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1.
实验研究了菲在土壤 /沉积物上的吸附 解吸过程。CHL土壤和HFH沉积物中有机质的固相13 CCPMASNMR谱图很相似 ,表明样品中有机质的组成差异不大 ;菲在土壤 /沉积物上的吸附过程表现出明显的非线性 ;线性模型不适合拟合菲的吸附等温线 ,Freundlich模型和双区位反应模型 (DRDM)较好地拟合了菲的吸附等温线 ,其中DRDM模型还清楚地反映菲在低浓度和高浓度下不同的吸附方式 ;另外 ,研究表明菲在土壤 /沉积物上的解吸过程中存在明显的滞后现象 ,这可能和土壤 /沉积物有机质的异质性和土壤胶团微小孔隙的存在有关。  相似文献   

2.
Sluszny  C.  Graber  E. R.  Gerstl  Z. 《Water, air, and soil pollution》1999,115(1-4):395-410
Fresh amendment of soil with sewage sludge and composted sewage sludge resulted in increased sorption of three s-triazine herbicides: atrazine, ametryn and terbuthylazine. The extent of increased sorption (as evaluated by sorption coefficients Kd or Kf) was a function of soil type, such that sorption in amended organic carbon-poor soil (0.4% OC) was more enhanced than in amended organic carbon-rich soil (1.55% OC). Despite significant differences between the organic amendments in terms of humic and fulvic acid content, humin content, soluble organic matter content, total organic matter content, and H/C and O/C atomic ratios, organic matter composition had no discernible effect on either sorption distribution coefficients or on isotherm linearity in amended soils. Soils amended with composted sludge had the same sorption potential as did soils amended with the analogous uncomposted sludge. After incubating soil-sludge mixtures for a year at room temperature, organic matter content decreased to original pre-amendment levels. Sorption coefficients for the three compounds similarly decreased to initial pre-amendment values. Organic carbon normalized sorption coefficients (Koc) were essentially identical in the soils, amended soils, and incubated amended soils, indicating that sludge and compost derived organic matter does not have a significantly different sorption capacity as compared with the original soils, despite compositional differences.  相似文献   

3.
The sorption and penetration of 63Ni at the cuticular level were investigated using enzymatically isolated tomato fruit cuticles. The high values of the partition coefficients determined by immersing cuticular material in a nickel chloride solution indicated that Ni was well retained by cuticular constituents. They were assayed by both direct and indirect methods and increased more than twofold between 1 and 6 days revealing that equilibration between the cuticular material and the bathing solution proceeds very slowly. Ni concentrations at 6 days were about 1,000 times higher in cuticles than in the immersion solution. No significant difference appeared between the immersion with buffer (pH : 8) and without buffer (pH: 6.5). Only 3.2% of sorbed 63Ni was removed by successive rinses in water. The remainder of the radioactivity appeared to be ionically bound to negatively charged exchange sites on the cuticle since 99% of bound 63Ni could be exchanged by rinsing with IN HC1. The cuticular permeability coefficient (P) and the diffusion coefficient (D) determined under self‐diffusion conditions at pH 8, were 1.6 x 10‐8 cm.8‐l and 37.4 x 10‐12 cm2.s‐1 respectively. High variability was noted between cuticles isolated from the same fruit sample. By comparison the permeability coefficient of 45Ca at pH 8 was 16 times higher than for Ni.

The agronomical and ecotoxicological implications of these results are considered.  相似文献   

4.
阿特拉津在土壤, 矿物质及堆肥中的吸附, 运输和转化   总被引：2，自引：0，他引：2  
A. MUDHOO  V. K. GARG 《土壤圈》2011,21(1):11-25
Atrazine is a widely used herbicide for controlling weeds on both agricultural and nonagricultural land,which is equally detected in water supplies beyond safe concentrations.Although the presence of atrazine metabolites is an indication of herbicide degradation,some of them still exhibit toxicity,greater water solubility and weaker interaction with soil components than atrazine.Hence,studies with atrazine in the environment are of interest because of its potential to contaminate drinking water sources.Data on atrazine availability for transport,plant uptake,and microbial degradation and mineralization are therefore required to perform more comprehensive and realistic environmental risk assessments of its environmental fate.This review presents an account of the sorption-desorption phenomenon of atrazine on soil and other sorbents by revisiting the several mechanisms of atrazine-sorbent binding reported in the literature.The retention and transport of atrazine in soils;the influence of organic matter on atrazine sorption;the interactions of atrazine with humic substances,atrazine uptake by plants,atrazine bioccumulation and microbial degradation;atrazine transformation in composting environments;and finally atrazine removal by biosorption are discussed.  相似文献   

5.
The raw cutin (i.e., extractive-free isolated cuticular membrane) fraction from Finnish berries, sea buckthorn (Hippopha? rhamnoides), black currant (Ribes nigrum), cranberry (Vaccinium oxycoccos), lingonberry (Vaccinium vitis-idaea), and bilberry (Vaccinium myrtillus), was depolymerized by NaOMe-catalyzed methanolysis. The composition of cutin monomers was determined by GC-(EI)MS analysis either as methyl esters or as TMSi esters, with OH groups derivatized to TMSi ethers. There was a notable difference in the degree of depolymerization, ranging from 6 to 47%. The extractive-free berry cuticle, that is, raw cutin, thus contains <50% polyester polymer cutin. The predominant cutin monomers were C(16) and C(18) omega-hydroxy acids with midchain functionalities, mainly epoxy and hydroxyl groups. Typically, the major compounds were 9,10-epoxy-18-hydroxyoctadecanoic acid, 10,16-dihydroxyhexadecanoic acid, 9,10,18-trihydroxyoctadecanoic acid, 9,10-epoxy-18-hydroxyoctadec-12-enoic acid, and 18-hydroxyoctadec-9-enoic acid. The amount of epoxyacids was rather high in sea buckthorn ( approximately 70%) and cranberry ( approximately 60%), compared with the other berries. The black currant cutin differed from that of the other berries with a significant portion of hydroxyoxohexadecanoic acid ( approximately 12% of total monomers). This investigation of the cuticular hydroxy acids of five Finnish berries is part of the exploitation of the northern natural resources related to the chemical composition, nutritional value, and sensory properties.  相似文献   

6.
As a source of organic matter, crop residues affect the behaviour of pesticides in agricultural soils. The fate of [U‐ring‐13C] and [U‐ring‐14C] atrazine (6‐chloro‐N‐ethyl‐N‐isopropyl‐1,3,5‐triazine‐2,4‐diamine) was investigated during laboratory incubation under controlled conditions in a loamy soil amended with wheat straw at two different states of decomposition: no preliminary decomposition or 6 months’ preliminary decomposition. After 3 months, non‐extractable, so‐called ‘bound’, 13C‐atrazine residues were recovered in three particle‐size fractions (> 200, 50–200 and < 50 μm), and investigated with solid‐state 13C‐NMR spectroscopy. Parallel incubations with [U‐ring‐14C] atrazine were carried out to quantify the bound residues as well as the extractable and mineralized fractions. The effect of straw residues on atrazine behaviour depended on whether they had been previously decomposed or not. When straw was decomposed for 6 months prior to incubation, atrazine mineralization was enhanced to 50% of the initial 14C in contrast to 15% of the initial 14C in soil alone and soil amended with fresh straw. In parallel, atrazine bound residues were formed in greater amount representing up to 20% of the initial 14C. CP/MAS 13C‐NMR on soil size fractions of soil–straw mixtures after incubation with 13C‐atrazine showed that bound residues contained mostly triazinic C, corresponding to atrazine or primary metabolites. Non‐humified organic materials recovered in size fractions > 200 and 50–200 μm contained significant amounts of bound residues, especially when straw was added to the soil. CP/MAS 13C‐NMR analysis of humic acids obtained from < 50‐μm fractions was difficult due to overlapping of the native carboxyl 13C signal with the 13C‐atrazine signal.  相似文献   

7.
Atrazine is a widely used herbicide and is often a contaminant in terrestrial and freshwater ecosystems. It is uncertain, however, how the activity of soil macrofauna affects atrazine fate and transport. Therefore, we investigated whether earthworms enhance atrazine biodegradation by stimulating herbicide degrading soil microflora, or if they increase atrazine persistence by facilitating herbicide sorption. Short (43 d) and medium term (86 d) effects of the earthworms Lumbricus terrestris and Aporrectodea caliginosa on mineralization, distribution, and sorption of U-ring-14C atrazine and on soil C mineralization was quantified in packed-soil microcosms using silt loam soil. A priming effect (stimulation of soil C mineralization) caused by atrazine supply was shown that likely lowered the earthworm net effect on soil C mineralization in atrazine-treated soil microcosms. Although earthworms significantly increased soil microbial activity, they reduced atrazine mineralization to 14CO2-C from15.2 to 11.7% at 86 d. Earthworms facilitated formation of non-extractable atrazine residues within C-rich soil microsites that they created by burrowing and ingesting soil and organic matter. Atrazine sorption was highest in their gut contents and higher in casts than in burrow linings. Also, gut contents exhibited the highest formation of bound atrazine residues (non-extractable atrazine). Earthworms also promoted a deeper and patchier distribution of atrazine in the soil. This contributed to greater leaching losses of atrazine in microcosms amended with earthworms (3%) than in earthworm-free microcosms (0.003%), although these differences were not significant due to high variability in transport from earthworm-amended microcosms. Our results indicated that earthworms, mainly by casting activity, facilitated atrazine sorption, which increased atrazine persistence. As a consequence, this effect overrode any increase in atrazine biodegradation due to stimulation of microbial activity by earthworms. It is concluded that the affect of earthworms of atrazine mineralization is time-dependent, mineralization being slightly enhanced in the short term and subsequently reduced in the medium term.  相似文献   

8.
Sorption-desorption interactions of pesticides with soil determine the availability of pesticides in soil for transport, plant uptake, and microbial degradation. These interactions are affected by the physical and chemical properties of the pesticide and soil, and for some pesticides, their residence time in the soil. The objective of this study was to characterize sorption-desorption of two sulfonylaminocarbonyltriazolinone herbicides incubated in soils at different soil moisture potentials. The chemicals were incubated in clay loam and loamy sand soils for up to 12 wks at -33 kPa and at water contents equivalent to 50 and 75% of that at -33 kPa. Chemicals were extracted sequentially with 0.01 N CaCl(2) and aqueous acetonitrile, and sorption coefficients were calculated. Sufficient sulfonylaminocarbonyltriazolinone herbicides remained (>40% of that applied) during incubation to allow calculation of sorption coefficients. Aging significantly increased sorption as indicated by increased sorption coefficients. For instance, for sulfonylaminocarbonyltriazolinone remaining after a 12-wk incubation at -33 kPa, K(d) increased by a factor of 4.5 in the clay loam soils and by 6.6 in the loamy sand as compared to freshly treated soils. There was no effect of moisture potential on sorption K(d) values. These data show the importance of characterization of sorption-desorption in aged herbicide residues in soil, particularly in the case of prediction of herbicide transport in soil. In this case, potential transport of sulfonylaminocarbonyltriazolinone herbicides would be over-predicted if freshly treated soil K(d) values were used to predict transport.  相似文献   

9.
Dissolved organic matter enhances the sorption of atrazine by soil   总被引：6，自引：0，他引：6  
The influence of dissolved organic matter (DOM) on the sorption of atrazine (2-chloro-4-ethylamino-6-isopylamino-1,3,5-triazine) by ten soils was investigated. Batch sorption isotherm techniques were used to evaluate the important physiochemical properties of soil determining the sorption of atrazine in the presence of DOM. The sorption of atrazine as a representative of nonionic organic contaminants (NOCs) by soil with and without DOM could be well described by the Linear and Freundlich models. The n values of the Freundlich model were generally near to 1, indicating that linear partitioning was the major mechanism of atrazine sorption by soil samples. The apparent distribution coefficient, value, for atrazine sorption in the presence of DOM initially increased and decreased thereafter as the DOM concentration increased in the equilibrium solution. DOM at relatively lower concentrations significantly enhanced the sorption of atrazine by soil, while it inhibited the atrazine sorption at higher concentrations. For all the soil samples, the maximum of was 1.1~3.1 times higher than its corresponding K d value for the control (without DOM). The maximum enhancement of the distribution coefficient () in the presence of DOM was negatively correlated with the content of soil organic carbon (SOC) and positively correlated with the clay content. The critical concentration of DOM, below which DOM would enhance atrazine sorption, was negatively correlated with SOC. The influence of DOM on atrazine sorption could be approximately considered as the net effect of the cumulative sorption and association of atrazine with DOM in solution. Results of this study provide an insight into the retention and mobility of a NOC in the soil environment.  相似文献   

10.
The adsorption of three s-triazines (atrazine, terbutylazine, and simazine) on three different humic acids (HAs), before and after acidic hydrolysis, was studied at four diverse pH values from 3 to 4.5. The Freundlich sorption affinity (K(f)) and intensity (1/n) of s-triazines were related to the chemical and structural composition of HA and used in a multivariate statistical analysis. At low pH, the sorption values for s-triazines were not directly justified by the content of carboxyl groups in original HA, while only an increase of phenolic carbons in hydrolyzed HA supported the increased s-triazine adsorption. The structural composition of both s-triazines and humic samples explained 86% of the significance in multivariate analyses, whereas the role of pH remained hidden in only 14% of the statistical significance. Adsorption of s-triazines was mainly related to carbon content, hydrophobicity, and aromaticity of HA, thereby implying a predominant binding role of weak dispersive forces. Steric properties explained the larger adsorption affinity of atrazine and terbutylazine with respect to simazine. The occurrence of charge-transfer interactions between atrazine and mainly hydrolyzed HA was further suggested by the increased number of free radicals detected in atrazine-HA complexes at different pH values. Charge-transfer interactions were postulated to occur when HA conformations became progressively controlled by aromatic components. This work indicates that humic matter rich in hydrophobic and aromatic constituents is more likely to adsorb s-triazines and reduce their environmental mobility.  相似文献   

11.
The sorption and leaching of atrazine and MCPA (0.02 M CaCl(2) aqueous solution at 25 degrees C) by a calcareous soil from Southeastern Spain, after organic carbon (OC) amendment with a commercial peat (from 0.18% to 4.61% OC), were studied in batch and soil column experiments. Adsorption capacity (K(f)) values, obtained by fitting the experimental data to the Freundlich equation, ranged from 0.24 mg kg(-)(1) for MCPA sorption on the original soil to 5.47 mg kg(-)(1) for atrazine sorption on the peat-amended soil containing 4.61% OC. The breakthrough curves obtained from the step-function soil column experiments indicated that the amount of herbicide adsorbed ranged from 17.5 mg kg(-)(1) for MCPA in the original soil to 331 mg kg(-)(1) for atrazine in the peat-amended soil containing 1.67% OC. The results obtained from the pulse experiments indicate that the mobility of MCPA is much greater than that corresponding to atrazine.  相似文献   

12.
Effects of diethylsuberate (DESU), tributyl phosphate (TBP), and monodisperse ethoxylated alcohols (EAs) on rate constants of penetration (k) of model solutes across astomatous cuticular membranes isolated from Madagascar ivy (Stephanotis floribunda) and pear (Pyrus communis) leaves were studied. Model solutes (selected on the basis of their octanol/water partition coefficients, K(ow)) were iprovalicarb (log K(ow) = 3.18), metribuzin (log K(ow) = 1.60), and methyl glucose (MG) (log K(ow) = -3.0). K(ow) varied by more than 6 orders of magnitude. Accelerators had wax/water partition coefficients (log K(ww)) ranging from 1.75 (DESU) to 4.32 (C(12)E(2)), and their equilibrium concentrations in Stephanotis wax varied from 0 to about 160 g kg(-)(1). Accelerators increase solute mobility in cuticles by increasing fluidity of cutin and waxes. This effect was quantified by plotting log k versus the accelerator concentration in wax. With the lipophilic solutes metribuzin and iprovalicarb, these plots were linear. Slopes of these plots characterize the intrinsic activities of the accelerators, and they decreased in the order DESU (0.029) > TBP (0.015) > EAs (0.01). Using these intrinsic activities, the effects of accelerators on rate constants of penetration can be calculated for any accelerator concentration in wax. For instance, at 50 g kg(-)(1), rate constants for lipophilic solutes increased by factors of 28 (DESU), 5.6 (TBP), and 3.2 (C(12)E(n)()), respectively. Permeability of cuticles for the hydrophilic MG was not increased by DESU, TBP, C(12)E(2), and C(12)E(4), while C(12)E(6) and C(12)E(8) increased it. Small hydrophilic solutes such as MG can access aqueous pores in cuticles, and this pathway is not affected by changes in fluidity of amorphous waxes. After rate constants of penetration of ionic CaCl(2) were compared with those for nonionic MG, it was concluded that 60% of the MG diffused across aqueous pores, while 40% used an alternative pathway. Because the solubility of MG in wax is extremely low, it is unlikely that MG diffused along the lipophilic pathway used by metribuzin and iprovalicarb. This agrees with the observation that DESU and TBP had no effect on rate constants for MG. An alternative pathway of unknown properties is suggested. It is speculated that C(12)E(6) and C(12)E(8) sorbed in cuticles might have generated a polar pathway for MG.  相似文献   

13.
Infinite- and finite-dose laboratory experiments were used to study the penetrative and dislodgeable residue characteristics of (14)C-insecticides in apple fruit. The differences in dislodgeable and penetrated residues of three radiolabeled insecticides ((14)C-thiamethoxam, (14)C-thiacloprid, and (14)C-indoxacarb), applied in aqueous solution with commercial formulations, were determined after water and methanol wash extractions. The rate of sorption and extent of penetration into the fruit cuticles and hypanthium of two apple cultivars were measured after 1, 6, and 24 h of treatment exposure, using radioactivity quantification methods. For all three compounds, 97% or more of the treatment solutions were found on the fruit surface as some form of non-sorbed residues. For indoxacarb, sorption into the epicuticle was rapid but desorption into the fruit hypanthium was delayed, indicative of a lipophilic penetration pathway. For the neonicotinoids, initial cuticular penetration was slower but with no such delay in desorption into the hypanthium.  相似文献   

14.
Essential oil extracts from Callicarpa americana and Callicarpa japonica were investigated. Bioassay-guided fractionation of C. americana extracts using the yellow fever mosquito, Aedes aegypti, led to the isolation of alpha-humulene, humulene epoxide II, and intermedeol and a newly isolated terpenoid (callicarpenal). Similar work involving C. japonica resulted in the isolation of an additional compound, spathulenol, as well as the four compounds isolated from C. americana. Structure elucidation was performed on all isolated compounds using a combination of gas chromatography-mass spectrometry-electron ionization, high-resolution liquid chromatography-MS-electrospray ionization, and one- and two-dimensional NMR experiments. Heretofore, 13,14,15,16-tetranorclerodane, callicarpenal, has never been identified from natural sources. Complete (1)H and (13)C NMR assignment data are provided for this compound. In bite deterrent studies, spathulenol, intermedeol, and callicarpenal showed significant repellent activity against A. aegypti and Anopheles stephensi.  相似文献   

15.
In order to obtain a better understanding of the behaviour, at the cuticular level of Zn deposited on leaves in natural conditions, the cuticular retention and penetration of this element were studied in vitro, using enzymatically isolated cuticles from pear leaves (Pirns communis L. cv. Passe Crassane). The cuticular retention of Zn, supplied as 0,1 mM 65Zn Cl2 was related to plant species, increasing in the following order: Prunus armeriaca < Pirus malus cv. Golden < Pirus communis L. cv. William with a ratio Zn in cuticles (nmol/g)/Zn in the solution (nmol/g) varying from 282 to 613; it depended on the date of sampling of leaves, the results were apparently not connected with their age. Zn retained by the cuticular discs was lost partially by washing with water, and almost entirely with exchange solutions. The exchangeable fraction could not be precisely determined because of the progressive removal of 65Zn from cuticles, with water. This lability was between that observed with 54fin and 64Cu . Interactions with Cu and Ca were considered, the cuticular retention of 0.1 mM Zn was drastically reduced from 0.01 mM only with Cu suggesting a high cuticular selectivity of Cu over Zn. The cuticular retention of Zn was higher with dewaxed cuticles probably because of a better access of Zn to fixation sites on the cuticular matrix.

The cuticular penetration of Zn was very slow through carefully selected cuticles but was faster with diluted HCl or non radioactive ZnCl2 rather than with pure water in the receiver unit. The validity of results obtained with isolated cuticles is discussed.  相似文献   


16.
Study of the relationship between plant litter-derived dissolved organic matter（DOM） and organic pollutant transport in soil is important for understanding the role of forest litter carbon cycling in influencing pollutant behaviour and fate in forest soil.With the aim of providing insight into the capacity of plant litter-derived DOM to influence sorption and desorption of selected polycyclic aromatic hydrocarbons（PAHs） on soil, batch experiments were carried out with application of a sorption-desorption model incorporating DOM effects. Freshly fallen pine（Pinus elliottii） needles were used as the source of organic matter. Input of the pine needle litter-derived DOM was found to significantly decrease desorption hysteresis as well as soil adsorption capacity of phenanthrene（PHE） and fluoranthene（FLA）. Addition of 1 728 mg L-1dissolved organic carbon（DOC） lowered the organic carbon-normalized sorption distribution coefficient of PHE from 7 776 to 2 541 L kg-1C and of FLA from 11 503 to 4 368 L kg-1C. Decreases of the apparent sorption-desorption distribution coefficients of PHE and FLA with increased DOC concentration indicated that DOM favored desorption of PAHs from soil. Increases in the fraction of apparently dissolved PAHs were attributable to the dissolved PAH-DOM complexes, accounting for the dissolved proportions of 39% to 69% for PHE and 26% to 72% for FLA in the sorption and desorption processes as the concentration of the added DOM solution rose from 0 to 1 728 mg L-1. Our results suggest that pine needle litterderived DOM can have a substantial effect of inhibiting PAHs sorption and promoting PAHs desorption, thus leading to enhanced leaching in soil, which should be taken into account in risk assessment of PAHs accumulated in forest soil.  相似文献   

17.
Sorption and desorption behaviors of diuron in soils amended with charcoal   总被引：1，自引：0，他引：1  
Charcoal derived from the partial combustion of vegetation is ubiquitous in soils and sediments and can potentially sequester organic contaminants. To examine the role of charcoal in the sorption and desorption behaviors of diuron pesticide in soil, synthetic charcoals were produced through carbonization of red gum (Eucalyptus spp.) wood chips at 450 and 850 degrees C (referred to as charcoals BC450 and BC850, respectively, in this paper). Pore size distribution analyses revealed that BC850 contained mainly micropores (pores approximately 0.49 nm mean width), whereas BC450 was essentially not a microporous material. Short-term equilibration (< 24 h) tests were conducted to measure sorption and desorption of diuron in a soil amended with various amounts of charcoals of both types. The sorption coefficients, isotherm nonlinearity, and apparent sorption-desorption hysteresis markedly increased with increasing content of charcoal in the soil, more prominently in the case of BC850, presumably due to the presence of micropores and its relatively higher specific surface area. The degree of apparent sorption-desorption hystersis (hysteresis index) showed a good correlation with the micropore volume of the charcoal-amended soils. This study indicates that the presence of small amounts of charcoal produced at high temperatures (e.g., interior of wood logs during a fire) in soil can have a marked effect on the release behavior of organic compounds. Mechanisms of this apparent hysteretic behavior need to be further investigated.  相似文献   

18.
Degradation and binding of atrazine in surface and subsurface soils   总被引：1，自引：0，他引：1  
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.  相似文献   

19.
17O NMR spectroscopy and (13)C NMR spectroscopy have been used to study the mechanism of interaction of sugars with bovine and caprine caseins in D(2)O. The (17)O NMR relaxation results showed in all cases an increase in water of hydration, as a result of added sugar; this was predominantly associated with "trapped" water in the caseins. Analysis of the vir al coefficients, obtained from the (17)O relaxation data, suggested that preferential interactions occur in the sugar-protein solutions. This could be the result of either sugar binding or a solute-solute thermodynamic effect, preferential hydration. The addition of sugars to deuterated solutions of bovine casein and caprine casein high in alpha(s1)-casein had little or no effect on either line width or chemical shifts of the (13)C NMR spectra of these milk proteins. (13)C NMR studies of sucrose, at various concentrations (100-300 mM) in the presence of caprine casein high in alpha(s1)-casein, showed no changes in either chemical shifts or T(1) values. This indicates that the sugar molecules tumble isotropically and therefore neither bind to the protein nor affect viscosity in the protein-sugar studies. All of these data suggest that the preferential exclusion of the sugar from the domain of the caseins results in preferential hydration of the caseins.  相似文献   

20.
Organic matter (OM) is the most critical factor in controlling the sorption-desorption of SMZ in soil, however, few studies have explored the effects of OM removal on these important behaviors among different soils. Batch experiments were conducted to investigate the sorption and desorption characteristics of SMZ in three different soils: fluvo-aquic soil (FS), paddy soil (PS), and red soil (RS). The SMZ sorption in the evaluated soils was dominated by physisorption. The SMZ sorption capacities of FS and PS, which had a relatively higher OM content than RS, were higher than that of RS. The SMZ sorption in FS was dominated by linear partitioning. In contrast, the SMZ sorption in PS and RS was mainly nonlinear surface adsorption. After OM removal, the SMZ sorption capacity was significantly reduced in FS but increased in PS and RS. Furthermore, OM removal restrained the sorption intensity of SMZ in soils. Relatively higher OM and clay contents inhibited the SMZ desorption in FS and PS. The strong negative desorption hysteresis of SMZ in the three soils indicated that SMZ was able to move into the soil solution, thereby posing a risk to humans. Taken together, the findings of this study showed that OM indeed plays an important role during SMZ sorption-desorption in soil.  相似文献   

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