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1.
Chemosphere ; 351: 141205, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38219990

RESUMO

Powdered activated carbon (PAC) is commonly used by water treatment plants to remove harmful cyanotoxins such as microcystins (MCs) produced during seasonal harmful algal blooms. MC removal by PAC depends upon the properties of the PAC, the properties of the MC variant, and the presence and properties of dissolved organic matter (DOM). To identify which of these factors has the greatest impact on the removal of MC by PAC, we evaluated the removal of four different MC variants (MC-LR, MC-LA, MC-RR and desmethylated MC-RR) by three different PAC types (wood-based, coal-blend and coal-based). The role of DOM properties was evaluated using DOM isolated from two different sources, a terrestrial source (Suwannee River Fulvic Acid, SRFA) and a microbial source (Grand Lake St Marys DOM, GLSM). The results of adsorption experiments conducted over a period of 72 h demonstrated the wood-based PAC, which had the highest surface area and mesopore volume of the PAC tested, had the highest adsorption rate and capacity for all four MC variants. Of the variants studied, neutrally charged MC-RR was adsorbed more rapidly and to a greater extent on all of the PAC types than were the other variants. Although MC-LA and MC-LR had the greatest hydrophobicity, their negative charges resulted in their being adsorbed the least. As expected, DOM inhibited microcystin adsorption to PAC. The degree of inhibition, however, did not significantly vary for the two DOM types evaluated, indicating the properties of the DOM on MC adsorption to PAC was less important than the PAC properties or MC variant properties. Overall, PAC properties were a more important factor in MC removal than were the MC properties or DOM conditions.


Assuntos
Microcistinas , Purificação da Água , Carvão Vegetal , Matéria Orgânica Dissolvida , Pós , Purificação da Água/métodos , Adsorção , Carvão Mineral
2.
J Public Health Manag Pract ; 29(6): 845-853, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37738597

RESUMO

CONTEXT: Prior to the COVID-19 pandemic, wastewater influent monitoring for tracking disease burden in sewered communities was not performed in Ohio, and this field was only on the periphery of the state academic research community. PROGRAM: Because of the urgency of the pandemic and extensive state-level support for this new technology to detect levels of community infection to aid in public health response, the Ohio Water Resources Center established relationships and support of various stakeholders. This enabled Ohio to develop a statewide wastewater SARS-CoV-2 (severe acute respiratory syndrome coronavirus 2) monitoring network in 2 months starting in July 2020. IMPLEMENTATION: The current Ohio Coronavirus Wastewater Monitoring Network (OCWMN) monitors more than 70 unique locations twice per week, and publicly available data are updated weekly on the public dashboard. EVALUATION: This article describes the process and decisions that were made during network initiation, the network progression, and data applications, which can inform ongoing and future pandemic response and wastewater monitoring. DISCUSSION: Overall, the OCWMN established wastewater monitoring infrastructure and provided a useful tool for public health professionals responding to the pandemic.


Assuntos
COVID-19 , Águas Residuárias , Humanos , Ohio , Pandemias/prevenção & controle , Saúde Pública , COVID-19/epidemiologia , COVID-19/prevenção & controle , SARS-CoV-2
3.
Chemosphere ; 220: 696-705, 2019 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-30611067

RESUMO

In this study, microcystin-LR (MCLR) interactions with three representative silicate clays were studied using equilibrium batch experiments in order to provide insight into the role of clays on determining MCLR fate. The three tested clay minerals (kaolinite, montmorillonite and illite), saturated with sodium or calcium ions, were equilibrated with MCLR across a range of toxin concentrations at pH 5, 7 or 9. The results were fit to Freundlich and linear isotherm models, with the linear isotherm fits deemed most appropriate. In general, adsorption of MCLR was greater in the systems with Ca than in those with Na, however, regardless of the cation present, montmorillonite had the highest adsorption affinity for MCLR. Furthermore, except for Ca-montmorillonite, MCLR adsorption decreased with increasing pH. The pH-dependence of adsorption suggests the polar groups of MCLR, carboxylate associated with the glutamic acid and methylaspartic acid groups and amine associated with the arginine group, were more important in determining MCLR interactions with clays than the nonpolar ADDA group. Increased adsorption in systems enriched with calcium suggests Ca modified the clay interfacial properties and the availability of MCLR groups in a manner that increased MCLR affinity. Overall, the results suggest clays are capable of adsorbing MCLR from the aqueous phase, particularly at low pH and when saturated with Ca2+.


Assuntos
Adsorção , Argila/química , Microcistinas/química , Silicatos/química , Bentonita/química , Sítios de Ligação , Cálcio , Concentração de Íons de Hidrogênio , Caulim/química , Toxinas Marinhas , Microcistinas/metabolismo , Minerais/química , Sódio
4.
Environ Sci Technol ; 51(23): 13985-13994, 2017 Dec 05.
Artigo em Inglês | MEDLINE | ID: mdl-29110455

RESUMO

Hydraulic fracturing fluids are injected into shales to extend fracture networks that enhance oil and natural gas production from unconventional reservoirs. Here we evaluated the biodegradability of three widely used nonionic polyglycol ether surfactants (alkyl ethoxylates (AEOs), nonylphenol ethoxylates (NPEOs), and polypropylene glycols (PPGs)) that function as weatherizers, emulsifiers, wetting agents, and corrosion inhibitors in injected fluids. Under anaerobic conditions, we observed complete removal of AEOs and NPEOs from solution within 3 weeks regardless of whether surfactants were part of a chemical mixture or amended as individual additives. Microbial enzymatic chain shortening was responsible for a shift in ethoxymer molecular weight distributions and the accumulation of the metabolite acetate. PPGs bioattenuated the slowest, producing sizable concentrations of acetone, an isomer of propionaldehyde. Surfactant chain shortening was coupled to an increased abundance of the diol dehydratase gene cluster (pduCDE) in Firmicutes metagenomes predicted from the 16S rRNA gene. The pduCDE enzymes are responsible for cleaving ethoxylate chain units into aldehydes before their fermentation into alcohols and carboxylic acids. These data provide new mechanistic insight into the environmental fate of hydraulic fracturing surfactants after accidental release through chain shortening and biotransformation, emphasizing the importance of compound structure disclosure for predicting biodegradation products.


Assuntos
Fraturamento Hidráulico , Tensoativos , Biodegradação Ambiental , Biotransformação , RNA Ribossômico 16S , Microbiologia do Solo
5.
Environ Sci Technol ; 50(22): 12283-12291, 2016 11 15.
Artigo em Inglês | MEDLINE | ID: mdl-27767293

RESUMO

Predicting the environmental fate of lead relies on a detailed understanding of its coordination to mineral surfaces, which in turn reflects the innate reactivity of the mineral surface. In this research, we investigated fundamental dependencies in lead adsorption to hematite by coupling extended X-ray absorption fine structure (EXAFS) spectroscopy on hematite particles (10 and 50 nm) with resonant anomalous X-ray reflectivity (RAXR) to single crystals expressing the (001), (012), or (110) crystallographic face. The EXAFS showed that lead adsorbed in a bidentate inner-sphere manner in both edge and corner sharing arrangements on the FeO6 octahedra for both particle sizes. The RAXR measurements confirmed these inner-sphere adsorption modes for all three hematite surfaces and additionally revealed outer-sphere adsorption modes not seen in the EXAFS. Lead uptake was larger and pH dependence was greater for the (012) and (110) surfaces, than the (001) surface, due to their expressing singly- and triply coordinated oxygen atoms the (001) surface lacks. In coupling these two techniques we provide a more detailed and nuanced picture of the coordination of lead to hematite while also providing fundamental insight into the reactivity of hematite.


Assuntos
Compostos Férricos/química , Chumbo/química , Tamanho da Partícula , Espectroscopia por Absorção de Raios X , Adsorção , Minerais , Raios X
6.
Environ Sci Technol ; 50(22): 12214-12224, 2016 11 15.
Artigo em Inglês | MEDLINE | ID: mdl-27741391

RESUMO

We investigated the evolution in silver nanoparticle (AgNP) properties during a series of 10-50 day experiments on suspensions with different pH (5-9), electrolyte type (NaNO3 and NaCl) and concentration (2 and 6 mM), Suwannee River humic acid (SRHA) concentration (0-13.2 mg C/L), and light exposure (artificial sun light exposure for 8 h per day or dark). Of these factors, pH most influenced the AgNPs' properties as it modifies surface charge as well as AgNP dissolution and oxidation and Ag+ reduction reactions. As a result, particle behavior differed in basic and acidic conditions. Trends with pH varied, however, based on the electrolyte and SRHA concentration. In the presence of chloride which forms AgCl(s), for example, we observed the particle size decreased with increasing pH. The opposite was observed in identical systems in NaNO3. This behavior was modified by SRHA, with increasing SRHA reducing dissolution and enhancing stability. Light exposure enhanced processes resulting in AgNP dissolution, resulting in higher dissolved Ag concentrations than under similar conditions in the dark. Overall, our results highlight how AgNP properties evolve over time and provide insight needed to confidently extend model system behavior to predict the environmental fate of AgNPs.


Assuntos
Substâncias Húmicas , Prata/química , Concentração de Íons de Hidrogênio , Luz , Nanopartículas Metálicas/química
7.
Harmful Algae ; 54: 174-193, 2016 04.
Artigo em Inglês | MEDLINE | ID: mdl-28073475

RESUMO

Blooms of toxic cyanobacteria in water supply systems are a global issue affecting water supplies on every major continent except Antarctica. The occurrence of toxic cyanobacteria in freshwater is increasing in both frequency and distribution. The protection of water supplies has therefore become increasingly more challenging. To reduce the risk from toxic cyanobacterial blooms in drinking water, a multi-barrier approach is needed, consisting of prevention, source control, treatment optimization, and monitoring. In this paper, current research on some of the critical elements of this multi-barrier approach are reviewed and synthesized, with an emphasis on the effectiveness of water treatment technologies for removing cyanobacteria and related toxic compounds. This paper synthesizes and updates a number of previous review articles on various aspects of this multi-barrier approach in order to provide a holistic resource for researchers, water managers and engineers, as well as water treatment plant operators.


Assuntos
Cianobactérias/fisiologia , Água Potável/microbiologia , Purificação da Água/normas , Regiões Antárticas , Cianobactérias/química , Cianobactérias/isolamento & purificação , Abastecimento de Água/normas
8.
J Colloid Interface Sci ; 460: 36-46, 2015 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-26313711

RESUMO

We investigated the adsorption of citric acid on the surface of two different sized hematite nanoparticles using batch adsorption experiments, Fourier-transform infrared spectroscopy, surface complexation modeling and computational molecular modeling. Citrate adsorption reached a maximum between pH approximately 2.5 and 5.5 and declined as the pH was increased or decreased from that range. At high surface loading conditions, the dominant adsorbed citrate structure was outer-sphere in nature with a protonation state that varied with pH. At low pH, there was also evidence of an inner-sphere complex consistent with a binuclear, bidentate structure where the hydroxyl group was deprotonated and played an active role in the adsorption. An inner-sphere complex was also detected at low citrate surface loading conditions. Surface-area normalized surface coverages were similar for both sizes of hematite, however, the inner sphere complex appeared to be slightly more prevalent on the smaller hematite. Based on these structures, a triple layer surface complexation model comprised of two outer-sphere complexes and one inner-sphere complex was used to describe the adsorption data for both hematite sizes across a range of solution conditions with a single set of surface area dependent equilibrium constants.


Assuntos
Ácido Cítrico/química , Compostos Férricos/química , Adsorção , Simulação por Computador , Concentração de Íons de Hidrogênio , Modelos Moleculares , Nanopartículas/química , Nanotecnologia/métodos , Tamanho da Partícula , Soluções , Espectroscopia de Infravermelho com Transformada de Fourier , Propriedades de Superfície
9.
Environ Sci Technol ; 46(10): 5378-86, 2012 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-22502776

RESUMO

This study investigated aggregation and silver release of silver nanoparticles suspended in natural water in the absence and presence of artificial sun light. The influence of the capping layer was investigated using uncoated particles and particles coated with citrate or Tween 80. The experiments were conducted over 15 days in batch mode using a river water matrix. Silver release was monitored over this time while the aggregation state and morphological changes of the silver nanoparticles were tracked using dynamic light scattering and transmission electron microscopy. Results indicate sterically dispersed particles coated with Tween released silver quicker than did bare- and citrate-coated particles, which rapidly aggregated. A dissolved silver concentration of 40 µg/L was reached after just 6 h in the Tween-coated particle systems, accounting for ca. 3% of the total silver. Similar levels of dissolved silver were reached in the uncoated and citrate-coated systems at the end of the 15 days. Silver release was not significantly impacted by the artificial sun light; however, the light (and citrate) imparted significant morphological changes to the particles. Their impact was masked by aggregation, which seemed to be the controlling process in this study.


Assuntos
Água Doce/química , Nanopartículas Metálicas/química , Prata/química , Ácido Cítrico/química , Hidrodinâmica , Luz , Nanopartículas Metálicas/ultraestrutura , Ohio , Rios/química , Solubilidade/efeitos da radiação , Propriedades de Superfície/efeitos da radiação , Fatores de Tempo
10.
Langmuir ; 28(2): 1095-104, 2012 Jan 17.
Artigo em Inglês | MEDLINE | ID: mdl-22149007

RESUMO

Determining the fate of manufactured nanomaterials in the environment is contingent upon understanding how stabilizing agents influence the stability of nanoparticles in aqueous systems. In this study, the aggregation and dissolution tendencies of uncoated silver nanoparticles and the same particles coated with three common coating agents, trisodium citrate, sodium dodecyl sulfate (SDS), and Tween 80 (Tween), were evaluated. Early stage aggregation kinetics of the uncoated and coated silver nanoparticles were assessed by dynamic light scattering over a range of electrolyte types (NaCl, NaNO(3), and CaCl(2)) and concentrations that span those observed in natural waters. Although particle dissolution was observed, aggregation of all particle types was still consistent with classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The aggregation of citrate-coated particles and SDS-coated particles were very similar to that for the uncoated particles, as the critical coagulation concentrations (CCC) of the particles in different electrolytes were all approximately the same (40 mM NaCl, 30 mM NaNO(3), and 2 mM CaCl(2)). The Tween-stabilized particles were significantly more stable than the other particles, however, and in NaNO(3) aggregation was not observed up to an electrolyte concentration of 1 M. Differences in the rate of aggregation under diffusion-limited aggregation conditions at high electrolyte concentrations for the SDS and Tween-coated particles, in combination with the moderation of their electrophoretic mobilities, suggest SDS and Tween imparted steric interactions to the particles. The dissolution of the silver nanoparticles was inhibited by the SDS and Tween coatings, but not by the citrate coating, and in chloride-containing electrolytes a secondary precipitate of AgCl was observed bridging the individual particles. These results indicate that coating agents could significant influence the fate of silver nanoparticles in aquatic systems, and in some cases these stabilizers may completely prevent particle aggregation.


Assuntos
Nanopartículas Metálicas , Prata/química , Cinética , Microscopia Eletrônica de Transmissão , Solubilidade , Espectrofotometria Ultravioleta , Tensoativos/química
11.
Water Res ; 45(16): 4782-92, 2011 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-21767863

RESUMO

In this study, As leaching from five arsenic bearing solid residuals (ABSRs) comprised of the iron hydroxide adsorbent Bayoxide E33 used in long-term operations was evaluated in leaching trials using California Waste Extraction Test (CalWET) and Toxicity Characteristic Leaching Protocol (TCLP) leachate solutions, a landfill leachate (LL), and synthetic leachate (SL). The initial As loading of the media, which reflects the influence of source water chemistry and varying treatment conditions at the point of removal, strongly influenced the magnitude of As release. The chemical composition of the leachate also influenced As release and demonstrated the relative importance of different release mechanisms, namely media dissolution, pH-dependent sorption/desorption, and ion exchange. The CalWET solution, which partially dissolved the iron-based media, resulted in 100 times more As release than did the TCLP solution, which did not dissolve the media. The LL had a higher pH than the TCLP solution, and even though its organic carbon content was lower it tended to release more As. Tests with the SL were conducted to determine the influence of variations in leachate pH, phosphate, bicarbonate, sulfate, silicate, and natural organic matter (NOM). Release increased at high pH, in the presence of high concentrations of phosphate and bicarbonate, and in the presence of high NOM concentrations. For pH, this reflects the pH-dependence of sorption reactions, whereas for the anions and NOM, direct competition appeared important. Similar to the CalWET solution, excess NOM dissolved portions of the media thereby facilitating As release. In general, our results suggest that estimating As release into landfills will remain a challenge as it depends upon As loading, which reflects site-specific properties, and the composition of the leachate, which varies from landfill to landfill.


Assuntos
Arsênio/química , Abastecimento de Água/análise , Adsorção
12.
Langmuir ; 26(22): 16690-8, 2010 Nov 16.
Artigo em Inglês | MEDLINE | ID: mdl-20879768

RESUMO

Bare silver nanoparticles with diameters of 82 ± 1.3 nm were synthesized by the reduction of the Ag(NH(3))(2)(+) complex with D-maltose, and their morphology, crystalline structure, UV-vis spectrum, and electrophoretic mobilities were determined. Dynamic light scattering was employed to assess early stage aggregation kinetics by measuring the change in the average hydrodynamic diameter of the nanoparticles with time over a range of electrolyte types (NaCl, NaNO(3), and CaCl(2)) and concentrations. From this the critical coagulation concentration values were identified as 30, 40, and 2 mM for NaNO(3), NaCl, and CaCl(2), respectively. Although the silver nanoparticles were observed to dissolve in all three electrolyte solutions, the aggregation results were still consistent with classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The dissolution of the silver nanoparticles, which were coated with a layer of Ag(2)O, was highly dependent on the electrolyte type and concentration. In systems with Cl(-) a secondary precipitate, likely AgCl, also formed and produced a coating layer that incorporated the silver nanoparticles. Aggregation of the silver nanoparticles was also examined in the presence of Nordic aquatic fulvic acid and was little changed compared to that evaluated under identical fulvic acid-free conditions. These results provide a fundamental basis for further studies evaluating the environmental fate of silver nanoparticles in natural aquatic systems.

13.
J Colloid Interface Sci ; 345(2): 556-60, 2010 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-20227085

RESUMO

Low molecular weight organic acids comprise an important pool of reactive ligands in aquatic systems. These acids readily bind to nano-sized mineral particles and thereby strongly influence a particle's physicochemical behavior. Predicting this influence requires the integration of molecular-level details that control surface complexation mechanisms and structures with macro-scale observations of mineral colloid behavior. We report on the aggregation kinetics of nano-sized hematite in the presence of fumaric acid and maleic acid, which are naturally occurring dicarboxylic acids of similar size and structure. Our results indicate that the structure and orientation of the adsorbed dianion at the hematite surface, not the adsorption mechanism, defines the resulting effect. Maleate, which directs both carboxyl groups to the surface in the form of inner- and outer-sphere surface complexes, enhances colloidal stability. Fumarate, however, which binds to the hematite surface as an outer-sphere complex with just one carboxyl group only slightly influenced particle stability. This outcome suggests that subtle differences in the structure of adsorbed acids produce important differences in the physicochemical behavior of particles in dilute aquatic systems.


Assuntos
Compostos Férricos/química , Fumaratos/química , Nanopartículas de Magnetita/química , Maleatos/química , Adsorção , Coloides , Propriedades de Superfície
14.
Chemosphere ; 78(8): 1049-55, 2010 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-20015533

RESUMO

To better understand the behavior of low molecular weight organic acids in subsurface environments, the transport of three dicarboxylic acids (phthalic, maleic, and fumaric acid) in water-saturated columns packed with a hematite-coated sand was investigated in single and binary organic acid systems. Experiments were conducted at a single ionic strength (0.1M) and at two pH values (4.1 and 5.3). In single-acid systems, the order of breakthrough at both pH values was fumaric acid, followed by maleic acid, and then phthalic acid. The shape of the breakthrough curves for the acids at the two pH values were similar except at pH 5.3 phthalic acid showed two adsorption fronts. The initial front only partially broke through, whereas the second front proceeded to complete breakthrough. This behavior resulted from a marked pH increase during phthalic acid adsorption and suggests that the single-acid systems behaved as dual-component systems with the organic acid and hydrogen ion as variables. The breakthrough curves for the binary organic acid systems showed organic acids with a higher adsorption affinity (e.g., phthalic acid) competitively displace organic acids with a lower adsorption affinity (e.g., fumaric acid). The dual-component effect observed for phthalic acid in the single-acid systems was suppressed in the mixed acid systems, perhaps reflecting pH changes that accompanied the desorption of the weakly-binding acids. These results may provide an important step toward further elucidating the processes controlling organic acid fractionation in the subsurface.


Assuntos
Fumaratos/química , Maleatos/química , Ácidos Ftálicos/química , Dióxido de Silício/química , Adsorção , Cromatografia/métodos , Concentração de Íons de Hidrogênio , Porosidade
15.
J Colloid Interface Sci ; 336(1): 200-7, 2009 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-19394622

RESUMO

Recent spectroscopic and theoretical investigations provide evidence suggesting organic acids bind to mineral surfaces simultaneously as inner- and outer-sphere complexes and that the relative importance of these species varies with solution chemistry (e.g., pH), mineral type, and organic acid. Constraining surface complexation models (SCMs) with this information has proven difficult; however, as efforts to tune the surface complex stoichiometry within the SCM to match the structures and speciation trends observed in the spectra are seldom successful. In this study, the adsorption of phthalic acid on hematite was investigated using the Extended Constant Capacitance Model (ECCM) in a manner that was consistent with reported spectroscopic results. The influence of adjustable model parameters (capacitance, site density, and charge distribution) on model fit and the corresponding determination of surface speciation was tested. Although nearly equivalent fits were determined with a model comprised of a single outer-sphere complex and a dual-mode model that included one inner-sphere complex and one outer-sphere complex, results with the dual-mode model were more consistent with spectroscopic results from the literature. The surface speciation predicted by the dual-mode model was dependent on model parameter choice, with the concentration of the inner-sphere complex at low pH significantly increasing with decreasing inner-layer capacitance and site density. These results suggest to reliably use SCMs to describe adsorption over a wide range of experimental conditions requires direct knowledge of surface speciation to constrain the selection of surface complexation reactions and adjustable model parameters.

16.
J Colloid Interface Sci ; 319(1): 206-13, 2008 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-18076896

RESUMO

Potentiometric acid-base titration data for three hematite samples that differed on the basis of specific surface area (17.4, 33, 83 m2/g for hematite A, B, and C, respectively) was analyzed using the triple-layer model (TLM). The sensitivity of the TLM fits of the data to the choice of site density (N(s)) was evaluated from 1.5 to 22 sites/nm2. In general, little dependence in the quality of fit was determined, irrespective of the value of Ns. Values of the electrolyte adsorption equilibrium constants (log K cation 0 and log K anion 0) steadily increased with decreasing Ns. These constants are consistent with the commonly used 1.0 M standard state and when converted into comparable constants consistent with the site-occupancy standard state (log K cation theta and log K anion theta) a single value for each respective constant was determined. Values of the inner-layer capacitance (C1) were varied during these optimizations and increased with decreasing Ns, particularly below 5 sites/nm2. The optimized C1 values exhibited an apparent inverse relationship with specific surface area (i.e., C1 for hematite A>C1 for hematite B>C1 for hematite C). The magnitude of change in C1 with respect to Ns depended upon the magnitude of C1 for each hematite as the higher the C1 value, the greater was the change with respect to Ns. These results suggest when the site-occupancy standard state parameters are used to predict constants at different site density values without re-regression of titration data that variations in C1 should be accounted for, particularly for low specific surface area samples that have a high C1.

17.
Langmuir ; 24(24): 13934-43, 2008 Dec 16.
Artigo em Inglês | MEDLINE | ID: mdl-19360935

RESUMO

The adsorption at the hematite/water interface of a suite of C4-dicarboxylic acids (maleic, fumaric, and succinic acids) that differ with respect to the orientation of the carboxylic acid groups was studied using in situ attenuated total reflectance Fourier-transform infrared (ATR-FTIR) spectroscopy and batch adsorption experiments. Results of phthalic acid adsorption under similar experimental conditions from our previous study were compared with those observed for the C4-dicarboxylic acids. The batch adsorption experiments suggest that the orientation of the two carboxylic groups and pK(a) values of the organic acids noticeably influence the adsorption density as well as the position and characteristics of the pH adsorption edges. In particular, the adsorption capacity of fumaric acid was much lower than that observed for the other organic acids. The ATR-FTIR results also suggest that the adsorption modes of the organic acids on hematite depend on the orientation of the two carboxylic functional groups. Succinic acid with higher molecular flexibility, maleic acid with cis-configuration, and phthalic acid with ortho-position of the two carboxylic groups were similarly present as deprotonated bidentate inner- and outer-sphere complexes likely involving both carboxylic groups. The inner-sphere complex was more significant at acidic pH. Fumaric acid, however, with transconfiguration seems to bind to hematite primarily as a deprotonated outer-sphere complex utilizing only one carboxylic group.


Assuntos
Carbono/química , Ácidos Dicarboxílicos/química , Compostos Férricos/química , Água/química , Adsorção , Modelos Moleculares , Conformação Molecular , Espectroscopia de Infravermelho com Transformada de Fourier
18.
J Colloid Interface Sci ; 307(1): 124-34, 2007 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-17188289

RESUMO

The adsorption of o-phthalic acid at the hematite/water interface was investigated experimentally using batch adsorption experiments and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy over a wide range of solution pH, surface loading, and ionic strength conditions. Molecular orbital calculations for several possible surface complexes were also performed to assign atomistic structures to the features observed in the ATR-FTIR spectra. The results of the batch adsorption experiments exhibit typical anionic characteristics with high adsorption at low pH and low adsorption at high pH. The adsorption of phthalic acid also exhibits a strong dependence on ionic strength, which suggests the presence of outer-sphere complexes. ATR-FTIR spectra provide evidence of three fully deprotonated phthalate surface complexes (an outer-sphere complex and two inner-sphere complexes) under variable chemical conditions. A fully deprotonated outer-sphere complex appears to dominate adsorption in the circumneutral pH region, while two fully deprotonated inner-sphere complexes that shift in relative importance with surface coverage increase in importance at low pH. Comparison of experimental and theoretical calculations suggests the two inner-sphere complexes are best described as a mononuclear bidentate (chelating) complex and a binuclear bidentate (bridging) complex. The mononuclear bidentate inner-sphere complex was favored at relatively low surface coverage. With increasing surface coverage, the relative contribution of the binuclear bidentate inner-sphere complex increased in importance.

19.
Environ Sci Technol ; 38(1): 120-6, 2004 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-14740726

RESUMO

To better understand how interactions with the air phase influence the movement of natural organic matter (NOM) through the vadose zone, we measured the transport of soil-humic acid (SHA) through laboratory columns packed with partially saturated sand. Our results demonstrate that sorptive reactions at air-water interfaces reduce SHA mobility and that the affinity of SHA for the air phase increases as the porewater pH declines from 8 to 3.9. SHA desorption from air-water interfaces is negligible for conditions of constant pH, but release of bound SHA occurs in response to perturbations in porewater pH. We analyzed the effluent samples collected from our laboratory columns using high-performance size-exclusion chromatography. The results of this analysis demonstrate that the SHA did not fractionate appreciably during transport through the columns, suggesting that the various components of the SHA pool (as distinguished on the basis of molecular weight) express an equal affinity for the air-water interfaces over the range of pH conditions tested. A mathematical model incorporating irreversible, second-order rate laws to simulate adsorption at air-water and solid-water interfaces closely describes the SHA breakthrough data. The mass-transfer parameters that govern this model vary in a discernible fashion with changes in porewater pH, and the parameter trends are consistent with published theories for SHA adsorption.


Assuntos
Poluentes Ambientais/análise , Modelos Teóricos , Adsorção , Ar , Cromatografia em Gel , Concentração de Íons de Hidrogênio , Peso Molecular , Compostos Orgânicos , Porosidade , Água/química
20.
Environ Sci Technol ; 37(12): 2780-7, 2003 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-12854719

RESUMO

This research focuses on the effects of transients in porewater chemistry on colloid mobilization within water-saturated porous media. We develop a model that couples equations for solute transport with those for colloid release and transport. The model accounts for heterogeneity in the interaction energies between deposited colloids and the mineral grains by dividing the immobile-phase colloid population into a series of compartments. Each compartment releases colloids at a characteristic critical solute concentration, which is assigned on the basis of a piece-wise linear distribution function. We test this model against data from column experiments in which successive step-change reductions in porewater NaCl concentrations induced pulse-type releases of silica colloids from the surfaces of quartz sand. Comparison of experimental and computed results reveals that colloid release rates vary nonlinearly with the immobile-phase colloid concentration and depend on the chemical conditions under which the colloids were deposited on the quartz sand. Our work demonstrates that colloid mobilization kinetics can be quantified given knowledge of the spatiotemporal changes in porewater chemistry.


Assuntos
Coloides/química , Modelos Químicos , Dióxido de Silício/química , Poluentes Químicos da Água/análise , Eletroforese , Sedimentos Geológicos/análise , Cinética , Modelos Lineares , Porosidade , Cloreto de Sódio , Movimentos da Água
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