Hydrolytic and metabolic products of acephate in water and mouse liver

Acephate was incubated in distilled water of three different pH's at 37 degrees C for 7 days. Three hydrolytic products were formed: methamidophos, O,S-dimethyl phosphorothiolate (DMPT), and O-methylacetyl phosphoramidothiolate (OMPT). A single dose of acephate was also fed to mice, and their livers were excised and analyzed for metabolic products up to 30 hours. Three products were detected: methamidophos, DMPT, and S-methylacetyl phosphoramidothiolate (SMPT). The anticholinesterase properties of acephate, methamidophos, DMPT, SMPT, and OMPT were determined. Only acephate and methamidophos had measurable inhibitory effects on the mouse erythrocyte enzyme, methamidophos being about ten times more effective than acephate. The amount of methamidophos formed in the water and mouse liver was too low to have any direct effect on the toxicity of acephate. Acephate toxicity to aquatic insects would depend on its persistence in water, its uptake by the insects, its conversion to methamidophos, and the combined inhibitory effect of acephate and methamidophos on the cholinesterase enzyme. The toxicity of acephate to mammals would depend on the direct anticholinesterase effect of the chemical and to a small extent on methamidophos.     

Analysis and fate of acephate and its metabolite,methamidophos, in pepper and cucumber

Abstract

Levels of acephate (Orthene^R) and its principle metabolite, methamidophos, in/on greenhouse‐grown pepper and cucumber fruits and leaves in relation to the applied methamidophos were monitored. Dislodgeable and total residues of acephate and methamidophos were determined by gas‐liquid chromatography equipped with a flame ionization detector (GC‐FID) and were confirmed by nitrogen phosphorus detector (GC‐NPD). The dissipation curves of the residues followed first‐order kinetics (R²> 0.96). Initial residues of acephate on fruits varied between pepper (15.12 ppm) and cucumber (2.16 ppm) . Total residues in fruits and leaves determined at intervals following application revealed the greater persistence of acephate on pepper fruits (half‐life [t_1/2] of 6 d) than on cucumber fruits (t_1/2 was 3.7 d) . T_1/2 values for the applied methamidophos were 4.7 and 5.3 d on pepper and cucumber fruits, respectively. Deacety‐lation of acephate (formation of its metabolite) was detectable 1 d following acephate treatment and reached a maximum of 2.05% of initial acephate residues 3 d after application on pepper fruits. On cucumber fruits, acephate metabolite reached a maximum of 2.12% one wk following application. No acephate residues were detected above the limit of detection of 0.001 ppm in pepper fruits 50 d following acephate application while its metabolite was detectable at that time (detectability limit was 0.0001 ppm).     

The dissipation of nonlyphenol in stream and pond water under simulated field conditions

Abstract

The dissipation of 1.0 ppm nonylphenol in stream and pond water, incubated in flasks at 16°C under simulated field conditions up to 44 days indicated that the half‐life was 2.5 days if the flasks were open, and 16 days if they were closed. A transformed product was detected in the closed flasks.

Translocation of nonylphenol in water occurred when treated water samples were incubated in the presence of sediment. After 10 days, nonylphenol was detected only in the sediment, but not in water (detection limit = 10 ppb). About 80% of the nonylphenol was degraded in 71 days, but no degradation occurred if the water and the sediment were autoclaved prior to incubation.     

Studies on the toxicity, metabolism, and anticholinesterase properties of acephate and methamidophos

The toxicity of acephate to four species of aquatic insects, as well as the metabolism and cholinesterase-inhibiting properties of the chemical in the rat were studied. The results indicated that mayfly larvae were very sensitive to the toxic effects of acephate, whereas larvae of the stonefly, damselfly and mosquito were much less sensitive. In the rat, orally-administered acephate was rapidly absorbed from the intestines and severely inhibited the cholinesterases in the blood and brain. The enzymes began to recover after 24 hours, while the chemical was completely eliminated within three days. The amount of methamidophos observed in the liver was extremely low. The cholinesterase-inhibiting properties of acephate and methamidophos were compared in vitro to that of paraoxon, a known strong anticholinesterase. Enzymes from four vertebrates were used. In all cases, except one, acephate was found to be six orders of magnitude weaker than paraoxon, whereas methamidophos was three orders weaker. Trout brain cholinesterase was the exception; it was as sensitive to paraoxon as it was to methamidophos. Finally, four cholinesterases were inhibited with methamidophos, and their ability to reactivate spontaneously or to recover by induction with pyridine aldoxime methiodide (PAM) in vitro were determined. The results suggested that methamidophos-inhibited cholinesterases did not reactivate spontaneously; instead the enzymes remained inhibited either in a phosphorylated or an aged state. The significance of these results are discussed in relation to the use of acephate for forest insect pests.     

Effects of bacterial counts and temperature on the biodegradation of bisphenol A in river water

Total 15 surface river waters were collected from thirteen different rivers to investigate a relationship of bacterial counts and temperature to the degradation of bisphenol A (BPA). Autoclaved and non-autoclaved river water samples were spiked with 0.2 mg/l BPA. The spiked samples were placed at temperatures of 4, 20, and 30 degrees C and analyzed by high performance liquid chromatography. BPA was degraded at all temperatures in the non-autoclaved samples. However, BPA in the autoclaved samples was not changed at all temperatures for 20 d. These results show that the primary factor of BPA degradation in river water is bacteria. Moreover, three groups [group A (> 10000 CFU/ml), group B (2000-10000 CFU/ml), and group C (< 2000 CFU/ml)], were made on the basis of bacterial counts of the samples. Half-lives for BPA degradation in groups A, B, and C were 2, 3, and 6 d at 30 degrees C and were 4, 5, and 7 d at 20 degrees C, respectively. But at 4 degrees C, the loss of BPA was about 40%, 20%, and 10% in groups A, B, and C for 20 d, respectively. Bacterial counts exerted an influence on BPA degradation in river water with temperature. Our results also show that BPA-degrading bacteria are widely distributed in river waters.     

Effect of point source removal on mercury bioaccumulation in an industrial pond

A one hectare pond on the headwaters of a mercury-contaminated creek in Oak Ridge, Tennessee acted as a biochemical reactor for the production of methylmercury, increasing waterborne methylmercury concentrations in the stream below the pond discharge. The flow of the creek was diverted around the pond in order to eliminate this input. Waterborne total mercury, methylmercury, and mercury in fish, were monitored in the pond and stream before and after bypass. Waterborne methylmercury concentration in the creek downstream from the pond decreased over 800% following diversion of streamflow around the pond, but mercury in redbreast sunfish in the pond tailwater did not decline similarly. Within the pond, now isolated from fresh waterborne mercury inputs from the stream, methylmercury concentrations in the water column remained similar to levels present before bypass. However, mercury concentrations in sunfish in the pond decreased approximately 75% following bypass, despite the continued presence of highly contaminated sediments (approximately 50 mg Hg/kg dry weight). We concluded that a decrease in the fraction of 'dissolved methylmercury' in the isolated pond relative to pre-bypass conditions explained the decrease in mercury in fish within the pond. That observation also indicates that mercury associated with pond sediments was relatively unavailable for eventual bioaccumulation when compared to 'fresh' mercury contributed by upstream sources. The lack of a post-bypass decrease in mercury concentrations in tailwater fish was also likely to be associated with the particle-associated nature of waterborne methylmercury exported from the pond.     

Degradation of herbicides in two sandy aquifers under different redox conditions.

We examined the potential for complete degradation (mineralisation) of the four [ring-U-14C]herbicides mecoprop, isoproturon, atrazine, and metsulphuron-methyl in two sandy aquifers representing aerobic, denitrifying, sulphate-reducing, and methanogenic conditions. Slurries with sediment and groundwater were set-up aerobically or anaerobically in the presence of the electron-acceptor prevailing at the sampling site, amended with 25 microg l(-1) herbicide, and incubated at 10 degrees C. Considerable mineralisation was only observed in sediment from the plough layer incubated aerobically. Here, 30% of 14C-mecoprop was recovered as 14CO2 after 15 days and 15% of isoproturon was recovered as 14CO2 after 267 days. Only 7% of mecoprop was recovered as 14CO2 after 313 days in sediment from the aquifer below sampled at 1.95-3.00 mbs (m below the surface). In denitrifying and methanogenic slurries, 3% of 14C added as mecoprop was recovered as 14CO2. Isoproturon was not mineralised except in the aerobic plough layer, and atrazine and metsulphuron-methyl were not mineralised under any of the conditions applied.     

Influence of pH and aluminum on developing brook trout in a low calcium water

Eyed embryos of brook trout (Salvelinus fontinalis) were exposed to nominal pHs of 4.5, 5.5 and 7.5 with and without aluminum (300 microg liter(-1)) in extremely soft water (hardness <9mg liter (-1)) at 12 degrees C. Embryo mortality exceeded 80% at pH 4.5, averaged 15 to 18% in the pH 5.5 treatments and was less than 2% in the pH 7.5 treatments. Aluminum significantly reduced embryo mortality (85.3% vs 99.5%) at pH 4.5 but did not affect mortality at pH 5.5 or pH 7.5. Percent hatch and poor hatch were pH dependent and were not significantly influenced by aluminum. Brook trout larvae cumulative mortalities were 100% within 30 days at pH 4.5, with or without aluminum; 69% after 60 days at pH 5.5; 100% in 15 days at pH 5.5 with aluminum and 20% after 60 days at pH 7.5 with or without aluminum. Fish that survived the pH 5.5 treatment showed decreased growth and behavioral impairments compared to the controls (pH 7.5 without aluminum).     

Photosynthesis inhibition of soybean leaves by insecticides

Field grown soybean cv. Williams-82 plants were sprayed with malathion or carbaryl formulations at 30, 60 and 90 days after planting. Net photosynthesis (PN) was measured in the control (water-sprayed) and pesticide-treated plants, 1, 3 and 7 days after treatment, with a LICOR 6200 Portable Photosynthesis System. The pesticide-treated plants showed a significant reduction (24% with malathion and 20% with carbaryl) in PN after the first application. After the 60-day spray treatment PN suppression on day 1 and day 3 after treatment was the same as after the first application; but PN reached the same level as that of the water-sprayed control 7 days after treatment. After the 90-day treatment no change in PN was observed with the pesticide-treated plants compared to the control. These data indicate that malathion and carbaryl formulations may exert a detrimental influence on soybean physiology.     

Persistence and bioactivity of metsulfuron-methyl in three soils

The persistence of metsulfuron-methyl (methyl 2-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]aminosul fonyl]benzoate) in nonautoclaved and autoclaved Selangor, Lating, and Serdang series soils incubated at different temperatures and with different moisture contents was investigated under laboratory conditions using cucumber (Cucumis sativus L.) as the bioassay species. Significant degradation of metsulfuron-methyl was observed in nonautoclaved soil compared with the autoclaved soil sample, indicating the importance of microorganisms in the breakdown process. At higher temperatures the degradation rate in nonautoclaved soil improved with increasing soil moisture content. In nonautoclaved Selangor, Lating and Serdang series soils, the half-life was reduced from 4.79 to 2.78 days, 4.9 to 3.5, and from 3.3 to 1.9 days, respectively, when the temperature was increased from 20 degrees to 30 degrees C at 80% field capacity. Similarly, in nonautoclaved soil, the half-life decreased with an increasing soil moisture from 20% to 80% at 30 degrees C in the three soils studied. In the autoclaved soil, the half-life values were slightly higher than those obtained in the nonautoclaved soils, perhaps indicating that the compound may be broken down by nonbiological processes. The fresh weight of the bioassay species was reduced significantly in Serdang series soil treated with metsulfuron-methyl at 0.1 ppm. However, the reduction in fresh weight of the seedlings was least in Lating series soil, followed by Selangor series soil.     

Effects of a carbamate insecticide, carbaryl, on the summer phyto- and zooplankton communities in ponds

A carbamate insecticide, carbaryl (1-naphthyl-N-methylcarbamate), was applied in concrete ponds and the effects on plankton communities were studied. In a control pond, Cladocera declined following the increase in the density of inedible algae after a cladoceran peak. Once the density of Cladocera became low, Chaoborus larvae suppressed the increase of Cladocera and consequently supported the rotifer dominance in the zooplankton community by their selective predation on cladocerans. In a treated pond, the plankton community and its succession were similar to those in the control pond until the chemical application. 1 ppm of carbaryl killed all zooplankton and Chaoborus larvae. Cladocera reappeared soon and increased rapidly due to the absence of Chaoborus larvae. Consequently, rotifer populations were suppressed. Thus, the chemical application altered the dominance of rotifers to that of cladocerans. The same phenomenon was observed again after the second chemical application 12 days after. Although apparent direct effects of the chemical application on phytoplankton were not found, the phytoplankton community structure changed following the changes in the zooplankton density.     

Removal of emulsified fuel oils from brackish and pond water by dissolved air flotation with and without polyelectrolyte use: pilot-scale investigation for estuarine and near shore applications

In coastal areas, estuaries, and inland waters, dispersant use after oil spills is not allowed due to sensitivity of the ecosystems. The purpose of this study was to investigate the removal of emulsified fuel oils from brackish and pond water by dissolved air flotation (DAF) with and without use of coagulants. Experiments were conducted with a 60 L DAF system. Fuel oil-water emulsions were prepared with regular unleaded gasoline, jet fuel, and diesel fuel mixed at 1:1:1 (v/v/v) ratio. Batch and continuous runs were conducted at air pressurization of 354.6 kPa. During both batch and continuous modes, significant petroleum hydrocarbon (PHC) removal was achieved within 10 min. Coagulant addition initially increased the PHC removal by about 5-15%. However, effectiveness of the coagulant was not significant after 20 min due to breakage of the aggregates. In general, the pond water had higher PHC removal than the brackish water. With longer run times, PHC removal improved slightly and the effluent contained increasing fractions of higher molecular weight compounds indicating that PHC removal was due to both DAF and stripping processes. Results indicate that DAF process can be effective both with and without the use of coagulants for removing PHCs from brackish and pond waters.     

Development and evaluation of a method to determine indicator microorganisms in air emissions and residue from medical waste incinerators.

To allow testing of microbial destruction in medical waste incinerators, methods were developed to determine indicator microorganisms (Bacillus Stearothermophilus spores) in incinerator air emissions and residue. The emission trapping train consisted of a water cooled glass probe and impingers containing a neutral phosphate buffer. In field tests, spores were injected directly into the probe, and results showed that approximately 60 percent of the spores were recovered. Spores were analyzed with adequate precision using a microbial membrane filter unit. Lab experiments indicated that spores were stable in neutral pH phosphate buffer for up to 20 days, and heat shocking samples (heating to 80 degrees C for 20 minutes) reduced spore numbers in acidic or basic buffer. Laboratory tests also showed that 60 to 70 percent of spores initially added to ash were recovered up to 22 days after addition of the spores. In addition, lab tests showed that spores can be effectively recovered from residue test pipes spiked with indicator spores.     

Distribution and rate of disappearance of fluorene in pond ecosystems

Fluorene, an energy related polynuclear aromatic hydrocarbon, was applied to several experimental pond ecosystems to effect concentrations of 0.12, 0.5, 2.0, 5.0, and 10.0 mg/L. Water, benthic sediment, and rooted macrophytes were monitored for fluorene residues for 56 days after application. Most of the fluorene at concentrations greater than its water solubility appeared to sublime from the surface of the ponds. The rate of disappearance of fluorene from the water decreased as the application rate increased. This reduction was linked to high concentrations and a flux of fluorene from benthic sediments, macrophytes, and pond surfaces to water columns. Several parameters of photosynthetic primary production were statistically linked to the accelerated disappearance of fluorene from the water.     

Dynamics of suspended sediment exchange and transport in a degraded mangrove creek in Kenya

This study focuses on sediment exchange dynamics in Mwache Creek, a shallow tidal mangrove wetland in Kenya. The surface area of the creek is 17 km2 at high water spring. The creek experiences semidiurnal tides with tidal ranges of 3.2 m and 1.4 m during spring and neap tides, respectively. The creek is ebb dominant in the frontwater zone main channel and is flood dominant in the backwater zone main channel. During rainy season, the creek receives freshwater and terrigenous sediments from the seasonal Mwache River. Heavy supply of terrigenous sediments during the El Ni?o of 1997-1998 led to the huge deposition of sediments (10(60 tonnes) in the wetland that caused massive destruction of the mangrove forest in the upper region. In this study, sea level, tidal discharges, tidal current velocities, salinity, total suspended sediment concentrations (TSSC) and particulate organic sediment concentrations (POSC) measured in stations established within the main channel and also within the mangrove forests, were used to determine the dynamics of sediment exchange between the frontwater and backwater zones of the main channel including also the exchange with mangrove forests. The results showed that during wet seasons, the high suspended sediment concentration associated with river discharge and tidal resuspension of fine channel-bed sediment accounts for the inflow of highly turbid water into the degraded mangrove forest. Despite the degradation of the mangrove forest, sediment outflow from the mangrove forest was considerably less than the inflow. This caused a net trapping of sediment in the wetland. The net import of the sediment dominated in spring tide during both wet and dry season and during neap tide in the wet season. However, as compared to heavily vegetated mangrove wetlands, the generally degraded Mwache Creek mangrove wetland sediment trapping efficiency is low as the average is about 30% for the highly degraded backwater zone mangrove forest and 65% in the moderately degraded frontwater zone mangrove forest.     

Evaluation of bactericidal efficacy of silver ions on Escherichia coli for drinking water disinfection

Purpose

The purpose of this study is the development of a suitable process for the disinfection of drinking water by evaluating bactericidal efficacy of silver ions from silver electrodes.

Methods

A prototype of a silver ioniser with silver electrodes and control unit has been fabricated. Silver ions from silver electrodes in water samples were estimated with an atomic absorption spectrophotometer. A fresh culture of Escherichia coli (1.75?×?10³ c.f.u./ml) was exposed to 1, 2, 5, 10 and 20?ppb of silver ions in 100?ml of autoclaved tap water for 60?min. The effect of different pH and temperatures on bactericidal efficacy was observed at constant silver ion concentration (5?ppb) and contact time of 30?min.

Results

The maximum bactericidal activity (100%) was observed at 20?ppb of silver ion concentration indicating total disinfection after 20?min while minimum bactericidal activity (25%) was observed after 10?min at 01?ppb of silver ions. Likewise, 100% bactericidal activity was noticed with 2, 5 and 10?ppb of silver ions after 60, 50 and 40?min, respectively. Bactericidal activity at pH?5, 6, 7, 8 and 9 was observed at 79.9%, 79.8%, 80.5%, 100% and 100%, respectively, whereas it was 80.4%, 88.3%, 100%, 100% and 100% at 10°C, 20°C, 30°C, 40°C and 50°C, respectively.

Conclusion

The findings of this study revealed that very low concentrations of silver ions at pH?8?C9 and temperature >20°C have bactericidal efficacy for total disinfection of drinking water. Silver ionisation is suitable for water disinfection and an appropriate alternative to chlorination which forms carcinogenic disinfection by-products.     

Persistence and biodegradation of carbaryl in soils

Abstract

The persistence of the methylcarbamate pesticide carbaryl was studied in four soils under flooded conditions. A substantial portion of the pesticide was recovered from all soils even after 15 days of its application, with the recovery ranging from 37% in an alluvial soil to 73% in an acid sulfate soil. The degradation of carbaryl was more rapid under flooded conditions than under nonflooded conditions. A bacterium, Pseudomonas cepacia, isolated from a flooded soil amended with a related methylcarbamate pesticide carbofuran, degraded carbaryl in a mineral medium supplemented with yeast extract.     

Dissipation of 14C carbaryl and quinalphos in soil under a groundnut crop (Arachis hypogaea L.) in semi-arid India

The dissipation of 14C carbaryl in undisturbed soil cores, and of quinalphos (25EC and 20AF) after seed and soil treatments, was investigated under field use conditions, in a semi-arid groundnut field. Residues were analyzed by TLC and HPLC and additionally by LSC for 14C carbaryl. The harvested seed kernels were also tested for the presence of insecticide residues. The movement of carbaryl was limited to 15 cm depth in the loamy sand of Jaipur and was detected till 120 days (DT50 of 14.93 days) after application. Bound residues and 1-naphthol had a DT50 of 11.45 and 13.68 days, respectively. Irrespective of the three types of soil samples investigated, the principal metabolite formed on seed and soil treatments with quinalphos, was 2-hydroxyquinoxaline. With seed treatment, a thiol metabolite of quinalphos was also detected. Higher yields of groundnut were realized with quinalphos treatments in comparison to those from control. Post-harvest, no pesticide residues were found in seeds.     

The hydrolysis of Zectran in buffered and natural waters.

The analyses and rates of hydrolysis of Zectran, 4-dimethylamino-3,5-xylyl methylcarbamate are reported in aqueous media. These rates were measured in phosphate buffered, distilled water and in natural waters where tempteratures of 10 degrees, 20 degrees, and 28 degrees C. and pH values of 5.94, 7.00, and 8.42 were used. Intial concentrations of Zectran exceeded 60 mg/l (0.27 mMol 1(-1), whereas in the natural waters initial concentrations were 30 mg/l (0.135 mMol 1(-1). This study shows that the persistance of Zechtran in natural waters is, in large part, dependent upon the pH value and the temperature.     

Optimization of analytical methods to improve detection of erythromycin from water and sediment

Analytical methods to improve the detection of erythromycin in water and sediment were developed to optimize for erythromycin's recovery of extractable and bound residues from the aquatic environment. The objective of this study was to determine optimal recovery of erythromycin from water and sediment to improve its detection in environmental samples through solid-phase extraction (SPE) and sediment-extraction methods. SPE methods examined included previously reported methods for macrolide and sulfonamide antibiotics with erythromycin recoveries ranging from 75.5 % to 94.7 %. Extraction of erythromycin was performed from sand employing various solvents and buffers to determine the best method for extraction from two sandy loam pond sediments. Various extraction times were also examined, and all extraction procedures were performed in duplicate. The greatest recovery of ¹⁴C-erythromycin in the Iowa sediment was 84 % using 0.3 M ammonium acetate at pH 4.2: acetonitrile (15:85, v/v) solution. The Oklahoma sediment yielded the greatest recovery of ¹⁴C-erythromycin at 86.7 % with 0.3 M ammonium acetate at pH 7: acetonitrile (30:70, v/v) with a 60-minute shake time. The present results demonstrate improved extraction methods for enhancing the accuracy of erythromycin detection from environmental samples.