Studies on bound 14C-prometryn residues in soil and plants

A high-temperature distillation technique was developed for determining and chemically identifying the bound (nonextractable) residues of ¹⁴C-prometryn in an organic soil and plants. A considerable portion of the bound ¹⁴C residues in the incubated organic soil was identified as prometryn. These residues were absorbed by plants grown in the soil. Hono-and di-$\text{N}$-dealkylated metabolites of prometryn were present in the plant bound ¹⁴C residues and a major portion of bound residues as associated with lignin. Soil-bound ¹⁴C residues were also released from soil by microbes. The bound ¹⁴C residues in soil were associated with humin, humic acid, and fulvic acid fractions. Thermoanalytical methods were used to obtained information on the nature and location of ¹⁴C bound residues in soil and humic materials.     

Phthalates and the aquatic environment: Part I The effect of di-2-ethylhexyl phthalate (DEHP) and di-isodecyl phthalate (DIDP) on the reproduction of Daphnia magna and observations on their bioconcentration

$\text{Daphnia magna}$ were exposed to di-2-ethylhexyl phthalate (DEHP) and to di-isodecyl phthalate (DIDP) at nominal concentrations up to 100 μg/1 over a 21 day period. The phthalates had no effect on reproduction, and the parent $\text{Daphnia}$ showed bioconcentration factors of 209 (DEHP) and 116 (DIDP) as determined by ¹⁴C analysis.     

Release of soil bound (nonextractable) residues by various physiological groups of microorganisms∗

Abstract

Soil bound ¹⁴C‐labeled residues were released by four different physiological groups of microorganisms from an organic soil treated with ¹⁴C‐ring‐labeled prometryn [2‐(methylthio) ‐4,6‐bis(isopropylamino)‐s‐triazine]. The extent to which the different microbial populations released bound ¹⁴C residues (25–30% of the total bound ¹⁴C) from the Y‐irradiated soil after 28 days incubation did not differ considerably. Analysis of the extractable material from the incubated soil showed the presence of small amounts of the parent compound, and its hydroxy and mono‐N‐dealkylated analogues. Low level of ¹⁴CO₂ (1.5–3.0% of the total bound ¹⁴C) was evolved from the microbial systems indicating ring cleavage of the released material as being a very minor reaction.     

Modular containers for microcosm and process model studies on the fate and effects of aquatic contaminants

Container modules are described for the laboratory simulation of selected processes and ecosystems that are representative of lentic environments. Emphasis is placed on design features permitting mass balance accountability of contaminant residues and procedural cautions required for the proper use of the described systems in environmental simulations. Experiments on the efficiency of container modules for microbial mineralization studies were conducted using ¹⁴CNaHCO₃, and acidification resulted in a ¹⁴CCO₂ recovery of $\text{97.3 ± 4.7\% (}\text{x}\text{?}\text{± SD}\text{)}$. The trapping efficiency of pesticides volatilized from water and glass surfaces was investigated using the same module and the mean recoveries of ¹⁴C-fonofos and ¹⁴C-trifluralin were 114.2 ± 3.2% and 95.2 ± 3.5%, respectively. The mass balance capabilities of the system was also demonstrated for extended microcosm exposures to ¹⁴C-trifluralin.     

Accumulation of bis(tributyltin) oxide by the mud crab, Rhithropanopeusharrisii

Accumulation of ¹⁴C labelled bis(tributyltin) oxide (TBTO) by the mud crab, $\text{Rhithropanopeus}$$\text{harrisii}$, was determined through short-term exposure to labelled water and food. The potential for trophic accumulation during chronic low level exposure is emphasized.     

Fate of hexachlorobenzene-14C in wheat plants and soil under outdoor conditions

Residues of hexachlorobenzene-¹⁴C were found in all parts of wheat plants grown from treated seeds or in contaminated soil. Besides the parent compound and bound residues in plants and soil, very small amounts of soluble acidic metabolites were present in plants, which were characterized and determined quantitatively.     

Phthalates and the aquatic environment: Part II The bioconcentration and depuration of di-2-ethylhexyl phthalate (DEHP) and di-isodecyl phthalate (DIDP) in mussels (Mytilus edulis)

Mussels ($\text{Mytilus edulis}$) were exposed to di-2-ethylhexyl phthalate (DEHP) and to di-isodecyl phthalate (DIDP) over a period of 28 days. The bioconcentration factor (BCF) as measured by ¹⁴C analysis, reached estimated plateau levels corresponding to mean BCF values of approximately 2500 and 3500 for the DEHP and DIDP respectively. The mussels were then held in clean seawater for a further 14 days and ¹⁴C analysis showed a depuration half-life of approximately 3.5 days for both phthalates. During the whole 42 days of the experiment general observations on the health of the animals showed no evidence of any adverse effects.     

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.     

Interaction of higher marine fungi with the herbicide atrazine. III. Adsorption of atrazine to the marine fungus Dendryphiellasalina

The adsorption of the herbicide ¹⁴C-atrazine to the marine fungus $\text{Dendryphiella}$$\text{salina}$ was studied using sodium azide as an inhibitor of active uptake. Adsorption of atrazine (94 ppb) was found to reach equilibrium within six hours. Adsorption as a function of concentration (9.4 to 468 ppb) conformed to the empirically derived Freundlich equation giving a K value of 6.2. Atrazine on the fungal cell surface was easily desorbed by successive artificial seawater washes indicating a relatively loose binding. The ability of the marine fungus $\text{D.}$$\text{salina}$ to remove ¹⁴C-atrazine from an artificial seawater medium suggests an environmental role in the transport and redistribution of atrazine in estuaries.     

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.     

Uptake,depuration and biotransformation of anthracene by the scud Pontoporeia hoyi

Uptake, depuration and biotransformation rates of ¹⁴C-anthracene were determined for Pontoporeia hoyi, the dominant benthic invertebrate in the Great Lakes, at 4°, 7°, 10° and 15°C. The uptake rate constants for anthracene increased from 136±22 h^?1 (n=4, $\text{X}\text{?}\text{±1}\text{SD}$) to 215±45 h^?1 (n=4) over the temperature range studied and were seasonally dependent. The depuration rate constant at the apparent optimum temperature of 7°C was 0.015 h^?1 for anthracene. The biotransformation ability of P. hoyi is low, and degradation of anthracene was undetectable even after exposures of 48 h. The bioconcentration factor can be predicted from the uptake and depuration kinetics to be approximately 16,800 at 4°C. These experiments imply that P. hoyi may be very important in food chain biomagnification of some toxic organics.     

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).     

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.     

Soil-catalyzed oxidation of aniline

Aniline partially degraded in sterile soil to azobenzene, azoxybenzene, phenazine, form=anilide, and acetanilide. Nitrobenzene, $\text{p}$-benzoquinone, and unidentified species were possible products; substantial bound residues may also have formed. Soil-catalyzed conversion of aniline or [$\text{d}$₅]aniline seems evidenced by 6-24X more product recovery in sterile soil than in sterile water alone, a process inhibited by Na₂S₂O₄. Freundlich adsorption constants showed: azobenzene > azoxybenzene > phenazine > aniline.     

Environmental dynamics of phosphate esters. III. Comparison of the bioconcentration of four triaryl phosphates by fish

Uptake, clearance and extent of metabolism of ¹⁴C-labelled t-butylphenyldiphenyl phosphate (t-BPDP), tri-m-cresyl phosphate (mTCP), tri-p-cresyl phosphate (pTCP) and triphenyl phosphate (TPP) were studied in rainbow trout ($\text{Salmo}$$\text{gairdneri}$) and fathead minnows ($\text{Pimephales}$$\text{promelas}$) using short-term static exposures (50 and 5 μmg/L). Bioconcentration factors for pTCP, mTCP, TPP and tBPDP calculated by use of total radioactivity in whole fish were 1420, 784, 573 and 1096 respectively, for rainbow trout and 928, 596, 561 and 1010 respectively, for fathead minnows. Differences in rates of clearance and biotransformation among the four compounds were more closely related to their ease of hydrolysis than to hydrophobicity.     

Enumeration of 2,4-D-degrading microorganisms in soils and crop plant rhizospheres using indicator media; high populations associated with sugarcane (Saccharum officinarum)

Population of microorganisms able to degrade 2,4-D (2,4-dichlorophenoxyacetate) were estimated in 4 non-rhizosphere and 5 rhizosphere soils in Natal by a most probable number (MPN) method using 2,4-D-bromocresol purple media to show 2,4-D degradation with the formation of HC1. Confirmation of herbicide degradation in acid 2,4-D tubes was required by subculturing into fresh 2,4-D-and control indicator media. The MPN estimates of 2,4-D-degrading organisms per g of corresponding rhizosphere/control soils were 6100/212 with African clover ($\text{Trifolium africanum}$ L.) soils, and $\text{46400}\text{178}$, $\text{156000}\text{1480}$ and $\text{40700}\text{6170}$ with sugarcane ($\text{Saccharum officinarum}$ L.) soils. The high, stimulated populations of 2,4-D-degrading microorganisms in the sugarcane rhizospheres suggest the possibility of rapid degradaton in the rhizosphere as an additional mechanism for the protection of certain plants against soil-applied herbicides.     

The effect of cadmium ion on the growth,photosynthesis, and nitrogenase activity of Anabaenainaequalis

The growth of $\text{Anabaena}$$\text{inaequalis}$ was significantly inhibited by Cd²⁺ concentrations greater than 0.02 ppm (μg/ml) and completely inhibited at 0.06 ppm (Day 12). Cadmium had no significant effect upon the lag phase of growth or the culture doubling time, but caused the retardation phase to arrive sooner. One ppm Cd²⁺ significantly inhibited the rates of both photosynthesis and acetylene reduction, by $\text{A}$. $\text{inaequalis}$, with complete inhibition at 4 and 20 ppm respectively. Cell sensitivity increased directly with exposure time. Cadmium caused some cell lysis of $\text{A}$. $\text{inaequalis}$ and induced an increase in filament length, heterocyst frequency, and a loss of cellular contents from filament apical cells. The cellular abnormalities observed and the fact that toxicity increased with longer exposure times, suggested that metal toxicity resulted from effects of Cd²⁺ taken up by cells rather than Cd²⁺ at the cell surface.     

Fate in soil of 14C-sulfadiazine residues contained in the manure of young pigs treated with a veterinary antibiotic

The fate of ¹⁴C-labeled sulfadiazine (¹⁴C-SDZ) residues was studied in time-course experiments for 218 days of incubation using two soils (A_p horizon of loamy sand, orthic luvisol; A_p horizon of silt loam, cambisol) amended with fresh and aged (6 months) ¹⁴C-manure [40 g kg^?1 of soil; 6.36 mg of sulfadiazine (SDZ) equivalents per kg of soil], which was derived from two shoats treated with ¹⁴C-SDZ. Mineralization of ¹⁴C-SDZ residues was below 2% after 218 days depending little on soil type. Portions of extractable ¹⁴C (ethanol-water, 9:1, v/v) decreased with time to 4–13% after 218 days of incubation with fresh and aged ¹⁴C-manure and both soils. Non-extractable residues were the main route of the fate of the ¹⁴C-SDZ residues (above 90% of total recovered ¹⁴C after 218 days). These residues were high immediately after amendment depending on soil type and aging of the ¹⁴C-manure, and were stable and not remobilized throughout 218 days of incubation. Bioavailable portions (extraction using CaCl₂ solution) also decreased with increasing incubation period (5–7% after 218 days). Due to thin-layer chromatography (TLC), 500 μg of ¹⁴C-SDZ per kg soil were found in the ethanol-water extracts immediately after amendment with fresh ¹⁴C-manure, and about 50 μg kg^?1 after 218 days. Bioavailable ¹⁴C-SDZ portions present in the CaCl₂ extracts were about 350 μg kg^?1 with amendment. Higher concentrations were initially detected with aged ¹⁴C-manure (ethanol-water extracts: 1,920 μg kg^?1; CaCl₂ extracts: 1,020 μg kg^?1), probably due to release of ¹⁴C-SDZ from bound forms during storage. Consistent results were obtained by extraction of the ¹⁴C-manure-soil samples with ethyl acetate; portions of N-acetylated SDZ were additionally determined. All soluble ¹⁴C-SDZ residues contained in ¹⁴C-manure contributed to the formation of non-extractable residues; a tendency for persistence or accumulation was not observed. SDZ's non-extractable soil residues were associated with the soluble HCl, fulvic acids and humic acids fractions, and the insoluble humin fraction. The majority of the non-extractable residues appeared to be due to stable covalent binding to soil organic matter.     

Behavior of atrazine in soils of tropical zone

Abstract

Movement and degradation of ¹⁴C‐atrazine (2‐chloro 4‐(ethylamino)‐6‐(isopropylamino)‐s‐triazine, was studied in undisturbed soil columns (0.50m length × 0.10m diameter) of Gley Humic and Deep Red Latosol from a maize crop region of Sao Paulo state, Brazil. Atrazine residues were largely confined to the 0–20cm layers over a 12 month period Atrazine degraded to the dealkylated metabolites deisopropylatrazine and deethylatrazine, but the major metabolite was hydroxyatrazine, mainly in the Gley Humic soil. Activity detected in the leachate was equivalent to an atrazine concentration of 0.08 to 0.11μg/1.

The persistence of ¹⁴C‐atrazine in a maize‐bean crop rotation was evaluated in lysimeters, using Gley Humic and Deep Red Latosol soils. Uptake of the radiocarbon by maize plants after 14‐days growth was equivalent to a herbicide concentration of 3.9μg/g fresh tissue and was similar in both soils. High atrazine degradation to hydroxyatrazine was detected by tic of maize extracts. After maize harvest, when beans were sown the Gley Humic soil contained an atrazine concentration of 0.29 μg/g soil and the Deep Red Latosol, 0.13 μg/g soil in the 0–30 cm layer. Activity detected in bean plants corresponded to a herbicide concentration of 0.26 (Gley Humic soil) and 0.32μg/g fresh tissue (Deep Red Latossol) after 14 days growth and 0.43 (Gley Humic soil) and 0.50 μg/g fresh tissue (Deep Red Latossol) after 97 days growth. Traces of activity equivalent to 0.06 and 0.02μg/g fresh tissue were detected in bean seeds at harvest. Non‐extractable (bound) residues in the soils at 235 days accounted for 66.6 to 75% (Gley Humic soil and Deep Red Latossol) of the total residual activity.     

Effect of organic amendment on degradation and formation of bound residues of methabenzthiazuron in soil under constant climatic conditions

Abstract

The degradation of [phenyl‐U‐¹⁴C]methabenzthiazuron (MBT) and formation of bound residues in the surface soil of an orthic luvisol were studied under constant climatic conditions (20°C, 40 % of maximum water holding capacity). In two treatments (with and without preincubation in the soil) maize straw was amended at a rate of 1.5 g/100 g dry soil in addition to the application of MBT. The mineralization of uniformly labeled maize straw was studied simultaneously. In additional flasks, MBT was incubated at 0, 10 and 30°C with and without addition of maize straw.

The turnover of the amended maize straw led to an enhanced dissipation of MBT which was mainly due to the formation of bound residues. This corresponded to a higher microbial activity in the soil after straw amendment and the intensive mineralization of the radiolabeled maize straw. About 2–3 % of the applied radioactivity from the radiolabeled maize straw was measured in the soil microbial biomass 10 and 40 days after application whereas ¹⁴C from MBT was only incorporated into soil microbial biomass in the treatments with straw amendment.

Within the bound residue fractions relatively more radioactivity was measured in fulvic and humic acids after straw amendment. Increasing temperatures promoted the dissipation of MBT and the formation of bound residues in both treatments, but without amendment of maize straw these effects were far less pronounced. The laboratory scale degradation experiment led to similar results as were found in a corresponding lysimeter study. Differences that were observed could be explained by different temperature regimes of the experiments and time of aging in soil.