Influence of soil pH and contents of organic carbon and clay on the volatilization of [14C]fenpropimorph after application to bare soil

The behaviour of the morpholine fungicide fenpropimorph applied to soil was investigated in a laboratory chamber. The volatility and metabolism of a ¹⁴C-labelled fenpropimorph formulation (Corbel^®) was studied after application to three soils (sandy loam, loamy clay and loamy sand), simulating a four-day weather scenario in the volatilization chamber. Additional experiments were conducted under standard climatic conditions over a period of 24 h using sandy soils with different pH values. The results of the first experiments showed that most of the radioactivity applied remained in the soils as unchanged fenpropimorph four days after application. In the experiments with the sandy loam and loamy clay, less than 5% of the applied radioactivity was removed by volatilization whereas 11·4% volatilized from the surface of the loamy sand. The comparatively higher volatilization of the fungicide from the loamy sand was confirmed by the later experiments indicating that higher soil pH favoured volatilization of [¹⁴C]fenpropimorph from sandy soils. Thus 5·6% (pH 5·0), 18·9% (pH 5·8) and 28·3% (pH 6·6) of the radioactivity applied volatilized within one day after application. The overall recoveries were between 93·8% and 111·3% in these experiments. © 1998 SCI     

Influence of temperature on the volatilization of triallate and terbutryn from two soils

The rate of volatilization of the formulated herbicides triallate and terbutryn was studied in a volatilization chamber under controlled laboratory conditions using two soils with sand and loam textures, respectively. The influence of the most relevant experimental variables was investigated by measuring the amount of volatilized herbicides after their incorporation to the soils. The effect of soil temperature was studied in the range from 5 °C to 25 °C. Initial soil water content was fixed at field capacity depending on the physical characteristics of each soil. The volatilized herbicide was trapped in C18 cartridges during different time intervals and analyzed by HPLC. The volatilization losses for triallate ranged from 7 to 58%, whereas the losses for terbutryn ranged from 1 to 6%. Sorption and volatilization resulted in two coupled effects of major importance in these experiments: the sorption process was favoured as temperature decreased, whereas volatilization increased as temperature increased. © 2000 Society of Chemical Industry     

Persistence of gamma-BHC and beta-BHC in Indian rice soils under flooded conditions

The relative persistence of [¹⁴C]-gamma-BHC and [¹⁴C]-beta-BHC in Indian rice soils under flooded conditions was studied. In alluvial, laterite and pokkali (acid sulphate, saline) soils, rapid degradation of both isomers occurred; in sandy and kari (acid sulphate, saline) soils, both isomers persisted even after 41 days of flooding. The rapid degradation of BHC isomers in the former three soils was related to highly negative redox potentials within 20 days of flooding in contrast to oxidised conditions in sandy and kari soils even after 41 days. During the degradation in the soils, beta-BHC showed longer lag than gamma-BHC. Results suggest that the degradation of beta-BHC commences at a potential lower than that required for gamma-BHC degradation. Greater decomposition of gamma-BHC occurred in rice straw-amended soils than in unamended soils when the insecticide was incorporated to the soils in an aqueous solution. Addition of BHC isomers to the soils in ethanol resulted in comparable rates of rapid decomposition in both rice straw-amended and unamended soils, since ethanol was as effective as rice straw in lowering the redox potentials of the soils favouring BHC decomposition in unamended soil as well.     

水分对不同栽培年限日光温室土壤氮矿化的影响

采用室内短期（84 d）好气培养法评价了不同水分供应水平下（田间持水量的60%、80%及100%,分别用60FC、80FC和100FC表示）陕西杨凌地区不同栽培年限（种植前、种植第二年及种植第三年）日光温室土壤（0~20 cm及20~40 cm土层）氮素矿化特性。结果表明：随着日光温室栽培年限的延长,0~20 cm土层累积净矿化氮量显著增加,且随栽培年限的增加,20~40 cm 土层氮矿化势呈增加的趋势;土壤水分含量由60FC增加到80FC,土壤累积矿化氮量呈增加趋势,但当含水量达到100FC时,土壤累积矿化氮量降低。回归分析结果表明,土壤有机质含量每增加1 g·kg^-1, 60FC、80FC、100FC土壤含水量条件下土壤氮矿化势分别增加 1.62、1.88 mg·kg^-1和1.57 mg·kg^-1;土壤全氮含量每增加1 g·kg^-1,土壤氮矿化势分别增加28.93、33.42 mg·kg^-1和27.82 mg·kg^-1。因此,建议日光温室蔬菜栽培中应综合考虑温室年限及灌溉量对土壤氮素矿化过程的影响。     

Metabolism of DDT and related compounds in cell suspension cultures of soybean (Glycine max L.) and wheat (Triticum aestivum L.)

Cell suspension cultures of wheat and soybean were incubated with [¹⁴C]-1,1,1-trichloro-2,2-bis-(4-chlorophenyl)ethane (DDT), [¹⁴C]-1,1-dichloro-2,2-bis-(4-chlorophenyl)ethene (DDE), and [¹⁴C]-2,2-bis-(4-chlorophenyl)acetic acid (DDA) under standardized conditions. Polar metabolites were formed in yields of 1–2.5% in the cases of DDT and DDE, and of 56% in the case of DDA. A nonpolar metabolite was only observed in the case of DDT in soybean. This metabolite was identified as DDE on the basis of cochromatography and mass spectroscopy. By the same methods DDA was identified as a major polar DDT metabolite of both soybean and wheat. The further conversion of DDA to hexose esters was demonstrated by chromatographic and mass spectroscopic comparison with synthetic DDA-β-d-glucopyranosyl tetraacetate. These studies suggest the metabolic sequence, DDT → DDA → DDA-hexose ester.     

The metabolism of DDT in vivo by the Japanese quail (Coturnix coturnix japonica)

Male and female Japanese quail (Coturnix coturnix japonica) were given intraperitoneal injections of [¹⁴C]DDT in ethanol at a rate of 13.4 mg/kg body wt. Fifty-six days later the tissues and droppings were analysed for total ¹⁴C and metabolites. The rate of loss of ¹⁴C in droppings was very similar in males and females. The maximal rate was reached on the third day, and 65–66% of the injected dose was voided by the fifty-sixth day. Ninety-three to ninety-four percent of the ¹⁴C in droppings and 83–90% of the ¹⁴C in tissues were extracted by solvents. Combined extracts from males and females were used for determination of DDT and its metabolites. Expressing all results as percentages of injected dose, the following were isolated from droppings: DDA (24%), DDT (3%), DDD (5.1%), DDE (11%), and uncharacterised polar metabolites (17%). Twenty-five percent of the dose was retained in the tissues and this was largely accounted for as DDT (10.4%) and DDE (10.5%). Of the total metabolites found 31% was DDE (almost equally divided between tissues and droppings) and 35% was DDA (almost entirely in droppings). Since DDD was not found in significant quantities in tissues, the substantial quantities in droppings were probably produced from DDT by the action of microorganisms.     

Residual effects of cultivation methods on weed seed banks and weeds in Cambodia

The effects of the planting method (transplanting vs. direct seeding), rice cultivar (Sen Pidao vs. Phka Rumduol), and herbicide application (admixture of bentazone and cyhalofop‐butyl) on weeds and weed seed banks were quantified in unflooded, shallowly flooded, and deeply flooded paddy fields in Cambodia in 2005 and 2006. Broad‐leaved weeds infested more toward maturity in 2006 than in 2005, particularly in directly seeded plots. Weed dry weights at pre‐heading and/or maturity were consistently reduced by herbicide application and Phka Rumduol cultivar, while weed numbers increased under unflooded condition. The proportion of sedges was consistently larger in directly seeded and non‐herbicide plots at pre‐heading. Larger numbers and dry weights of sedges and total weeds in 2005 caused larger seed bank sizes of sedges and total weeds in 2006, which further caused their infestation in 2006. A greater weed dry weight at 62 days after sowing in 2005 resulted in larger seed banks of Cyperus iria and Fimbristylis miliacea, which were most severe under non‐herbicide, direct‐seeded treatment, while that at rice maturity resulted in larger seed banks of Cyperus difformis, Scirpus juncoides, and Lindernia antipoda. Overall, sedges shared the majority of the total weed seed bank, followed by broad‐leaved weeds and then grasses. A lower yield in 2005 led to significantly larger seed bank sizes of sedges, but not of grasses or broad‐leaved weeds. Rice yield reduction was consistently related to larger numbers of sedges by heading and those of grasses at maturity.     

DDE inhibition of marine algal cell division and photosynthesis per cell

Exuviella baltica, a marine dinoflagellate, was exposed to DDE, the major metabolite of DDT, at a concentration of 25 μg/liter of medium. At intervals of 1 hr and 1, 2, 3, and 4 days, cells were withdrawn from the culture, washed, and reseeded in DDE-free medium, and their growth (cell division) and photosynthesis were monitored for 14 days. No increase in cell numbers occurred until cells were removed from DDE, and lag phases, proportional to the duration of DDE exposure and lasting up to 5 days, preceded exponential growth. Cell densities comparable to controls were eventually reached in all treated cultures. A similar pattern of ¹⁴C uptake per milliliter of culture and per cell was observed. A 1-hr exposure to DDE resulted in a maximum reduction of 45% in carbon fixed per cell, while longer exposures caused reductions as great as 91%, relative to controls.     

Occurrence of chlorinated hydrocarbon insecticides, southern Florida--1968-72.

The frequency with which chlorinated hydrocarbon insecticides appear in samples of southern Florida surface waters decreased sharply between 1968 and 1972. Sediment analyses attest to the earlier widespread use of chlordane, DDT, and dieldrin. Insecticide residues are more frequently detected in southern Florida than in other U.S. cropland soils. Transport of DDT, DDD, and DDE from the Everglades agricultural area into water conservation areas and undeveloped parts of the Everglades of southeastern Florida is facilitated by a system of water-management canals. Canal sediments within the urban area of southern Florida have high DDD, DDE, and dieldrin residue concentrations which may reflect local use of insecticides rather than their transport from adjacent agricultural areas.     

Influence of nitrogen fertilisers on the persistence of carbaryl and carbofuran in flooded soils

Ammonium sulphate and urea, but not potassium sulphate, increased the persistence of carbaryl in a flooded laterite soil with a low native nitrogen content (0.04%), but not in an alluvial soil with a higher nitrogen content (0.11%). Thus, NH₄⁺ but not SO₄^2-, contributed to the increased persistence of carbaryl. Likewise, ammonium sulphate increased the persistence of carbofuran in the laterite soil, but not in the alluvial soil. Significant accumulations of 1-naphthol and 2,3-dihydro-2, 2-dimethylbenzofuran-7-ol (‘carbofuran phenol’), in soils treated with carbaryl or carbofuran, suggested hydrolysis as the major pathway of degradation. Treatment of the two soils with ammonium sulphate, urea or potassium sulphate led to a decrease in soil-bound residues and an increase in the respective hydrolysis products, compared with untreated soils. Sorption studies indicated that NH₄⁺ and SO₄^2- compete with carbaryl, 1-naphthol and carbofuran for sorption and exchange sites in the complex soil system. Evolution of [¹⁴C]carbon dioxide from ring-¹⁴C in carbaryl and carbofuran was negligible. Consequently, after 40 days, more than 50% of the ¹⁴C in [¹⁴C]carbaryl and [¹⁴C]carbofuran remained in the soils as hydrolysis products (1-naphthol or 2,3-dihydro-2,2-dimethylbenzofuran-7-ol) plus soil-bound residues.     

Environmental fate of herbicides trifluralin, metazachlor, metamitron and sulcotrione compared with that of glyphosate, a substitute broad spectrum herbicide for different glyphosate-resistant crops

The introduction of crops resistant to the broad spectrum herbicide glyphosate, N-(phosphonomethyl)glycine, may constitute an answer to increased contamination of the environment by herbicides, since it should reduce the total amount of herbicide needed and the number of active ingredients. However, there are few published data comparing the fate of glyphosate in the environment, particularly in soil, with that of substitute herbicides. The objective of this study is to compare the fate of glyphosate in three soils with that of four herbicides frequently used on crops that might be glyphosate resistant: trifluralin, alpha,alpha,alpha-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine, and metazachlor, 2-chloro-N-(pyrazol-1-ylmethyl)acet-2',6'-xylidide for oilseed rape, metamitron, 4-amino-4,5-dihydro-3-methyl-6-phenyl-1,2,4-triazin-5-one for sugarbeet and sulcotrione, 2-(2-chloro-4-mesylbenzoyl)cyclohexane-1,3-dione for maize. The distribution of herbicides between the volatilized, mineralized, extractable and non-extractable fractions was studied, along with the formation of their metabolites in laboratory experiments using 14C-labelled herbicides, over a period of 140 days. The main dissipation pathways were mineralization for glyphosate and sulcotrione, volatilization for trifluralin and non-extractable residues formation for metazachlor and metamitron. The five herbicides had low persistence. Glyphosate had the shortest half-life, which varied with soil type, whereas trifluralin had the longest. The half-lives of metazachlor and sulcotrione were comparable, whereas that of metamitron was highly variable. Glyphosate, metazachlor and sulcotrione were degraded into persistent metabolites. Low amounts of trifluralin and metamitron metabolites were observed. At 140 days after herbicide applications, the amounts of glyphosate and its metabolite residues in soils were the lowest in two soils, but not in the third soil, a loamy sand with low pH. The environmental advantage in using glyphosate due to its rapid degradation is counterbalanced by accumulation of aminomethylphosphonic acid specifically in the context of extensive use of glyphosate.     

The metabolism of p,p′-DDT by the feral pigeon (Columba livia)

Male feral pigeons were dosed with ring-labeled $\text{[}{}^{14}\text{C}\text{]p,p′-}\text{DDT}$ and the tissues and droppings analyzed for total ¹⁴C, extractable ¹⁴C, and metabolites. Only 16% of an intraperitoneal dose of 1.5–2.2 mg kg^?1 was voided in the droppings over 28 days; the rate of loss reached a maximum on the 14th day and then fell quickly away. The rate of removal of ¹⁴C in droppings was low in comparison to that found in the rat and the Japanese quail. When pigeons were dosed with 32–38 mg kg^?1 DDT per bird, and killed after 77 days, 5.4% of the dose was eliminated in droppings and 87% was recovered in the body. The tissues and droppings from this experiment were analyzed for DDT and its metabolites. Of the ¹⁴C remaining in tissues 88% was accounted for as the apolar compounds DDE, DDT, and DDD. Approximately half of the ¹⁴C in droppings was present as DDE, DDT, and DDD, whereas 27–35% was apparently in conjugated form, extractable from aqueous solutions by ethyl acetate after prolonged acid hydrolysis. Two polar metabolites were isolated from the acid-released material. One was p,p′-DDA; the other was extractable from aqueous solution at pH 8 and was tentatively identified as a monohydroxy derivative of p,p′-DDT. DDE accounted for 93% of the ¹⁴C present as metabolites in tissues and droppings, clearly indicating the importance of this intermediate in this study. The metabolism of DDT in the feral pigeon is discussed in relation to its metabolism by other species.     

Inhibition of biological hydrolysis of parathion in rice straw-amended flooded soil and its reversal by nitrogen compounds and aerobic conditions

The effect of nitrogen compounds and moisture regimes on the inhibition of the biological hydrolysis of parathion in rice straw-amended soil under flooded conditions was studied. Single applications of rice straw, potassium nitrate or ammonium sulphate to the flooded soil, inoculated with parathion-hydrolysing enrichment culture, inhibited the hydrolysis of the insecticide; the inhibition was reversed, however, in combined applications of rice straw with potassium nitrate or with ammonium sulphate. Aqueous extracts of rice straw-amended soils incubated under flooded undisturbed conditions as well as at 100% moisture inhibited the hydrolysis. The inhibitory factor was not formed in rice straw-amended flooded soils incubated at 50 and 75% moisture levels.     

The sensitivity of mitochondrial Mg2+ ATPase to DDT and analogs at different temperatures

Oligomycin-sensitive (O-S) Mg²⁺ ATPase from American cockroach muscle was more sensitive to DDT, TDE, methoxychlor, and DDE at cool temperatures than at warm temperature, thus showing a negative temperature effect. In contrast, inhibition by acaricides dicofol, chlorfenethol, and Plictran shows a positive temperature effect. Oxidative phosphorylation in a mitochondrial preparation from cockroach coxal muscle was reduced by DDT, but the reduction was greater at a higher temperature (32°C) than at a cooler temperature (22°C). In addition, Na⁺K⁺ ATPase from cockroach nerve cord showed a positive temperature effect with DDT. The inhibition by DDT was much less on Na⁺K⁺ ATPase than on O-S Mg²⁺ ATPase. The negative temperature effect by DDT and analogs on O-S Mg²⁺ ATPase parallels toxicity effects on insects and fish as reported by numerous researchers. The results provide further evidence for this energy-regulating enzyme being a critical component in the biological action of DDT.     

长期秸秆和地膜覆盖对旱作冬小麦农田土壤碳组分的影响

地表覆盖秸秆和地膜是我国西北旱作农田土壤固碳的重要田间管理措施,但其对土壤碳组分的长期影响尚不明确。基于田间定位试验,设生育期高量秸秆覆盖(9 000 kg·hm^-2,HSM)、生育期低量秸秆覆盖(4 500 kg·hm^-2,LSM)、夏闲期秸秆覆盖(9 000 kg·hm^-2,FSM)、生育期地膜覆盖(PM)和无覆盖对照(CK)共5个处理,研究了秸秆覆盖和地膜覆盖12 a和13 a后旱作冬小麦农田土壤总有机碳(SOC)、颗粒有机碳(POC)、潜在矿化碳(PCM)和微生物量碳(MBC)含量的变化规律。2 a平均结果表明：与CK相比,HSM和LSM处理均显著提高了0～10 cm土层各碳组分含量以及10～20 cm土层SOC、POC、MBC含量,同时还显著提高了0～20 cm土层POC和MBC占SOC的比例;而FSM和PM处理对各土层土壤碳组分含量及其占SOC的比例均无显著影响。土壤碳组分含量相互之间均存在极显著正相关关系。综上可知,长期生育期秸秆覆盖能有效提高旱作冬小麦农田耕层土壤有机碳及其组分含量,且提高覆盖量有助于促进...     

The in vivo sensitivity of ATPases to DDT,DDE, and physical immobilization in American cockroaches

American cockroaches injected with sublethal doses of DDT (0.75 μg/roach) at 5-day intervals showed a 40% reduction in oligomycin-sensitive Mg²⁺ATPase from muscle homogenates, and a 23% reduction of Na⁺-K⁺ATPase from nerve cords. Thus, the maximum effect measured occurred with the same enzyme and tissue as determined from in vitro studies. The metabolite, DDE, used at 15 μg per roach, gave no significant change in activity of the ATPase system following injection. In contrast, high single doses of DDT (7.5 μg/roach) and 100 μg DDE and dicofol per roach caused over 30% increase in oligomycin-sensitive Mg²⁺ATPase of muscle and a 10–15% increase in Na⁺-K⁺ATPase of nerve cords measured 24 and 48 hr later. While a similar response was observed for Mg²⁺ATPase activities in cockroaches that were immobilized, the increase in enzyme activities were much greater than that caused by the pesticides.     

Degradation of [14C]Terbuthylazine and [14C]Atrazine in Laboratory Soil Microcosms

The degradation and formation of major chlorinated metabolites of terbuthylazine and atrazine in three soils (loamy clay, calcareous clay and high clay) were studied in laboratory experiments using molecules labelled with ¹⁴C on the s-triazine ring. Soil microcosms were treated with the equivalent of 1 kg ha^-1 of herbicide and incubated in the dark for 45 days at 20(±1)°C. The quantity of [¹⁴C]carbon dioxide evolved in the soils treated with atrazine was negligible and could not be attributed to mineralization of the parent molecule. The mineralization of terbuthylazine accounted for 0·9–1·2% of the initial radioactivity. In the soils studied, the extrapolated half-lives varied from 88 to 116 days for terbuthylazine and 66 to 105 days for atrazine, with no significant differences for the three soils and the two molecules. The deethyl metabolites of the two s-triazines and the deisopropyl-atrazine metabolite appeared during the incubation in the three soils. The completely dealkylated metabolite was not detected in any of the soils. After 45 days of incubation, the non-extractable soil residues for the high clay, loamy clay and calcareous clay soils represented for terbuthylazine, 33·5, 38·3 and 43·1% and for atrazine, 19·8, 20·8 and 22·3% of the initial radioactivity. © 1997 SCI.     

The adsorption and degradation of glyphosate in five Hawaiian sugarcane soils*

The rate of aerobic evolution of ¹⁴CO₂ from ¹⁴C-glyphosate labelled in the methylphosphonyl carbon, varied 100-fold within a group of five Hawaiian sugarcane soils. The rate depended inversely on the degree of soil binding, probably associated with the phosphonic acid moiety, and to a less certain extent on soil pH and soil organic matter. After an initial rapid degradation, the rate of ¹⁴CO₂ evolution in three soils reached a constant at 16–21 days which continued to the 60-day termination. The other two soils showed a continually decreasing rate throughout. Two soils released over 50% of the labelled carbon in 60 days, a third released 35%, while the remaining soils released 1.2 and 0.8% respectively. Labelled carbon in the soils after 60 days consisted of glyphosate and one metabolite, aminomethyl-phosphonic acid, with glyphosate predominating in high fixing soils. The ¹⁴C could be extracted almost completely with NaOH solution, and remained mainly in solution after acidification.     

Dichlorodiphenyltrichloroethane determination in air by thermal desorption gas chromatography-mass spectrometry

BACKGROUND: Current quantitative methods for airborne dichlorodiphenyltrichloroethane (DDT) require collection and extraction times of ≥ 12 h. The aim of this study was to develop a method for quantifying airborne DDT with a short (<4 h) collection and analysis time. RESULTS: Precision [relative standard deviation (RSD)] for each calibration point (0.8–9.0), linearity (R² = 0.99) and apparent recovery (R′ = 96.5%) were determined from thermal desorption (TD) gas chromatography–mass spectrometry (GC-MS) analyses of Tenax-TA-packed sampling tubes spiked with 1–250 ng of DDT. Recovery of ¹³C-labeled 4,4′-DDT from tubes spiked before and after air sampling was 97.3 and 90.3% respectively. DDT was detected and quantified in 1–3 L samples of air collected during 10–180 min sampling events. A significant difference was observed in DDT air concentration between 28 and 33 °C during microchamber studies. CONCLUSIONS: The results demonstrate that the TD GC-MS method developed in this study is precise, reproducible and linear over the span of 1–250 ng of DDT spiked onto TD tubes. By avoiding dilution of the sample, the method described allows the measurement of DDT vapor concentrations during short sampling periods (10–180 min) relevant to mosquito behavior studies. Published 2012 by John Wiley & Sons, Ltd.     

The accumulation and distribution of pp′DDT and related compounds in an apple orchard .I. residues in the soil

Soils from an orchard sprayed annually (1953-1969) with technical DDT (77% pp′DDT and 22 % pp′DDT) were analysed for residues from 1964 until 1969. The amount of DDT found after 17 years was 21 %pp′DDTout of 27.1 kg/ha applied, and 7 % of pp′DDT out of 7.6 kg/ha. The vertical distribution of residues (pp′DDT, pp′DDE, pp′TDE and pp′DDT) showed a linear relationship between log amount and depth, with approximately 80% in the top 10 cm of soil. At depths from 50 to 210 cm, residue values were too small to be determined (i.e. < 1 ng/g dry wt). The surface distribution in the orchard showed a systematic pattern of circular areas of residues, with maximum values centred at each trunk (7.5 μg/g) and decreasing rapidly to each alley (1.9 ug/g). The levels of pp′DDT had reached a steady state (3-4 kg/ha) and the half-life time was calculated as 3.0 j′ears. pp′DDE (1.8 kg/ha) was the main metabolite of pp′DDT. Small amounts of pp′TDE were also found, pp′DDT was less persistent than pp′DDT, with a half-life time of 1.5 years.