchard by high volume sampling through XAD-4 macroreticular resin. Levels of paraoxon in excess of 100 ng/m3 were found in orchard air, along with parathion, during the early days of two 21-day sampling studies. Paraoxon:parathion ratios in the orchard air were relatively constant, averaging ca. 0.5 for days 1 to 21 following treatment. Likely sources of airborne paraoxon include vaporization and dislodgement from soil and leaf surfaces, and chemical conversion of parathion in the air. Support for the latter came from observation of an increased paraoxon:parathion ration in air samples collected downwind from the orchard. Atmospheric conversion of parathion to paraoxon, accelerated by sunlight, was indicated by both field and laboratory studies. Overall dissipation of parathion from the orchard air, soil, and leaf tissue proceeded to a considerable extent through breakdown to paraozon under the dry climatic conditions of these studies. Eventual conversion to the relatively stable breakdown product, p-nitrophenol, was indicated from analysis of air in the orchard vicinity.

Air↗