Photodegradation of rotenone in soils under environmental conditions

An environmental fate study was performed to analyze the effects of soil components on the photochemical behavior of rotenone. Photodegradation experiments were carried out on three types of soil collected in southern Italy, Valenzano (VAL), Turi (TUR), and Conversano (CON), from April to June 2006. Soil thin-layer plates (1 mm thick) were spiked with 1.5 mg/kg of rotenone and exposed under natural conditions of sunlight and temperature. The plates were removed from the sunlight at predetermined intervals of continuous irradiation. Other soil samples, control and sterilized, were kept in the dark to evaluate possible effects of chemical and microbiological degradation during the irradiation experiment. The time for 50% loss of the initially applied rotenone varied from 5 to 7 h, following the order TUR < CON < VAL. In environmental studies, changes in temperature and/or moisture affected the degradation rate and caused deviations from first-order kinetics. The photolysis reaction fit the two compartment or the multiple compartment model pathways better. A fast initial decrease during the first 5 h of rotenone irradiation was followed by a much slower decline, which clearly indicates the rather complex chemical process of rotenone photodegradation on soil surfaces. Also, the degradation was shown to be directly related to the soil concentration of clay and organic matter. Rotenolone (12abeta-hydroxyrotenone) was detected by HPLC/DAD/MS analysis as the only photodegradation byproduct of rotenone in soil thin layers. Results provide additional insights on the rates and the mechanisms of rotenone degradation, aiming to describe more clearly the degradation performance of chemical residues in the environment.     

Production and persistence of urease activity in soils

Addition of urea to Iowa soils did not induce urease activity, but production of urease activity was observed on addition of glucose and other organic materials that promote microbial activity. The persistence of the urease activity produced on addition of these materials varied with the soil, but, with each soil studied, the urease activity after addition of organic materials eventually was identical to that of the unamended soil. No increase or decrease in urease activity was observed when unamended or urea-treated soils were incubated under aerobic conditions for several months. It is concluded that soil constituents protect urease against microbial degradation and other processes leading to inactivation of enzymes and that every soil has a stable level of urease activity determined by the ability of its constituents to provide this protection.     

Degradation of PCP in soils

In laboratory experiments, the degradation of PCP in soil with regard to the relationship to soil properties was studied under upland and flooded conditions using gas-chromatographic techniques. The degradation products and their behavior were elucidated by using 10 diCferent soils collected from rice fields and adjacent upland fields and one sample of a subsoil from the forest. The results are as follows:

1) The degradation of PCP in soils was faster under flooded conditions than upland conditions.

2) The degradation under flooded conditiont was more rapid in soils collected from rice fields than in those from adjacent upland fields, Tbe reverse was true under upland conditions.

3) The degradation rate was highly correlated with the organic matter content of the soil. Almost 100% of the PCP remained in the subsoil sample even after 50 days of incubation. The rate was slightly correlated with the clay mineral composition, free iron content, phosphate absorption coefficient and C.E.C., but hardly at all with texture, clay content, degree of base saturation, soil pH and available phosphorus content.

4) As the degradation products of PCP, 3 tetrachlorophenols, 4 or 5 trichlorophenols and PCP methyl ether were detected, PCP methyl elher and 2, 3, 4, 5-tetrachlorophenol were the major products, but the amount of the latter varied greatly during the course of incubation.     

Salinity and the persistence of parathion in flooded soils

The persistence of parathion in five coastal saline soils of varying electrical conductivity and in one nonsaline soil sample was studied under flooded conditions. Parathion was decomposed faster in nonsaline soil than in saline soils and its stability increased with increasing electrical conductivity. The addition of salts to the nonsaline soil at 4, 8 and 16 dS^?1 increased the persistence of parathion. Nitro-group reduction, and not hydrolysis, was the major route of parathion degradation in saline and nonsaline soils. The accumulation of aminoparathion was less pronounced in saline soils than in nonsaline soil concomitant with slow degradation of parathion in saline soils. The inhibition of nitro-group reduction in saline soils was related to low microbial activities as reflected in decreased dehydrogenase activity and slow iron reduction.     

Urine enhances the leaching and persistence of estrogens in soils

The release of endocrine disrupting chemicals (EDCs) into the environment is of concern due to their potential deleterious effects on freshwater ecosystems and human health. Estrogen losses from agricultural land to freshwater have been implicated as a diffuse source of EDC pollution, however, uncertainty exists about the magnitude of this flux in comparison to other point sources (e.g. sewage treatment plants). Recent reviews have all highlighted the need for more mechanistic studies on hormone behaviour in soil environments. The aim of this study was to investigate the influence of aqueous matrix on the leaching, sorption and persistence of two naturally occurring hormones, estrone and 17β-estradiol in three agricultural grassland soils. The hormones were applied to the surface of the soil in two solvents, distilled water and natural sheep urine. Rainfall was subsequently applied to the top of the soil columns and the leachate collected. In comparison to distilled water, the presence of sheep urine both enhanced and prolonged the amount of estrogen leaching from soil. We hypothesized that this enhanced rate of estrogen migration in soil was due to changes in either estrogen sorption or microbial activity. While the presence of urine did not greatly affect the rate and amount of estrogen sorption to soil (K_d = 4-16) it did significantly reduce the rate of hormone mineralization. Overall, our study shows that vertical estrogen movement is rapid, soil type dependent and regulated by the aqueous matrix in which the hormones are contained. In terms of risk assessment and environmental fate modelling, we conclude that previous studies performed using hormones contained in artificial matrices (e.g. distilled water) may have underestimated their rate of dissipation in the environment.     

Sorption and persistence of wastewater-borne psychoactive and antilipidemic drugs in soils

Purpose  

Although the ubiquity of pharmaceuticals in treated wastewater has now been well documented, their fate and risk during beneficial wastewater reuse are far less understood. Soil sorption and degradation are important processes affecting the leaching potential of trace contaminants in irrigated soil. To this end, we examined the sorption and attenuation of six psychoactive and antilipidemic drugs, i.e., carbamazepine, diazepam, Dilantin, meprobamate, primidone, and gemfibrozil, in a loam (LVL) and a loamy sand representative of golf course soils in the southwestern United States.     

Degradation of diphenyl ether herbicides in soils

The gas chromatographic determination of CNP (2,4,6-trichlorophenyl 4-nitrophenyl ether), nitrofen (2,4-dichlorophenyl 4′-nitrophenyI ether), chlomethoxynil (2,4-dieblorophenyl 3′-methoxy-4′-nitrophenyl ether), CFNP (2,4-dichloro-6-fluorophenyl 4-nitrophenyl ether) and their amino derivatives in soils were carried out. Good recoveries from soils were obtained for the diphenyl ethers. On the other hand, satisfactory recoveries from soils were also obtained for the amino derivatives at high concentrations, but the recoveries at lower concentrations averaged about 66% for the least recovered compound.

The degradation of several diphenyl ether herbicides in two paddy soils were compared under flooded and upland conditions. The degradation was much slower under upland than under flooded conditions. Considerable amounts of their amino derivatives were produced in soils under flooded conditions, but not under upland conditions. It was suggested that the diphenyl ethers to the amino derivatives involved both chemical and microbial processes. CNP and chlomethoxynil degraded faster at lower concentrations than at higher ones.     

Degradation of trichloroacetic acid in Saskatchewan soils

The persistence of ¹⁴C-trichloroacetic acid in three Saskatchewan soils was investigated at different moisture regimes under laboratory conditions at 25 ± 1°C. Following soil extraction with 0.1 m calcium chloride soln, radiochemical analytical procedures were used to monitor the breakdown. At rates equivalent to 4.4 kg/ha, degradation was most rapid in a high organic soil, with complete breakdown occurring within 3 weeks at moisture levels in excess of the wilting point. On a sandy loam and on a heavy clay breakdown was somewhat slower.     

Degradation processes and nutrient constraints in sodic soils

Accumulation of excess sodium (Na⁺) in a soil causes numerous adverse phenomena, such as changes in exchangeable and soil solution ions and soil pH, destabilization of soil structure, deterioration of soil hydraulic properties, and increased susceptibility to crusting, runoff, erosion and aeration, and osmotic and specific ion effects on plants. In addition, serious imbalances in plant nutrition usually occur in sodic soils, which may range from deficiencies of several nutrients to high levels of Na⁺. The structural changes and nutrient constraints in such soils ultimately affect crop growth and yield. The principal factor that determines the extent of adverse effects of Na⁺ on soil properties is the accompanying electrolyte concentration in the soil solution, with low concentration promoting the deleterious effects of exchangeable Na⁺ even at exchangeable sodium percentage (ESP) levels less than 5. Consequent to an increase in the use of poor quality waters and soils for crop production, the problems of sodic soils can be expected to increase in future. The mechanisms that explain sodic behaviour can provide a framework in which slaking, swelling and dispersion of clay together with nutrient constraints in sodic soils may be assessed so that the practices to manage such soils can be refined for long‐term sustainable agriculture. Copyright © 2002 John Wiley & Sons, Ltd.     

Degradation and sorption of pirimiphos-methyl in two Nigerian soils

This research is a continuation of a study on the behavior of hydrophobic organic compounds in the environment and describes the simultaneous abiotic degradation and sorption of pirimiphos-methyl (O-2-diethylamino-6-methylpyrimidin-4-yl O,O-dimethylphosphorothioate) under controlled conditions in soil/water slurries. A microfiltration-HPLC technique was employed to follow these processes in two well-characterized soils from the Middle Belt region of Nigeria. Rapid sorption of the pesticide occurs during the first 10 min of equilibration and accounted for 37% of the original pirimiphos-methyl in the Rhodic Kandiustalf soil and for 41% of the original concentration in Aquic Ustropept soil. Subsequent slow processes were followed during the remaining 30 days of the experiment. During this time, first-order rate constants for disappearance from solution of pirimiphos-methyl were found to have values of 6.1 x 10(-)(7) and 9.8 x 10(-)(7) s(-)(1) for the Rhodic and Aquic soils, respectively. Similarly, rate constants for production of the product, pyrimidinol, were calculated to be 6.0 x 10(-)(7) and 9.4 x 10(-)(7) s(-)(1) for the Rhodic and Aquic soils, respectively, giving pesticide degradation half-lives of 13 and 8.5 days. Disappearance of the pesticide is discussed in terms of a scheme involving both sorptive uptake by the soil and degradation by hydrolysis in the presence of the soil matrix. The labile sorption capacities for pirimiphos-methyl in the Rhodic and Aquic soils were found to be 0.75 and 0.90 micromol g(-)(1), respectively.     

Degradation and binding of atrazine in surface and subsurface soils

Understanding the dissipation rates of chemicals in unsaturated and saturated zones of subsurface soils will help determine if reductions of concentrations to acceptable levels will occur. Chemical properties and microbial biomass and activity were determined for the surface (0-15 cm), lower root (50-105 cm), and vadose (175-220 cm) zones in a Huntington silty clay loam (Fluventic Hapludoll) collected from an agricultural field near Piketon, OH. The rates of sorption, mineralization, and transformation (formation of bound residues and metabolites) of atrazine were determined. Microbial activity was estimated from the mineralization of (14)C-benzoate. We observed decreased levels of nutrients (total organic carbon, N, and P) and microbial biomass with depth, while activity as measured with benzoate metabolism was higher in the vadose zone than in either the surface or the root zones. Sorption coefficients (K(f)) declined from 8.17 in the surface to 3.31 in the vadose zone. Sorption was positively correlated with organic C content. Rates of atrazine mineralization and bound residues formation were, respectively, 12-2.3-fold lower in the vadose than in the surface soil. Estimated half-lives of atrazine ranged from 77 to 101 days in the surface soil, but increased to over 900 days in the subsurface soils. The decreased dissipation of atrazine with increasing depth in the profile is the result of decreased microbial activity toward atrazine, measured either as total biomass or as populations of atrazine-degrading microorganisms. The combination of reduced dissipation and low sorption indicates that there is potential for atrazine movement in the subsurface soils.     

Establishment and persistence of Rhizobium trifolii in western australian soils

Large scale experiments with inoculated and drill sown Trifolium subterraneum, T. hirtum, and T. cherleri showed that recent isolates of Rhizobium trifolii from healthy plants in problem pastures were superior to the strains used in commercially available inoculants. The new rhizobia are also shown to persist in the soil longer than the commercial strains. Evidence was obtained of different levels of performance by R. trifolii strains on different soils. Following the inclusion of one of the superior isolates in commercial peat inoculants, a number of farmer-sown pastures were examined for strain persistence. The new isolates showed much improved persistence over the older inoculant strains.     

Degradation of organotin compounds in organic and mineral forest soils

Broad industrial application of organotin compounds (OTC) leads to their release into the environment. OTC are deposited from the atmosphere into forest ecosystems and may accumulate in soils. Here, we studied the degradation of methyltin and butyltin compounds in a forest floor, a mineral, and a wetland soil with incubation experiments at 20 °C in the dark. OTC degraded slowly in soils with half‐lives estimated from 0.5 to 15 years. The first order degradation rate constants of OTC in soils ranged from 0.05 to 1.54 yr^–1. The degradation rates in soils were generally in the order mono‐ ≥ di‐ > tri‐substituted OTC. Stepwise dealkylation was observed in all cases of di‐substituted OTC, but only in some cases of tri‐substituted OTC. Decomposition rates of OTC in the forest floor were higher than in wetland and mineral soils. Tetramethyltin in the gas phase was not detected, suggesting little tin methylation in the wetland soils. Slow degradation of OTC in soils might lead to long‐term storage of atmospherically deposited OTC in soils.     

The influence of variations in soil copper on the yield and nutrition of spinach grown in microplots on two organic soils

Abstract

Spinach (Spinacia oleracea L. cv. Symphony) was grown in spring 1982 in field microplots of an organic soil (site I a mucky peat) containing 81 to 1063 μg Cu.g^‐1 soil, and cv. America of the same crop taken in summer 1982 on a peaty organic soil (site II) varying in Cu content from 13 to 1659 μg.g^‐1. The variations in soil Cu were mainly due to three rates of Cu applications in 1978 at site II and in 1979 at site I. At site I, the diversity in soil‐Cu had no effect on yield or foliar‐Cu levels in the crop. At site II soil‐Cu was positively correlated with yield and foliar Cu; and negatively with leaf Fe due to a dilution effect. Neither soil Cu nor foliar Cu had any significant effect on Mo in leaves at both sites, except that the increase in yield due to the highest level of Cu at site II was accompanied by an increased plant uptake of Mo. Also, foliar Cu was positively correlated with P, Mg and Mn levels in leaves at site I; and foliar Ca, Mg and Mn at site II.

Residual soil Cu up to 1063 μg.g^‐1 in a mucky peat and 16 59 μg.g^‐1 in a peat showed no signs of causing phytotoxocity or significant nutritional imbalance.     

Degradation and sorption of fluometuron and metabolites in conservation tillage soils

Soil sorption and dissipation of fluometuron (FLM) and three metabolites, desmethyl fluometuron (DMF), trifluoromethyl phenyl urea (TFMPU), and trifluoromethyl aniline (TFMA), were assessed in conservation tillage soils. In study I, surface Dundee silt loam soils from no-tillage (NT) and reduced-tillage (RT) areas were treated with 14C ring-labeled FLM or TFMA or unlabeled DMF, incubated for 34-42 days, extracted, and analyzed. Mineralization and volatilization of 14C-labeled FLM or TFMA were monitored. In study II, batch sorption assays (solute concentrations 2-50 micromol L-1; 2:1 solution:soil; 18 h) were conducted using various soils from reduced- (RT) and conventional-tillage (CT) areas to determine the relative affinity of FLM and metabolites for soils with differing characteristics. Mineralization of FLM (3%, day 42) or TFMA (4%, day 34) and FLM volatilization (approximately 2%) were low for both soils. FLM and DMF dissipated more rapidly in RT soil than in NT soil. In FLM-treated RT soil, DMF and TFMPU accumulated more rapidly than in NT as FLM degraded. TFMA dissipated rapidly, primarily as nonextractable residues (approximately 70%, day 42) and volatilization (approximately 16%). For all respective soils in study II, sorption of all four compounds was higher for organic C-enriched RT soils than for CT soils, indicating strong relationships between organic C and FLM and metabolite sorption. For either tillage treatment, the percentage sorption was greater for metabolites (e.g., at lowest initial dosing concentration, TFMPU range, 45-91%; DMF range, 45-90%; and TFMA range, 45-98%) than for FLM (RT soils range, 19-65%). Nonsubstituted amino groups likely facilitated sorption to organic C, with nonsubstituted aniline in TFMA having the greatest affinity. NMR spectra of humic acid extracts from NT and CT Dundee soils indicated similar patterns of humic acid functional groups, but the potential capacity for sorption was greater in NT than in CT. The greater capacity for FLM and metabolite sorption in NT soil helps explain their longer persistence.     

Degradation and remediation of soils polluted with oil-field wastewater

The changes in the properties of gray forest soils and leached chernozems under the impact of contamination with highly saline oil-field wastewater were studied in a model experiment. It was shown that the soil contamination results in the development of technogenic salinization and alkalization leading to worsening of the major soil properties. The salinization of the soils with oil-field wastewater transformed the soil exchange complex: the cation exchange capacity decreased, and the exchangeable sodium percentage increased to up to 25% of the CEC upon the wastewater infiltration and up to 60% of the CEC upon the continuous soil saturation with the wastewater independently of the soil type. The content of exchangeable magnesium also increased due to the phenomenon of super-equivalent exchange. Despite the saturation of the soil adsorption complex with sodium, no development of the soil alkalization took place in the presence of the high concentration of soluble salts. However, the soil alkalization was observed upon the soil washing from soluble salts. The gypsum application to the washed soils lowered the exchangeable sodium concentration to acceptable values and normalized the soil reaction. The gypsum application without the preliminary washing of the soils from soluble salts was of low efficiency; even after six months, the content of exchangeable sodium remained very high. The subsequent soil washing resulted in the removal of the soluble salts but did not affect the degree of the soil alkalization.     

Effect of temperature on nitrification in soils

Nitrification plays an important role in nitrogen transformation in soils. As a practical problem the fact is noteworthy that by nitrification, the loss of nitrogen from soils is caused at higher temperatures in the summer. On the contrary, it is quite slow at the lower temperatures of early spring. Recently much Work has been done on the effect of temperature on nitrification in soils. It was noticed that its effect is not the same according to the difference of soils. Soils which have high nitrifying activities at ordinary temperatures (around 25°C) show fairly good nitrification even at lower temperatures (1, 2, 5). However, in nitrification by usual experimental methods, the amount of nitrate produced can be only estimated while nitrifying organisms are increasing or decreasing in soil. As the growing Process of microbes is extremely influenced by both the properties of the soil and the cultural conditions, it is necessary to examine the effect of temperature on the growing process of microbes rather than biochemical nitrification by a unit cell. In usual methods nitrification can hardly be treated in these separate aspects. The author has succeeded in obtaining soils in which nitrifying organisms increase to the maximum limit, and no increase can be expected in number of these organisms. By using such samples, experiments were made concerning the effect of temperature on nitrification by a unit cell and its direct effect on the growth of organisms. Furthermore, the author prepared favorable cultural conditions for various kinds of soils by the “washing cultivation method” (6), and examined the effect of temperature on the increasing process of nitrifying ability.