Fate and residues of 14C‐chloramphenicol in laying chickens 1

Abstract

Studies were conducted to determine the metabolic fate of chloramphenicol (CAP) in White Leghorn using the ^l4C‐labelled compound. In one experiment birds were administered orally via intra‐crop, a single dose of 100 mg (equivalent to 66 mg kg^‐1 body weight) of CAP containing 14 μCi ¹⁴C‐CAP, and its absorption, elimination and distribution in plasma were recorded. Orally dosed ¹⁴C‐compound was rapidly absorbed, efficiently distributed in plasma and eliminated in excreta (>70% in 5 hr). After 5 h, CAP equivalent residues in tissues were lower than 15 μg g^‐1 for this treatment. In a second experiment birds were given intra‐crop dose of either 0.5 or 5 mg of CAP (each dose contained 2.5 μCi ¹⁴C‐CAP) daily for five consecutive days followed by a seven day withdrawal period and elimination of ¹⁴C in excreta and eggs was monitored. More than 95% of the administered ¹⁴C was eliminated within the first 24 h after dosing. Radiocarbon (¹⁴C) was deposited preferentially in yolks compared to albumen or other tissues. Residues declined when feeding was stopped. Various metabolites were isolated and identified by a combination of TLC, LC, and LC‐MS. The main metabolic route of CAP in laying hens appears to be the glucuronidation. Cleavage of the dichloroacetate moiety was only a minor route.     

Metabolism of 14C‐carbaryl and 14C‐1‐naphthol in moist and flooded soils

Abstract

The metabolism of ¹⁴C‐carbaryl and ¹⁴C‐1‐naphthol in moist and flooded soils was studied in a continuous flow‐through system over a period of 28 days permitting ¹⁴C‐mass balance. The percent distribution of radiocarbon in organic volatiles, carbon dioxide, extractable and non‐extractable (bound) fractions of soils were determined. Organic volatiles could not be detected in both carbaryl and 1‐naphthol treated soils. More of ¹⁴CO₂ (25.6%) was evolved from moist than flooded soil (15.1%) treated with carbaryl. However, the mineralization of ¹⁴C‐1‐naphthol was negligible. The extractable radiocarbon was more in flooded soil (28.9%) than moist soil (5.5%) from carbaryl treatment. Less than one percent was present as parent compound, whereas carbaryl was mainly metabolized to 5‐hydroxy carbaryl in moist soil and to 4‐ and 5‐hydroxy carbaryl in flooded soil. The extractable radiocarbon amounted to 18.2 and 24.3% in moist and flooded soils respectively and the parent compound was less than one percent with 1‐naphthol treatment. Most of the radiocarbon was found as soil bound residues; the formation being more with 1‐naphthol than carbaryl. Humin fraction of the soil organic matter contributed most to soil bound residues of both carbaryl and 1‐naphthol.     

Biological activity and bioavailability of grain bound 14C‐malathion residues in rats

Abstract

Paddy (unmilled rice), milled rice and maize‐bound ¹⁴C residues were prepared using ¹⁴C‐succinate‐labelled malathion at 10 and 152 ppm. After 3 months, the bound residues accounted for 12%, 6.5% and 17.7% of the applied dose in paddy, milled rice and maize respectively in the grains treated at 10 ppm. The corresponding values for the 152 ppm were 16.6%, 8.5% and 18.8%. Rats fed milled rice ‐ bound ¹⁴C‐residues eliminated 61% of the ¹⁴C in the faeces and 28% in the urine. The corresponding percentages for paddy and maize were 72%, 9% and 53%, 41% respectively; indicating that bound residues from milled rice and maize were moderately bioavailable. When rice‐bound malathion residues (0.65 ppm in feed) were administered to rats in a 5 week feeding study, no signs of toxicity were observed. Plasma and RBC cholinesterase activities were slightly inhibited: blood urea nitrogen was significantly elevated in the test animals. Other parameters examined showed no or marginal changes.     

Fate of 14C‐lindane in a rice‐fish model ecosystem*

Abstract

A model ecosystem has been used to evaluate the impact of ¹⁴C‐lindane on rice‐fish agricultural system. The distribution of ¹⁴C‐residues among the constituents of the model ecosystem was studied over a period of 90 days. The insecticide was found to be readily absorbed by the roots and translocated to all parts of the rice plant. The peak level in the shoots (26 ppm) and roots (105 ppm) of plants was reached to within three weeks. Lindane was concentrated in fish and residues as high as 90 ppm could be detected after 30 days.

The major part of the residues present in the different constituents of the ecosystem could be extracted with hexane and proved to contain soley the parent compound. The data obtained show that lindane possesses a relatively low biodegradability in fish and in rice plant. The insecticide accumulates in fish and rice plant to considerable extent.     

Aged and bound herbicide residues in soil and their bioavailability part 2: Uptake of aged and non‐extractable (bound) [carbonyl‐14C] methabenzthiazuron residues by maize

Abstract

[Carbonyl‐ C]methabenzthiazuron (MBT) was applied to growing winter wheat in an outdoor lysimeter. The amount applied corresponded to 4 kg Tribunil/ha. 140 days after application the 0–2,5 cm soil layer was removed from the lysimeter. This soil contained about 40 % of the applied radioactivity. Using 0,01 M CaCl₂ solution or organic solvents, the extractable residues were removed from the soil. The bioavailability of the non‐extractable as well as aged residues remaining in the soil was investigated in standardized microecosystems containing 1.5 kg of dry soil. During a 4 weeks period the total uptake (4 maize plants/pot) amounted up to 3,6; 2,2; and 0,9 % of the radioactivity from soils containing aged MBT residues, MBT residues non‐extractable‐with 0,01 MCaCl₂ or MBT residues non‐extractable with organic solvents, respectively. About 20 % of the radioactivity found in maize leaves represented chromatographically characterized parent compound. At the end of the plant experiment the soil was extracted again with 0,01 M CaCl₂ and with organic solvents. The soil extracts and also the organic phases obtained from the aqueous fulvic acid solution contained unchanged parent compound.     

Bioavailability to rats of 14C‐lindane residues in stored potato tubers

Abstract

Potato tubers were applied with radiolabelled lindane (U‐¹⁴C γ‐ 1,2,3,4,5,6 hexachlorocyclohexane) at three dose levels 30, 150, and 300 ppm and stored for 30, 60 and 90 days at room temperature. The data revealed that lindane penetrated into the pulp tissues through the epidermal layer. The amounts recovered in the peel were found to increase with a greater storage period up to 60 days followed by a drop at 90 days. On the other hand, there was a slight increase in radioactivity in the pulp tissue from 30 to 60 days followed by significant increase after 90 days. The incorporation of the compound in the tubers was dose independent. Methanol extraction showed binding of about 8.1% and 5.8% ofthe applied dose in peel and pulp tissues, respectively. The insecticide was found to be bioavailable when rats health hazard. It is therefore, desirable to demonstrate that the quantity of the terminal residues may be safe for the consumer. In the present investigation an attempt was made to determine the fate and bioavailability of lindane when applied to stored potato tubers.     

Chemical and biological release of 14C‐bound residues from soil treated with 14C‐p,p'‐DDT

Abstract

¹⁴C‐p,p'‐DDT‐bound residues in soil can be released by treatment with concentrated sulphuric acid at ambient temperatures. Within 6 days, about 70% of the bound residues was released. Bound residues released after 9 months incubation with ¹⁴C‐DDT showed the presence of DDT and DDE only while bound residues released after 18 months, contained in addition 13% DDD.

Release of bound ¹⁴C‐residues also occurs readily following inoculation of the soil‐bound residues with fresh soil or with individual microorganisms. Almost complete release of bound residues was observed after incubation for 45 days. The rate of release was rapid during the first two weeks and decreased thereafter. TLC and HPLC analysis showed that the released residues contained DDE (about 80%) and a smaller amount of DDD. The disappearance of DDT from the released residues may be attributed to its microbiological degradation to DDE and DDD, shortly after its release.     

14C‐dimethoate residues in olive oil during oil processing

Abstract

An olive tree was treated twice in the field with ¹⁴C‐dimethoate (237.7 (μCi, 2.4 g) and ¹⁴C residues were determined in the olive fruits at harvest. The fruits were crushed and pressed to extract the crude oil, then refined by neutralization, bleaching and deodorization. The crude oil contained 14.1% of the total ¹⁴C in the olive fruits. Neutralization resulted in a reduction of ¹⁴C by about 50% of the total ¹⁴C residues in oil. Bleaching and deodorization processes further reduced the ¹⁴C residues and the refined oil contained 31.6% (which corresponds to 4.4% of ^I4C residues of the total ¹⁴C in olive fruits) of the total ¹⁴C in the crude oil. Industrially extracted crude oil was fortified with ¹⁴C‐dimethoate at 1.8 mg kg^‐1 (0.02 μCi) level and subjected to the same refining process. A sharp decrease in the amount of ¹⁴C was observed by neutralization and the amount of ¹⁴C remaining in the refined oil was about 7.3% of the total ^l4C in the crude fortified oil. The data suggest that the ¹⁴C residues in the aged and the fortified oil amples were not of the same nature. The terminal ¹⁴C residue in the refined oil obtained from the field experiment did not contain dimethoate and/or its oxon.     

Comparative studies of the fate of atrazine‐14C and pentachlorophenol‐14C in various laboratory and outdoor soil‐plant systems

Abstract

Mass balance and fate of atrazine‐ ¹⁴C and pentachlorophenol‐ ¹⁴C (PCP‐ ¹⁴C) were studied in short‐term tests in a closed aerated laboratory soil‐plant system, using two concentrations in soil and two plant species, as well as under outdoor conditions for one vegetation period. In the laboratory, for both pesticides bioaccu‐mulation factors of radiocarbon taken up by the roots into plants were low. They were higher for lower (1 ppm) than for higher soil concentrations (6 ppm for atra‐zine, 4 ppm for pentachlorophenol) and varied with the plant species. Mineralization to ¹⁴CO₂ in soil was negatively related to soil concentration only for PCP‐ ¹⁴C. Conversion rates in soil including the formation of soil‐bound residues were higher for the lower concentrations of both pesticides than for the higher ones; conversion rates in plants were species‐dependent. In 14 terms of CO₂ formation and of conversion rates, PCP was less persistent in soil than was atrazine. For both pesticides, laboratory data on conversion and mineralization gave a rough prediction of their persistence in soil under long‐term outdoor conditions, whereas bio‐accumulation factors in plants under long‐term outdoor conditions could not be predicted by short‐term laboratory experiments.     

Degradation of atrazine,metolachlor, and pendimethalin in pesticide‐contaminated soils: Effects of aged residues on soil respiration and plant survival

Abstract

This study was conducted to determine the effects of pesticide mixtures on degradation patterns of parent compounds as well as effects on soil microbial respiration. Bioavailability of residues to sensitive plant species was also determined. Soil for this study was obtained from a pesticide‐contaminated area within an agrochemical dealer site. Degradation patterns were not affected by the presence or absence of other herbicides in this study. Atrazine concentrations were significantly lower at 21 through 160 days aging time compared to day 0 concentrations. Metolachlor and pendimethalin concentrations were not significantly different over time and remained high throughout the study. Microbial respiration was suppressed in treated soils from day 21 to day 160. Soybean and canola were the most successful plant species in the germination and survival tests. Generally, with increased aging of pesticides in soil, germination time decreased. Survival time of plants increased over time for some treatments indicating possible decreased bioavailability of pesticide residues. In some cases, survival time decreased at the longer 160‐day aging period, possibly indicating a change in bioavailability, perhaps as the result of formation of more bioavailable and phytotoxic metabolites. No interactive effects were noted for mixtures of pesticides compared to individually applied pesticides in terms of degradation of the parent compound or on seed germination, plant survival, or microbial respiration.     

Cyhalofop‐p‐butyl mobility and distribution of residues in soil at various depths

This study was conducted to evaluate cyhalofop‐p‐butyl mobility in a sandy loam soil and subsequent distribution of residues at various depths under field conditions. Soil samples were taken from 0 to 150 cm depths at 3–90 d after rains in lysemeter of 1 and 2 m depths. Cyhalofop‐p‐butyl application at two rates and subsequent precipitation had a significant impact on soil, physico‐chemical properties and herbicide mobility. Precipitation caused substantial mobility of cyhalofop‐p‐butyl in the soil and 1.1–7.6 μg L^?1 of cyhalofop‐p‐butyl was found in leachates. Cyhalofop‐p‐butyl residues in the leachates were probably due to preferential flow through the soil. Cyhalofop‐p‐butyl residues were detected in significant amounts from the soil up to 10 d, later, residues were found below the detection limit but its three transformation products viz., cyhalofop acid, diacid, and phenol were detected.     

Persistence of metsulfuron‐methyl in two soils

Abstract

The persistence of metsulfuron‐methyl in sandy loam and clay soil incubated at different temperatures and moistures contents was investigated under laboratory conditions using longbean (Vigna sesquipedalis L.) as bioassay species. A significant degradation of metsulfuron‐methyl was observed in non‐autoclaved soil rather than the autoclaved soil sample. At higher temperature, the degradation rate in non‐autoclaved soil improved with increasing soil moisture content. In non‐autoclaved sandy loam and clay soil, the half‐life was reduced from 9.0 to 5.7 and from 11.2 to 4.6 days, respectively when moisture level of sandy loam increased from 20 to 80% field capacity at 35°C. In the autoclaved soil, herbicide residue seems to have been broken down by non‐biological process. The rate of dissipation was slightly increased after the second application of the herbicide to non‐autoclaved soils but not in autoclaved soil, indicating the importance of microorganisms in the breakdown process.     

Effects of metsulfuron‐methyl on microbial biomass and populations in soils

Abstract

Effects of the herbicide metsulfuron‐methyl on soil microorganisms and their activities in two soils were evaluated under laboratory conditions. Measurements included their populations, soil respiration, and microbial biomass. In the clay soil, bacterial populations decreased with increasing concentration of metsulfuron‐methyl during the first 9 days of incubation but exceeded that of the control soil from day 27 onward. In the sandy loam soil, the herbicide reduced bacterial populations during the first 3 days after application, but these increased to the level of untreated controls after 9 days’ incubation. Fungal populations in both soils increased with increasing metsulfuron‐methyl concentrations, especially in the sandy loam soil. CO₂ evolution was stimulated in both soils in the presence of the herbicide initially, but decreased during days 3 to 9 of the incubation period before increasing again afterward. The presence of metsulfuron‐methyl in the soil increased microbial biomass, except in sandy loam soil at the first day of incubation.     

Laboratory studies on volatilization and mineralization of 14c‐p,p'‐DDT in soil,release of bound residues and dissipation from solid surfaces

Abstract

In support of field data, laboratory studies were conducted on volatilization, mineralization and binding of ¹⁴C‐p,p'‐DDT in soils at Sao Paulo. Incubation of soil for 6 weeks did not result in volatilized organics or mineralization; with >95% extractable radiocarbon in the form of p,p'‐DDT. Small amounts of bound residues (1.8%) were detected in soil. These data confirm the very slow dissipation of DDT in the field which presumably relates to the acidic pH of soil (4.5–4.8).

Bound ¹⁴C‐residues in soils treated with ¹⁴C‐p,p'‐DDT at Praia Grande and Sao Paulo could be released (5–21%) by sulphuric acid treatment. The released residue had the composition: 69–90% DDT, 7–32% DDD and 0–3% DDE. Incubation of soil bound ¹⁴C‐residues with fresh inoculum for 3 months did not result in release of ¹⁴C.

Dissipation from wooden surfaces was fairly slow. After 20 weeks, 74% of the applied radioactivity could be recovered; 44% hexane‐non‐extractable.     

Fate of parathion in soil under sub‐tropical field conditions

Abstract

Persistence, metabolism and binding of ¹⁴C‐parathion in alkaline sandy loam soil under sub‐tropical conditions of Delhi were studied for 545 days. After 3 days of treatment, ¹⁴C‐residues declined to 41% of the amount applied. The dissipation curve was biphasic; an initial rapid phase (up to 7 days) followed by slow dissipation. The half life of dissipation was only 3.36 days for the first phase and 84 days for the slow phase. The overall half life was 64.5 days. The total residues at zero‐time were 10.65 μg/g dry soil and were almost totally extractable. The extracts consisted of parathion, 4‐aminophenol, 4‐nitrophenol and paraoxon. The bound residues gradually increased and accounted for the total residue at the end of one year (0.7 μg/g).     

Laboratory studies of dissipation of 14C‐DDT from soil and plywood surfaces

Abstract

The effects of temperature and solar radiation on dissipation of ¹⁴C‐p,p'‐DDT from a latosol soil were studied under laboratory conditions. Volatilization was measured by trapping organic volatiles during 6 weeks and was found to increase with rise of temperature from 3.8% of initial amount at ambient temperature to 5.9% at 45°C.

Studies on the effect of solar radiation using quartz tubes under sterilized and non‐sterilized conditions have shown that volatilized organics were highest in quartz tubes, with soil microflora presumably playing a very minor role in volatilization. Mineralization was shown to be low in sterilized systems and highest in non‐sterilized quartz systems. Studies on binding suggest that soil bioactivity may be involved in the formation of a portion of the bound residue. These laboratory experiments seem to support data from the field, where it is maintained that volatilization is a major mechanism for dissipation. Degradation in soil and to a lesser extent solar irradiation contribute also substantially to the dissipation mechanisms. Radiocarbon dissipated from plywood surfaces under indoor conditions in a biphasic fashion. Loss of 50% occurred after 5.5 weeks while the remainder dissipated at a very slow rate.     

A laboratory study of the persistence of carbofuran and its 3‐hydroxy‐ and 3 keto‐metabolites in sterile and natural mineral and organic soils

Abstract

In a laboratory study, the persistence of carbofuran and its 3‐hydroxy‐ and 3‐keto‐metabolites was examined separately over 16 wk in sterile and natural organic (muck) and mineral (loam) soils. Carbofuran was relatively persistent in sterile soils; at 8 wk 77% remained in the sterile muck and about 50% remained in the sterile loam. In the natural muck 25% of initial carbofuran remained at 8 wk whereas in the natural loam carbofuran had completely disappeared by that time. The 3‐ketocarbofuran was very short‐lived even in the sterile muck where only 50% remained at 1 wk. The 3‐hydroxycarbofuran degraded appreciably on zero day in the natural soils (with conversion to 3‐ketocarbofuran) and about 90% had disappeared in 1 wk. A more detailed study of the persistence of 3‐hydroxycarbofuran in the natural soils showed complete disappearance in 2 days in loam and in 3 days in muck. The 3‐ketocarbofuran produced from the 3‐hydroxy‐carbofuran reached a maximum concentration in 1 day and then disappeared within 4 days in loam and about 1 wk in muck.     

Toxic effects of 2,4‐D herbicide on fish

Abstract

Acute and subacute 2,4‐D toxicity to carp (Cyprinus carpio L.) were investigated. Acute toxicity (LC‐ 50) was investigated in semi‐static test during a 24, 48, and 96‐ hours exposition. Subacute toxicity was investigated by exposing fish to different 2,4,‐D concentrations (150, 200, and 250 mg/L) for 14 days. Biochemical and morphological changes in certain organs and tissues were investigated.

LC‐ 50 values at 24 hours exposure was 310.0 mg/L, 295.0 mg/L for 48 hours, and 270.0 mg/L for 96 hours exposure.

Subacute toxicity tests show that 2,4‐D induce changes in the enzyme activities (AP, GOT, GPT) and morphological changes in the gills, liver and kidneys, but changes are of limited biological importance.     

Soil bound residues of carbaryl and 1‐naphthol: Release and mineralization in soil,and uptake by plants

Abstract

¹⁴C‐carbaryl and ¹⁴C‐1‐naphthol form soil bound residues which get partially released when barley was grown. ¹⁴C‐residues could be detected in both shoot and root in the case of carbaryl treatment while only roots showed ¹⁴C‐residues in the case of 1‐naphthol. Flooding enhanced release of the bound residues while soil amendment did not. There was greater mineralization of bound residues of carbaryl than that of 1‐naphthol. Rice straw amendment enhanced mineralization.