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1.
J Contam Hydrol ; 252: 104108, 2023 01.
Artigo em Inglês | MEDLINE | ID: mdl-36404181

RESUMO

The mobility of contaminants in soil is controlled by sorption reactions which can be affected by the presence of other solutes that compete for sorption sites. The ability to model such effects is necessary for evaluating the environmental risk of a given contaminant. In this study, the competitive sorption and transport of nickel (Ni) and zinc (Zn) in Olivier and Windsor soils was investigated using batch equilibration and miscible displacement experiments. During batch experiments, the sorption of Ni and Zn was mutually reduced in multicomponent systems, indicating that the metal cations compete for sorption sites. When applied concurrently, the retardation of both ions decreased and peak effluent concentrations increased relative to single ion experiments, demonstrating that competition increased the mobility of both ions during miscible displacement experiments. A novel Freundlich-type multicomponent isotherm (CDI) and its kinetic analog (CDIT) were developed and compared to the commonly used SRS isotherm and SRS-based kinetic approach (SRST) in describing the experimental data. The CDI provided a superior description of the competitive batch data, especially at low surface coverage, and may therefore be more applicable to multicomponent sorption than the SRS. The Olivier and Windsor transport data were best described by the CDIT and SRST, respectively, however, both models generally described the data well. Since both approaches gave comparable descriptions of the transport data while the CDI outperformed the SRS in describing the batch data, the CDI/CDIT may be more generally applicable to multicomponent systems and warrants further study.


Assuntos
Metais Pesados , Níquel , Níquel/análise , Solo , Zinco/análise , Íons , Adsorção , Metais Pesados/análise
2.
J Environ Qual ; 51(6): 1168-1180, 2022 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-35985791

RESUMO

The behavior of metal cations in oxide-dominated systems is controlled by sorption reactions, which in turn depend on pH. Descriptions of such reactions are of interest for contaminant monitoring or remediation efforts; however, widely used isotherms such as Freundlich or Langmuir neglect the effect of pH and are therefore limited in their applicability. Two pH-dependent isotherms and their kinetic analogs were developed and evaluated regarding their ability to describe equilibrium and time-dependent sorption of Ni and Zn by Mn oxide-coated sand (MOCS). The sorption of Ni and Zn by MOCS at pH 4.0, 5.5, and 7.0 was investigated using batch equilibration and stirred-flow techniques. The affinity of MOCS for either metal cation was highly pH dependent, with greater affinity at higher pH. Both isotherms described the batch data well. Flow interruption during stirred-flow experiments indicated that chemical nonequilibrium existed between solution and sorbed phases of both Ni and Zn and that such nonequilibrium was greater with increasing pH. Both kinetic models provided good descriptions of the solution data from stirred-flow experiments and correctly captured the effect of pH on chemical nonequilibrium. These models offer simple alternatives to surface complexation approaches and are expected to be easily applied to describe equilibrium and time-dependent sorption of a wide range of metal cations by variably charged minerals or oxide-coated media.


Assuntos
Óxidos , Areia , Cinética , Zinco
3.
Environ Sci Pollut Res Int ; 27(16): 20227-20234, 2020 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-32239403

RESUMO

In this investigation, batch and column experiments were conducted to investigate the molybdenum (Mo) sorption and transport processes on a neutral-pH soil (Webster loam) and an acidic soil (Mahan sand) in Ca2+ and K+ background solutions. Batch results showed that the adsorption of Mo was strongly non-linear in both soils and amount of Mo sorbed in the acidic soil was larger than the neutral soil. The Freundlich distribution coefficients (Kf) and Langmuir sorption maxima (Smax) in Ca2+ background solution are larger than that in K+ solution, indicating greater Mo sorption in Ca2+ than in K+. Experimental breakthrough curves (BTCs) demonstrated that mobility of Mo was higher at neutral condition than that at acidic condition. A multi-reaction transport model (MRTM) formulation with two kinetic retention reactions (reversible and irreversible) well described Mo transport for Webster soil. However, MRTM model which accounts for equilibrium and kinetic sites is recommended for Mo transport in Mahan soil, reflecting different soil properties. Based on inverse modeling, the sorption forward rate coefficients (k1) obtained from Ca2+ in both soils are larger than that from K+, which consistent with batch experiment. Overall, MRTM model was capable of describing the Mo transport behavior under different geochemical conditions.


Assuntos
Poluentes do Solo/análise , Solo , Adsorção , Cinética , Molibdênio
4.
J Environ Qual ; 48(3): 686-693, 2019 May.
Artigo em Inglês | MEDLINE | ID: mdl-31180437

RESUMO

Quantitative understanding of the mechanisms controlling the competitive retention and transport of V and phosphate on soils is essential for accurately evaluating the environmental risks of contaminants in the environment. Batch and stir-flow chamber experiments were performed to quantify the extent of kinetics of V and phosphate competitive retention in an acidic soil (Sharkey clay). In this study, a stir-flow model was used to describe tracer and competitive reactive solute adsorption, and desorption processes in soils. Based on optimized and predictive modeling results, a fully reversible-irreversible multi-reaction model successfully described the time-dependent competitive V and phosphate retention and transport process in Sharkey soil. Adsorption for V and phosphate were highly nonlinear and time dependent, where V binding affinities were stronger than those for phosphate. Results from batch experiments indicated that that the rate and extent (amount) of V released increased significantly in the presence of phosphate. Breakthrough curves for V, from stir-flow experiments, were asymmetrical and exhibited slow release or tailing, indicating that nonequilibrium retention on the surface of soil was the dominant mechanism of the time-dependent adsorption of V. Results of stir-flow experiments indicated that increased mobility of V was observed in the presence of phosphate caused by direct competition for available retention sites. In conclusion, increased addition of phosphate causes decreasing sorption capacity and increasing mobility of V and needs to be considered in modeling the fate and transport of V in soil.


Assuntos
Poluentes do Solo , Solo , Adsorção , Cinética , Fosfatos , Vanádio
5.
J Environ Qual ; 48(1): 156-163, 2019 01.
Artigo em Inglês | MEDLINE | ID: mdl-30640360

RESUMO

The purpose of this study was to determine the effect of PO on the sorption and transport of glyphosate [-(phosphonomethyl) glycine, GPS] in soils. The results of batch experiments indicated significant competition between PO and GPS in two different soils, with PO being preferentially sorbed. The 24-h Freundlich partitioning coefficients for GPS sorption were decreased by 50 to 60% with PO in solution. High sorptive capacities exhibited by soils in the presence of PO suggest the existence of both competitive and ion specific sites in either soil. Miscible displacement transport studies indicated limited effects of competition when GPS was applied in conjunction with or subsequent to pulses of PO. However, when a PO pulse was applied after the application of a GPS pulse, a secondary GPS breakthrough was observed where an additional 4% of the applied herbicide mass was recovered in the effluent solution. This is likely attributed to the PO-mediated displacement of GPS bound to competitive sites. These results are further emphasized by the distribution of residual herbicide in this column, with enrichment of mass at lower depths in the column and a corresponding decrease in GPS mass closer to the column surface. These results indicate that the timing of inorganic P fertilizers relative to GPS applications has a significant impact on the fate of the herbicide in soils. In particular, these findings suggest that GPS may be more liable to leaching in scenarios in which P fertilizers are applied after the application of GPS-based herbicidal formulations.


Assuntos
Poluentes do Solo , Solo , Adsorção , Glicina/análogos & derivados , Fosfatos , Glifosato
6.
J Environ Qual ; 47(3): 504-512, 2018 May.
Artigo em Inglês | MEDLINE | ID: mdl-29864189

RESUMO

Much uncertainty exists in mechanisms and kinetics controlling the adsorption and desorption of molybdenum (Mo) in the soil environment. To investigate the characteristics of Mo adsorption and desorption and predict Mo behavior in the vadose zone, kinetic batch experiments were performed using three soils: Webster loam, Windsor sand and Mahan sand. Adsorption isotherms for Mo were strongly nonlinear for all three soils. Strong kinetic adsorption of Mo by all soils was also observed, where the rate of retention was rapid initially and was followed by slow retention behavior with time. The time-dependent Mo sorption rate was not influenced when constant pH was maintained. Desorption or release results indicated that there were significant fractions of Mo that appeared to be irreversible or slowly reversibly sorbed by Windsor and Mahan. X-ray absorption near edge structure (XANES) analysis for Windsor and Mahan soils indicated that most of Mo had been bound to kaolinite, whereas Webster had similar XANES features to those of Mo sorbed to montmorillonite. A sequential extraction procedure provided evidence that a significant amount of Mo was irreversibly sorbed. A multireaction model (MRM) with nonlinear equilibrium and kinetic sorption parameters was used to describe the adsorption-desorption kinetics of Mo on soils. Our results demonstrated that a formulation of MRM with two sorption sites (equilibrium and reversible) successfully described Mo adsorption-desorption data for Webster loam, and an additional irreversible reaction phase was recommended to describe Mo desorption or release with time for Windsor and Mahan soils.


Assuntos
Molibdênio/química , Poluentes do Solo/química , Adsorção , Cinética , Solo
7.
J Vet Intern Med ; 30(4): 1356-68, 2016 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-27255433

RESUMO

BACKGROUND: Bovine respiratory disease (BRD) is a worldwide animal health concern especially in feedlot, dairy, and veal calves. One of the greatest challenges is the absence of a gold standard for achieving an accurate antemortem diagnosis. Various blood markers, including the acute-phase proteins (AAP), have been proposed as potential valuable tools for BRD diagnosis. OBJECTIVES: To perform a systematic review of the literature to assess the accuracy of selected APP (haptoglobin [Hp], serum amyloid A [SAA], and fibrinogen [Fb]) as diagnostic tools for cattle with naturally occurring BRD when compared with clinical reference standards of diagnosis. METHODS: This review was performed with eligible studies selected from CAB Abstract and MEDLINE from 1946 to 2015, as well as the "gray literature." Methodological quality of included studies was assessed using the QUADAS-2 tool developed for diagnostic accuracy studies. The accuracy parameters sensitivity (Se) and specificity (Sp) were obtained from the articles or through contact with the authors when not directly reported. RESULTS: A total of 314 studies were identified, from them, 23 met inclusion criteria as diagnostic studies for naturally occurring BRD. Quality of studies showed high risk of bias for case selection (70% of articles) and unclear risk of bias for index test (65%), reference standard (74%), and flow and timing (61%). There were high concerns regarding applicability for case selection (61% of studies) and reference standards used for defining BRD (48%). The concerns regarding index test application were low (83% of the studies). Only 4-8 studies could be included in the meta-analysis for each APP. No pooled estimates or pooled accuracy measurements were performed due to the low number of studies and multiple differences between studies, including reference standard definitions. CONCLUSIONS AND CLINICAL IMPORTANCE: On the basis of these findings, it is not possible to make conclusions regarding the accuracy of APP for BRD diagnosis. The reporting of accuracy of APP for BRD detection is inconsistent among studies. Recommendations to improve capability for future meta-analyses in this area include reporting studies on diagnostic tests following the Standard for the Reporting of Diagnostic Accuracy Studies (STARD), as well as trying to standardize BRD definition across future studies.


Assuntos
Complexo Respiratório Bovino/sangue , Fibrinogênio/metabolismo , Haptoglobinas/metabolismo , Proteína Amiloide A Sérica/metabolismo , Animais , Bovinos , Padrões de Referência
9.
J Environ Qual ; 42(3): 640-53, 2013.
Artigo em Inglês | MEDLINE | ID: mdl-23673929

RESUMO

Competition among various heavy metal species for available adsorption sites on soil matrix surfaces can enhance the mobility of contaminants in the soil environment. Accurate predictions of the fate and behavior of heavy metals in soils and geologic media requires the understanding of the underlying competitive-sorption and transport processes. In this review, we present equilibrium and kinetic models for competitive heavy metal sorption and transport in soils. Several examples are summarized to illustrate the impact of competing ions on the reactivities and mobility of heavy metals in the soil-water environment. We demonstrate that equilibrium Freundlich approaches can be extended to account for competitive sorption of cations and anions with the incorporation of competition coefficients associated with each reaction. Furthermore, retention models of the multiple-reaction type including the two-site nonlinear equilibrium-kinetic models and the concurrent- and consecutive-multireaction models were modified to describe commonly observed time-dependent behaviors of heavy metals in soils. We also show that equilibrium Langmuir and kinetic second-order models can be extended to simulate the competitive sorption and transport in soils, although the use of such models is limited due to their simplifying assumptions. A major drawback of the empirically based Freundlich and Langmuir approaches is that their associated parameters are specific for each soil. Alternatively, geochemical models that are based on ion-exchange and surface-complexation concepts are capable of quantifying the competitive behavior of several chemical species under a wide range of environmental conditions. Such geochemical models, however, are incapable of describing the time-dependent sorption behavior of heavy metal ions in competitive systems. Further research is needed to develop a general-purpose model based on physical and chemical mechanisms governing competitive sorption in soils.


Assuntos
Metaloides , Solo , Adsorção , Metais Pesados , Poluentes do Solo , Oligoelementos
10.
J Contam Hydrol ; 126(3-4): 121-9, 2011 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-22115079

RESUMO

Rate limited processes including kinetic adsorption-desorption can greatly impact the fate and behavior of toxic arsenic compounds in heterogeneous soils. In this study, miscible displacement column experiments were carried out to investigate the extent of reactivity during transport of arsenite in soils. Arsenite breakthrough curves (BTCs) of Olivier and Windsor soils exhibited strong retardation with diffusive effluent fronts followed by slow release or tailing during leaching. Such behavior is indicative of the dominance of kinetic retention reactions for arsenite transport in the soil columns. Sharp decrease or increase in arsenite concentration in response to flow interruptions (stop-flow) further verified that non-equilibrium conditions are dominant. After some 40-60 pore volumes of continued leaching, 30-70% of the applied arsenite was retained by the soil in the columns. Furthermore, continued arsenite slow release for months was evident by the high levels of residual arsenite concentrations observed during leaching. In contrast, arsenite transport in a reference sand material exhibited no retention where complete mass recovery in the effluent solution was attained. A second-order model (SOM) which accounts for equilibrium, reversible, and irreversible retention mechanisms was utilized to describe arsenite transport results from the soil columns. Based on inverse and predictive modeling results, the SOM model successfully depicted arsenite BTCs from several soil columns. Based on inverse and predictive modeling results, a second-order model which accounts for kinetic reversible and irreversible reactions is recommended for describing arsenite transport in soils.


Assuntos
Arsenitos/química , Poluentes do Solo/química , Solo/química , Arsenitos/análise , Cinética , Modelos Químicos , Poluentes do Solo/análise , Água/química , Movimentos da Água
11.
J Environ Qual ; 39(4): 1290-7, 2010.
Artigo em Inglês | MEDLINE | ID: mdl-20830917

RESUMO

The bioavailability and mobility of nickel (Ni) is highly dependent on the mechanisms associated with Ni adsorption-desorption and its kinetics in soils. To examine the characteristics of Ni retention and release, kinetic sorption batch experiments were performed on three soils having different properties, followed by Ni desorption using successive dilutions. Sorption of Ni by all soils was highly nonlinear and strongly kinetic, where the rate of Ni retention was rapid initially and was followed by gradual or somewhat slow retention behavior with increasing reaction time. Desorption of Ni was strongly irreversible and hysteretic in nature, indicating lack of equilibrium retention and/or irreversible or slowly reversible processes. A sequential extraction procedure provided evidence that a significant amount of Ni was irreversibly adsorbed on all soils. A nonlinear multireaction model with equilibrium-kinetic-irreversible reaction sites successfully described the retention (adsorption) and subsequent release of Ni on the different soils. The model was also capable of predicting Ni desorption kinetics based on adsorption data sets only.


Assuntos
Níquel/química , Poluentes do Solo/química , Solo/análise , Cinética , Modelos Químicos
12.
J Hazard Mater ; 181(1-3): 778-87, 2010 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-20561748

RESUMO

In order to identify spatial relationship of heavy metals in soil-rice system at a regional scale, 96 pairs of rice and soil samples were collected from Wenling in Zhejiang province, China, which is one of the well-known electronic and electric waste recycling centers. The results indicated some studied areas had potential contaminations by heavy metals, especially by Cd. The spatial distribution of Cd, Cu, Pb and Zn illustrated that the highest concentrations were located in the northwest areas and the accumulation of these metals may be due to the industrialization, agricultural chemicals and other human activities. In contrast, the concentration of Ni decreased from east to west and the mean concentration was below the background value, indicating the distribution of Ni may be naturally controlled. Enrichment index (EI) was used to describe the availability of soil heavy metals to rice. The spatial distribution of EIs for Cd, Ni and Zn exhibited a west-east structure, which was similar with the spatial structures of pH, OM, sand and clay. Cross-correlograms further quantitatively illustrated the EIs were significantly correlated with most soil properties, among which; soil pH and OM had the strongest correlations with EIs. However, EI of Cu showed relative weak correlations with soil properties, especially soil pH and OM had no correlations with EI of Cu, indicating the availability of Cu may be influenced by other factors.


Assuntos
Metais Pesados/análise , Oryza , Poluentes do Solo/análise , China , Produtos Agrícolas , Geografia , Solo
13.
J Environ Qual ; 38(4): 1608-16, 2009.
Artigo em Inglês | MEDLINE | ID: mdl-19549937

RESUMO

Kinetic sorption and column miscible displacement transport experiments were performed to quantify the extent of retention/release and the mobility of mercury in different soils. Results indicated that adsorption of mercury was rapid and highly nonlinear with sorption capacities having the following sequence: Sharkey clay > Olivier loam > Windsor sand. Mercury adsorption by all soils was strongly irreversible where the amounts released or desorbed were often less than 1% of that applied. Moreover, the removal of soil organic matter resulted in a decrease of mercury adsorption in all soils. Adsorption was described with limited success using a nonlinear (Freundlich) model. Results from the transport experiments indicated that the mobility of mercury was highly retarded, with extremely low concentrations of mercury in column effluents. Furthermore, mercury breakthrough curves exhibited erratic patterns with ill-distinguished peaks. Therefore, mercury is best regarded as strongly retained and highly "immobile" in the soils investigated. This is most likely due to highly stable complex formation (irreversible forms) and strong binding to high-affinity sites. In a column packed with reference sand material, a symmetric breakthrough curve was obtained where the recovery of mercury in the leachate was only 17.3% of that applied. Mercury retention by the reference sand was likely due to adsorption by quartz and metal-oxides.


Assuntos
Mercúrio/química , Poluentes do Solo/química , Adsorção , Cinética , Termodinâmica
14.
Dentomaxillofac Radiol ; 38(5): 274-80, 2009 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-19474254

RESUMO

OBJECTIVES: Distraction osteogenesis is considered an important reconstruction armamentarium in the management of mandibular deformities and deficiency disorders. The duration of the consolidation period is still a debatable issue among the clinicians. Evaluation of the newly formed bone is the cornerstone for terminating the consolidation period safely. The aim of this study is to find a more conservative protocol for the evaluation of callus distraction by monitoring bone healing using two different examination tools: ultrasonography and dental CT. METHODS: Four adult patients (three women and one man) underwent mandibular distraction (using two intraoral and two extraoral devices). The latency period was 5-7 days and the distraction was at a rate of 2 mm per day, with 12-14 weeks of consolidation. All patients were evaluated during activation, 3 months, 6 months and 1 year post-distraction. Evaluation included clinical examination, plain radiographs, CT and ultrasonography examinations. RESULTS: Ultrasonographic examination of the healing callus revealed four different phases of maturation. These phases were similar to the degree of tissue calcification as measured by CT. Tissue density across the distraction wound at the time of distractor removal (12-14 weeks) was equal to or less than one-third of normal bone density. CONCLUSIONS: Clinical monitoring of mandibular distraction wounds can be successfully achieved through frequent use of ultrasonographic examinations. Standardization of ultrasonography based on CT findings will expand the reliability of ultrasound in monitoring callus maturation. An algorithm for evaluation of distraction wound healing is suggested.


Assuntos
Calo Ósseo/diagnóstico por imagem , Mandíbula/diagnóstico por imagem , Osteogênese por Distração , Adulto , Algoritmos , Densidade Óssea , Calcificação Fisiológica , Feminino , Humanos , Masculino , Avanço Mandibular/métodos , Radiografia , Ultrassonografia , Cicatrização/fisiologia , Adulto Jovem
15.
J Environ Qual ; 36(5): 1273-80, 2007.
Artigo em Inglês | MEDLINE | ID: mdl-17636288

RESUMO

Colloid generation and transport in soils is of significance because of suspected colloid-facilitated transport of contaminants to the groundwater. In this study, colloid mobilization and its effect on the transport of arsenite [As(III)] were investigated in Olivier (fine-silty, mixed, active, thermic Aquic Fraglossudalfs) and Windsor (mixed, mesic typic Udipsamments) soil columns. Input solution of 10 mg L(-1) As(III) in 0.01 M NaCl was applied to water-saturated columns, and followed by leaching with deionized water (DIW). Flow interruptions were performed during the As(III) input and DIW leaching phases. Turbidity, electrical conductivity (EC), and pH of column effluents were monitored with time. Total and dissolved concentrations of As, Fe, and Al were analyzed. Effluent results demonstrated that colloid-facilitated transport contributed little to arsenic movement when the solution ionic strength was maintained constant. Mobilization of colloidal amorphous material and enhanced transport of As(III) were observed as a result of changes in ionic strength of the input solution. The peak of colloid generation coincided with peak concentrations of Fe, suggesting mobilization of Fe oxides and facilitated transport of As(III) adsorbed on oxide surfaces. Colloid mobilization was enhanced due to flow interruption in the Olivier column, which suggests slow dissociation of aggregated colloidal particles. Moreover, effluent results indicate significant effect of organic matter in stabilizing aggregates of colloidal particles.


Assuntos
Arsênio/análise , Poluentes do Solo/análise , Poluentes da Água/análise , Alumínio/análise , Alumínio/química , Coloides/química , Monitoramento Ambiental , Compostos Férricos/química , Ferro/análise , Ferro/química , Concentração Osmolar , Oxirredução , Porosidade , Solo
16.
Environ Sci Technol ; 39(16): 6101-8, 2005 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-16173569

RESUMO

Adsorption-desorption of arsenic is the primary factor that impacts the bioavailability and mobility of arsenic in soils. To examine the characteristics of arsenate [As(V)] adsorption-desorption, kinetic batch experiments were carried out on three soils having different properties, followed by arsenic release using successive dilutions. Adsorption of As(V) was highly nonlinear, with a Freundlich reaction order N much less than 1 for Olivier loam, Sharkey clay, and Windsor sand. Adsorption of arsenate by all soils was strongly kinetic, where the rate of As(V) retention was rapid initially and was followed by gradual or somewhat slow retention behavior with increasing reaction time. Freundlich distribution coefficients and Langmuir adsorption maxima exhibited continued increase with reaction time for all soils. Desorption of As(V) was hysteretic in nature and is an indication of lack of equilibrium retention and/or irreversible or slowly reversible processes. A sequential extraction procedure provided evidence that a significant amount of As(V) was irreversibly adsorbed on all soils. A multireaction model (MRM) with nonlinear equilibrium and kinetic sorption successfully described the adsorption kinetics of As(V) for Olivier loam and Windsor sand. The model was also capable of predicting As(V) desorption kinetics for both soils. However, for Sharkey clay, which exhibited strongest affinity for arsenic, an additional irreversible reaction phase was required to predict As(V) desorption or release with time.


Assuntos
Arseniatos/análise , Arseniatos/química , Arsênio/química , Poluentes do Solo/análise , Adsorção , Arsênio/farmacocinética , Disponibilidade Biológica , Cinética , Modelos Químicos
17.
J Environ Qual ; 34(1): 325-35, 2005.
Artigo em Inglês | MEDLINE | ID: mdl-15647562

RESUMO

Sorption and desorption kinetics are essential components for modeling the movement and retention of applied agricultural chemicals in soils and the fraction of chemicals susceptible to runoff. In this study, we investigated the retention characteristics of sugarcane (Saccharum spp. hybrid) mulch residue for atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) based on studies of sorption-desorption kinetics. A sorption kinetic batch method was used to quantify retention of the mulch residue for a wide range of atrazine concentrations and reaction times. Desorption was performed following 504 h of sorption using successive dilutions, followed by methanol extraction. Atrazine retention by the mulch residue was well described using a linear model where the partitioning coefficient (K(d)) increased with reaction time from 10.40 to 23.4 cm3 g(-1) after 2 and 504 h, respectively. Values for mulch residue K(d) were an order of magnitude higher than those found for Commerce silt loam (fine-silty, mixed, superactive, nonacid, thermic Fluvaquentic Endoaquepts) where the sugarcane crop was grown. A kinetic multireaction model was successful in describing sorption behavior with reaction time. The model was equally successful in describing observed hysteretic atrazine behavior during desorption for all input concentrations. The model was concentration independent where one set of model parameters, which was derived from all batch results, was valid for the entire atrazine concentration range. Average atrazine recovery following six successive desorption steps were 63.67 +/- 4.38% of the amount adsorbed. Moreover, a hysteresis coefficient based on the difference in the area between sorption and desorption isotherms was capable of quantifying hysteresis of desorption isotherms.


Assuntos
Atrazina/química , Herbicidas/química , Modelos Teóricos , Adsorção , Agricultura , Monitoramento Ambiental , Cinética , Eliminação de Resíduos , Saccharum , Temperatura
18.
J Environ Qual ; 33(2): 488-95, 2004.
Artigo em Inglês | MEDLINE | ID: mdl-15074799

RESUMO

Understanding sulfate transport and retention dynamics in forest soils is a prerequisite in predicting SO4 concentration in the soil solution and in lake and stream waters. In this study forest soil samples from the Gårdsjön catchments, Sweden, were used to study SO4 transport in soil columns from the upper three soil horizons (E, Bs, and BC). The columns were leached using a sequential leaching technique. The input solutions were CaSO4 equilibrated with forest floor material. Leaching behavior of SO4 and concentration in the effluent were measured from columns from individual horizons. Sulfate was always retained in the Bs and BC horizons, while the pattern for the E horizon varied. Attempts were also made to model SO4 breakthrough results based on miscible displacement approaches and solute convection-dispersion equation (CDE) in porous media. Several retention mechanisms were incorporated into the CDE to account for possible reversible and irreversible SO4 reactions in individual soil layers. Our modeling efforts were inadequate in describing the mobility of SO4 in the top (E) horizon. Moreover, a linear equilibrium approach was generally inadequate for describing SO4 sorption during transport in the Bs and BC horizons. In contrast, we found that the model provided good descriptions of all breakthrough results when SO4 reactivity was accounted for based on nonlinear equilibrium or first-order kinetic processes. Moreover, based on model parameter estimates, the reactivity or retention of SO4 during transport is concentration dependent. We conclude that sulfate retention during transport in this forest soil is most likely controlled by kinetic reactivity of SO4 of the reversible and irreversible mechanisms.


Assuntos
Modelos Teóricos , Solo , Sulfatos/análise , Árvores , Adsorção , Cinética , Sulfatos/química
19.
Sci Total Environ ; 320(1): 51-61, 2004 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-14987926

RESUMO

The purpose of this study was to quantify the solubility and distribution of As among solid-phase components in poultry wastes and soils receiving long-term poultry waste applications. Arsenic in the water-soluble, NaOCl-extractable (organically bound), NH(2)OH x HCl-extractable (oxide bound) and residual fractions were quantified in an Upper Coastal Plain soil (Neshoba County, MS) that received annual waste applications. After 25 years, As in the amended soil had a mean of 8.4 mg kg(-1) compared to 2.68 mg kg(-1) for a non-amended soil. Arsenic in the amended soil was mainly in the residual fraction (72% of total), which is generally considered the least bioavailable fraction. Arsenic in poultry waste samples was primarily water-soluble (5.3-25.1 mg kg(-1)), representing 36-75% of the total As. To assess the extent of spatial heterogeneity, total As in a 0.5-ha area within the long-term waste-amended field was quantified. Soil surface samples were taken on 10-m grid points and results for total As appeared negatively skewed and approximated a bimodal distribution. Total As in the amended soil was strongly correlated with Fe oxides, clay and hydroxy interlayered vermiculite concentrations, and negatively correlated with Mehlich III-P, mica and quartz contents.


Assuntos
Arsênio/análise , Arsênio/química , Esterco , Aves Domésticas , Eliminação de Resíduos , Poluentes do Solo/análise , Ração Animal , Animais , Solubilidade
20.
J Environ Qual ; 32(4): 1445-54, 2003.
Artigo em Inglês | MEDLINE | ID: mdl-12931901

RESUMO

Reducing surface and subsurface losses of herbicides in the soil and thus their potential contamination of water resources is a national concern. This study evaluated the effectiveness of sugarcane (Saccharum spp.) residue (mulch cover) in reducing nonpoint-source contamination of applied herbicides from sugarcane fields. Specifically, the effect of mulch residue on herbicide retention was quantified. Two main treatments were investigated: a no-till treatment and a no-mulch treatment. The amounts of extractable atrazine [2-chloro-4-(isopropylamino)-6-ethylamino-s-triazine], metribuzin [4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5(4H)-one], and pendimethalin [N-(ethylpropyl)-3,4-dimethyl-2,6-dinitroaniline] from the mulch residue and the surface soil layer were quantified during the 1999 and 2000 growing seasons. Significant amounts of applied herbicides were intercepted by the mulch residue. Extractable concentrations were at least one order of magnitude higher for the mulch residue compared with that retained by the soil. Moreover, the presence of mulch residue on the sugarcane rows was highly beneficial in minimizing runoff losses of the herbicides applied. When the residue was not removed, a reduction in runoff-effluent concentrations, as much as 50%, for atrazine and pendimethalin was realized. Moreover, the presence of mulch residue resulted in consistently lower estimates for rates of decay or disappearance of atrazine and pendimethalin in the surface soil.


Assuntos
Herbicidas/análise , Poluentes do Solo/análise , Poluentes da Água/análise , Poluição da Água/prevenção & controle , Conservação dos Recursos Naturais , Monitoramento Ambiental , Chuva , Saccharum , Movimentos da Água
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