Environmental factors influencing sorption of heterocyclic aromatic compounds to soil

Heterocyclic organic compounds containing nitrogen, sulfur, or oxygen (NSOs) are an important class of groundwater contaminants related to the production and use of manufactured gas, heavy oils, and coal tar. Surprisingly little is known about the processes that control sorption and transport of NSOs in the subsurface. In this study, the effects of various environmental factors including temperature, ionic strength, and dissolved/sorbed ion composition on the sorption of NSOs have been investigated by means of a soil column chromatography approach. For the investigated compounds, increased temperature normally decreases their sorption to soil. The enthalpy change of the sorption process corroborates earlier findings that van der Waals forces dominate the sorption of S- and O-heterocyclic compounds such as thiophene, benzothiophene, benzofuran, and 2-methylbenzofuran. Ionic strength and ion composition (Ca2+ vs K+ at given ionic strength) of the aqueous phase show no significant effects on the sorption of these compounds. Previous studies demonstrated that for N-heterocyclic compounds, cation exchange and surface complex formation rather than partitioning into soil organic matter control their overall sorption. In contrast to S- and O-heterocyclic compounds, increasing ionic strength reduced the sorption of ionizable N-heterocyclic compounds (pyridine, 2-methylpyridine, quinoline, 2-methylquinoline, and isoquinoline), due to increased electrostatic competition by cations. At given ionic strength, an increase of the K+/Ca2+ ratio in the mobile phase enhanced the sorption of N-heterocyclic compounds, consistent with cation exchange of the protonated organic species as the dominating sorption process. Among the investigated N-heterocyclic compounds sorption of benzotriazole showed a peculiar feature in that ternary surface complexation with Ca2+ appears to be the dominant sorption mechanism.     

Adsorption of nonionic aromatic compounds to single-walled carbon nanotubes: effects of aqueous solution chemistry

We systematically studied effects of pH, ionic strength, and presence of Cu2+ (50 mg/L) or a dissolved humic acid (HA, Fluka) (50 mg/L) on adsorption of three nonionic aromatic compounds, naphthalene, 1,3-dinitrobenzene, and 1,3,5-trinitrobenzene to single-walled carbon nanotubes. Presence of Cu2+ or variance in the ionic strength between 0.02 and 0.1 M (NaNO3) only slightly affected adsorption affinities. Presence of HA reduced adsorption of the three compounds by 29-57% for CNTs, as measured by change in distribution coefficient(Kd), and by 80-95% for graphite. In contrast to nonporous graphite, whose surface area was completely accessible in adsorption, CNTs formed aggregates with microporous interstices in aqueous solution, which blocked large HA molecules from competing with the surface area. Changing the pH from 2 to 11 did not affect adsorption of naphthalene, while it increased adsorption of 1,3-dinitrobenzene and 1,3,5-trinitrobenzene by 2-3 times. Increasing pH apparently facilitated deprotonation of the acidic functional groups (-COOH, -OH) of CNTs, which promoted the pi-electron-donor ability of the graphene surface, therefore enhancing pi-pi electron-donor-acceptor (EDA) interactions of the two nitroaromatics (pi-electron acceptors).     

Modeling tetracycline antibiotic sorption to clays

Sorption interactions of three high-use tetracycline antibiotics (oxytetracycline, chlortetracycline, tetracycline) with montmorillonite and kaolinite clays were investigated undervaried pH and ionic strength conditions. Sorption edges were best described with a model that included cation exchange plus surface complexation of zwitterion forms of these compounds. Zwitterion sorption was accompanied by proton uptake, was more favorable on acidic clay, and was relatively insensitive to ionic strength effects. Calcium salts promoted oxytetracycline sorption at alkaline pHs likely by a surface-bridging mechanism. Substituent effects among the compounds in the tetracycline class had only minor effects on sorption edges and isotherms under the same solution pH and ionic strength conditions. At low ionic strength, greater sorption to montmorillonite than kaolinite was observed at all pHs tested, even after normalizing for cation exchange capacity. These results indicate that soil and sediment sorption models for tetracyclines, and other pharmaceuticals with similar chemistry, must account for solution speciation and the presence of other competitor ions in soil or sediment pore waters.     

Probing the specific sorption sites on montmorillonite using nitroaromatic compounds and hexafluorobenzene

The objective of this work was to test two possible sorption mechanisms of organic chemicals to montmorillonite: n-π electron-donor-acceptor (EDA) interaction with lone electron pairs of siloxane oxygens (n-donors) and complexation with exchangeable cations. Batch sorption experiments were performed for 1,3-dinitrobenzene, 1,4-dinitrobenzene (π-electron acceptors and cation binders), and hexafluorobenzene (π-electron acceptor only) to homoionic montmorillonites in water or hexane. For all three sorbates, the aqueous sorption affinity showed large cation dependency (Cs(+) > K(+) > Na(+)), wherein sorption of hexafluorobenzene to Cs(+)-montmorillonite was the strongest (K(d) in the order of 10(4) L/kg). Change of the solvent media from water to hexane generally favored sorption, indicating suppressive effect by cation hydration. Cosorption of 1,4-dinitrobenzene prominently decreased sorption of 1,3-dinitrobenzene to all cation-exchanged montmorillonites; however, hexafluorobenzene caused strong competition only to Cs(+)-montmorillonite. Furthermore, complexation of exchangeable cations by 18-crown-6 ether dramatically suppressed sorption of 1,3-dinitrobenzene to K(+)-montmorillonite in water and all cation-exchanged montmorillonites in hexane, but not to the rest. The contrast patterns of binary competitive sorption between nitroaromatics and hexafluorobenzene indicated they sorbed to different sites on montmorillonite. It was proposed that sorption of hexafluorobenzene was dominated by n-π EDA interaction, while sorption of nitroaromatics was dominated by cation-polar interaction.     

Thermodynamics of nitroaromatic compound adsorption from water by smectite clay

Nitroaromatic compounds enter the environment through their use as explosives, pesticides, solvents, and synthetic intermediates in the manufacturing of dyes, perfumes, and drugs. Recent studies have found that many nitroaromatic compounds are strongly retained by smectites, especially K+-saturated smectites. Sorption occurs when nitroaromatic compounds replace water associated with the clay and form complexes between K+ and -NO2 groups. This study seeks to further understand nitroaromatic-clay interactions from the viewpoint of energetics. Adsorption isotherms of 1,3-dinitrobenzene, 1,4-dinitrobenzene, and 1,3,5-trinitrobenzene from aqueous solution by K+- and Ca2+-saturated smectite (SWy-2) were measured at several temperatures between 4 degrees C and 37 degrees C to determine the molar differential adsorption enthalpies. Adsorption was found to be an exothermic process on both homoionic K+- and Ca2+-smectite. The smaller adsorption enthalpy on Ca-SWy-2 was consistent with its much smaller adsorption capacity for nitroaromatics compared to K-SWy-2. Our best estimate forthe enthalpy of 1,3,5-trinitrobenzene interactions with K-SWy-2 is -124 kJ/mol, which is referenced to gas-phase 1,3,5-trinitrobenzene, corrected forthe displacement of interlayer water, and can be directly compared with quantum chemical enthalpies from the literature. Our comparable estimates for 1,3- and 1,4-dinitrobenzene interaction enthalpies are near -90 kJ/mol. We conclude that our adsorption enthalpy results are consistent with the hypothesis that nitroaromatic compounds are sorbed strongly by K-smectites because they form inner- and/or outer-sphere complexes with K+ cations in clay interlayers. Indeed, the basal spacings of rewetted clay films in the presence of nitroaromatic compounds imply that water molecules cannot effectively compete with the adsorbed nitrobenzenes for reactive sites on K-SWy-2.     

Geochemical modulation of pesticide sorption on smectite clay

Pesticide adsorption by soil clays can be dramatically influenced by the exchangeable cations present. Among the common exchangeable base cations in soils (Ca2+, Mg2+, K+, and Na+), K+-saturated clays frequently demonstrate the strongest affinity for pesticides. In the presence of multiple exchangeable cations in the system, we hypothesize that the magnitude of pesticide sorption to soil minerals is proportional to the fraction of clay interlayers saturated with K+ ions. To test this hypothesis, we measured sorption of three pesticides with different polarities (dichlobenil, monuron, and biphenyl) by homoionic K- and Ca-smectite (SWy-2) in KCl/CaCl2 aqueous solutions. The presence of different amounts of KCl and CaCl2 resulted in varying populations of K+ and Ca2+ on the clay exchange sites. The sorption of dichlobenil and, to a lesser extent monuron, increased with the fraction of K+ on clay mineral exchange sites. Ca- and K-SWy-2 displayed the same sorption capacities for nonpolar biphenyl. X-ray diffraction patterns indicated that at lower fractions of K+-saturation, exchangeable K+ ions were randomly distributed in clay interlayers and did not enhance pesticide sorption. At higher populations of K+ (vs Ca2+), demixing occurred causing some clay interlayers, regions, or tactoids to become fully saturated by K+, manifesting greatly enhanced pesticide sorption. The forward and reverse cation exchange reactions influenced not only K+ and Ca2+ populations on clays but also the nanostructures of clay quasicrystals in aqueous solution which plays an important, if not dominant, role in controlling the extent of pesticide sorption. Modulating the cation type and composition on clay mineral surfaces through cation exchange processes provides an environmental-safe protocol to manipulate the mobility and availability of polar pesticides, which could have applications for pesticide formulation and in environmental remediation.     

Effect of fluorotelomer alcohol chain length on aqueous solubility and sorption by soils

Fluorotelomer alcohols (FTOHs) are a group of polyfluorinated alkyl chemicals that have been widely studied as precursorsto perfluorocarboxylates such as perfluorooctanoic acid and for which knowledge on their fate in soils is sparse. The solubility and sorption by soil of the homologous 4:2 to 10:2 FTOHs were measured in water or cosolvent/ water solutions. For the smaller 4:2 and 6:2 FTOHs, solubility and sorption could be measured adequately in aqueous systems although transformation was apparent even in gamma-irradiated and autoclaved systems. Sorption coefficients estimated by measuring both sorbed and solution-phase concentrations were not significantly affected by the biotransformation process. The use of cosolvents was employed for probing the behavior of the longer-chain FTOHs with limited aqueous solubility. A single log-linear correlation between aqueous solubility and modified McGowan molar volumes resulted for the n-alkanols and FTOHs. Soil organic carbon (OC) consistently appeared to be the key soil property influencing sorption of the FTOHs while the perfluorocarbon chain length was the dominant structural feature influencing solubility and sorption. Each CF2 moiety decreased the aqueous solubility by -0.78 log units (compared to 0.60 log units for each CH2 addition in hydrogenated primary alcohols), and increased OC-normalized sorption coefficients (Koc) by -0.87 log units. Good log-log linear correlations between Koc and both octanol-water partition coefficients and solubility were observed for the FTOHs.     

Interaction of tetracycline with aluminum and iron hydrous oxides

The effect of solution chemistry (pH, sorbate-to-sorbent ratio, ionic strength (/)) and reaction time on the sorption of tetracycline to the hydrous oxides of Al (HAO) and Fe (HFO) was examined. Sorption to HAO increased with increasing pH upto pH 7 (no such trend for HFO) above which it decreased at higher pH values for both the hydrous oxides. Experimental results indicate that ligand-promoted dissolution is occurring during tetracycline sorption to these hydrous oxides. Ligand-promoted dissolution was more significantfor HAO than HFO attributable to the difference in labile surface sites between these two sorbents. The ability of tetracycline to form strong complexes with Al and Fe will increase the solubility of these minerals. Sorption of tetracycline was quite rapid and equilibrium was achieved after 8 h. However, soluble metal (Me: Al or Fe) concentrations attained equilibrium only after 24 h. Ligand-promoted dissolution appears to be a two-step process; initially, 1:1 Me-tetracycline soluble complexes are formed and as the reaction progresses 2:1 complexes existed. Increasing / (from 0.01 to 0.5 M) decreased the sorption extent only at higher sorbate-to-sorbent ratios suggesting the dominance of inner-sphere type complexes at low equilibrium tetracycline concentrations. Spectroscopic evidence indicates that tricarbonylamide and carbonyl functional groups of tetracycline could be responsible for sorption to mineral surfaces. Our research findings will increase understanding of the environmental occurrence, fate, and transport characteristics of antibiotics, which are considered as emerging organic contaminants.     

Effect of sodium and calcium cations on the ion-exchange affinity of organic cations for soil organic matter

Sorption of organic cations to soil organic matter was studied using dynamic column experiments with different compositions of electrolytes in aqueous eluents. The sorption affinity of the tested variety of charged compounds, including primary, secondary, and tertiary amines and quaternary ammonium compounds, all showed the same response to different medium compositions. The sorption affinity to Pahokee peat (i) strongly decreased with increasing electrolyte concentration, up to a factor 250 due to tested electrolyte compositions alone, (ii) was higher in NaCl solutions than in CaCl(2) solutions of similar ionic strength, and (iii) was more sensitive to a decrease in NaCl than to a decrease in CaCl(2), though the selectivity coefficients were not significantly different. For a weak base that was tested in eluent pH either above or below its pK(a), we demonstrated that the sorption affinity of (iv) the neutral base was hardly affected by different electrolyte compositions, comparable to a neutral reference compound, (v) the protonated weak base was strongly affected by different electrolyte compositions, and (vi) the protonated base was in the same range, or stronger, compared to the neutral base. Mass action law equations for ion-exchange reactions predicted similar trends in a qualitative but not in a quantitative way. More complex models are required to fully account for the contributions of ionic interactions to the sorption of organic cations. These results imply that risk assessment models for organic bases should take ion-exchange processes into account when estimating soil sorption coefficients and bioavailability.     

组氨酸与氯化钾混合液对兔肉肌球蛋白特性的影响

目的：研究组氨酸与氯化钾混合液对肌球蛋白溶出率、聚集特性和热凝胶特性的影响。方法：提取纯化兔腰大肌肌球蛋白,并用含有组氨酸的盐溶液透析处理,测定不同离子强度条件下蛋白溶出率、浊度以及热诱导凝胶的硬度和保水性（water holding capacity,WHC）。结果：经组氨酸处理后,在低离子强度（1 mmol/L KCl）条件下肌球蛋白的溶出率从17.2%提高到64.4%,聚集程度显著下降,热凝胶的硬度和保水性显著提高（P＜0.05）;而在生理离子强度（0.15 mol/L KCl）和高离子强度（0.6 mol/L KCl）条件下肌球蛋白的溶出率和聚集特性均未受组氨酸处理的影响,但其热凝胶硬度值显著降低（P＜0.05）;虽然在高离子强度条件下肌球蛋白热凝胶的保水性显著降低（P＜0.05）,但是在生理离子强度条件下凝胶保水性没有发生变化。结论：组氨酸处理可以显著增强低离子强度条件下肌球蛋白溶出率和其热凝胶形成能力,是低钠凝胶类肉制品生产和研发的一个新思路。     

Sorption and related properties of the swine antibiotic carbadox and associated N-oxide reduced metabolites

Carbadox (CBX) (methyl 3-[2-quinoxalinylmethylene]-carbazate N1, N4 dioxide) is a chemotherapeutic growth promoter and antibacterial drug added to feed for starter pigs. Toxicity of CBX and at least one of its metabolites (bis-desoxycarbadox; DCBX) has resulted in a number of studies regarding its stability and residence time in edible swine tissue; however, little is known on its environmental fate pertinent to the application of antibiotic-laden manure to agricultural fields. We measured sorption of CBX and DCBX by soils, sediment, and homoionic clays from 10 mM KCl and 5 mM CaCl2 solutions, sorption of two N-oxide reduced metabolites (N4 and N1) by a subset of soils from 5 mM CaCl2, octanol-water partition coefficients (Kow) of CBX and all three metabolites, and CBX solubility in water and mixed solvents. Sorption appeared well-correlated to organic carbon (OC) for the soils (e.g., log (Koc, L/kg OC) = 3.96 +/- 0.18 for CBX). However, sorption was enhanced in the presence of K+, competitive sorption from the metabolites was observed, and sorption by clay minerals was large (approximately 10(5) L/kg for SWy(-1)). Sorption by clays was inversely correlated to surface charge density (e.g., sorption decreased from 10(5) to 10 L/kg as charge density increased from 1 to 2 micromolc/m2), similar to what has been observed for nitroaromatic compounds. In the absence of a clay surface, hydrophobic-type forces dominated with Kow values and reverse-phase chromatographic retention times increasing with the loss of oxygen from the aromatic nitrogens. Therefore, it is likely that both OC and clay contribute significantly to sorption of carbadox and related metabolites by soils with relative contributions most dependent on clay type.     

Investigating the role of mineral-bound humic acid in phenanthrene sorption

Contaminant-soil interaction studies have indicated that physical conformation of organic matter atthe solid-aqueous interface is important in governing hydrophobic organic compound (HOC) sorption. To testthis, organo-clay complexes were constructed by coating montmorillonite and kaolinite with peat humic acid (PHA) in Na+ or Ca2+ dominated solutions with varying pH and ionic strength values. The solution conditions encouraged the dissolved PHA to adopt a "coiled" or "stretched" conformation prior to interacting with the clay mineral surface. Both kaolinite and montmorillonite organo-clay complexes exhibited higher phenanthrene sorption (Koc values) with decreasing pH, indicating that the coiled configuration provided more favorable sorption conditions. Evidence from 1H high-resolution magic angle spinning (HR-MAS) nuclear magnetic resonance (NMR) indicated that polymethylene groups were prevalent at the surface of the organo-clay complexes and may enhance sorptive interactions. Preferential sorption of polymethylene groups on kaolinite and aromatic compounds on montmorillonite may also contribute to the difference in phenanthrene sorption by PHA associated with these two types of clay. This study demonstrates the importance of solution conditions in the sorption of nonionic, hydrophobic organic contaminants and also provides evidence for the indirect role of clay minerals in sorption of contaminants at the soil-water interface.     

赖氨酸诱导低离子强度下罗非鱼肌球蛋白增溶及机制

以罗非鱼肉为原料提取肌球蛋白,研究5 mmol/L赖氨酸对低离子强度（1～150 mmol/L KCl）条件下肌球 蛋白（蛋白质量浓度为2.0 mg/mL）体系浊度、溶解度及分子结构和形态的影响,分析赖氨酸诱导肌球蛋白增溶 机理。结果表明,在低离子强度下,肌球蛋白分子聚集成纤丝,溶解度低,赖氨酸的添加能显著降低肌球蛋白体 系的浊度（P＜0.05）,抑制蛋白分子间的聚集,增溶效果明显,增溶后分子的表面疏水性增大,α-螺旋含量减小 （P＜0.05）,且与酸碱处理组比较,在1～40 mmol/L KCl范围内,赖氨酸增溶效果更好。增溶后的肌球蛋白Zeta- 电位的绝对值增大,丝状体解离。     

Heat-induced Gelation of Chicken Gizzard Myosin

Chicken gizzard myosin solution formed a gel when heated above 40°C. The rigidity of the gel was constant above 65°C. Maximum pH for gel formation was 5.9 at 0.6M and 5.7 at 0.15M KCl. Higher rigidity of the myosin gel was observed at low ionic strength than at high ionic strength. Rigidities of myosin at 0.6M KCl increased by (mg/mL)^2.5 and at 0.15M (mg/mL)^{1, 4} myosin concentration. The strength of gizzard myosin gels was comparable to that of myosin gels from chicken breast muscle under similar conditions.     

Hydrophilic and hydrophobic sorption of organic acids by variable charge soils: effect of chemical acidity and acidic functional group

Sorption of organic acids by variable-charge soil occurs through both hydrophilic and hydrophobic sorption. In this study, the effect of chemical acidity and the type of acidic functional group on the relative contribution of hydrophilic and hydrophobic processes to sorption by a gibbsite-dominated and a kaolinite-dominated variable-charge soils was quantified by measuring sorption isotherms from different electrolytes (CaCl2, Ca(H2PO4)2, and KCl). The A1 soil is dominated by gibbsite whereas the DRC soil is primarily kaolinite. The organic acids investigated include five chlorinated phenols (pentachlorophenol, 2,3,4,6-tetrachlorophenol, 2,4,6-trichlorophenol, 2,4,5-trichlorophenol, and 2,4-dichlorophenol) with pKa values ranging from 4.69 to 7.85 and two acidic herbicides (2,4-D (pKa = 2.8) and prosulfuron (pKa = 3.76)) that contain carboxyl and urea functional groups, respectively. Anion exchange of chlorinated phenols and prosulfuron on both variable-charge soils as well as 2,4-D sorption on the A1 soil was linearly correlated to chemical acidity. The effective positive surface charge [AEC/(AEC + CEC)] and the anionic fraction of the organic acid in solution, which are both pH-dependent, were sufficient to estimate the contribution of anion exchange to organic acid sorption except for 2,4-D sorption by DRC soil. The latter was much greater than would be predicted from the pKa of 2,4-D. Calcium bridging between silanol edge group and 2,4-D was hypothesized and corroborated by differences in sorption measured from KCl and CaCl2 solutions. For predicting contributions from hydrophobic processes, a log-log linear relationship between pH-dependent octanol-water (Kow(pH)) and organic carbon-normalized sorption coefficients (Koc(pH)) appeared adequate.     

Stability and removal of water soluble CdTe quantum dots in water

Commercial use of quantum dots (GDs) will lead to their entry into aquatic environments. This study examines the characteristics and stability of CdTe QDs with thioglycolate capping ligands in water as well as their removal by alum salts. The capping ligands of QDs are a key factor in determining their fate in water. Protonated thioglycolate capping ligands cause QDs to aggregate. The stability of QDs depends more on their ionic composition in water than on the ionic strength. In KCl solution, QDs remain stable even under 0.15 M ionic strength. Relatively low concentrations (< or = 2 meq/L) of divalent (Mg2+ and Ca2+) or trivalent (Al3+) cations, however, can induce aggregation. The proposed mechanism for this phenomenon is that multivalent metal cations (or their hydrated species) react with capping ligands to form complexes that bridge QDs or neutralize their surface charges. Because the complexation of hydrated Al3+ with capping ligands inhibits the formation of Al(OH)3 precipitates, alum dosages higher than the A3+ solubility are required to form settleable flocs and remove QDs from nanopure water by sedimentation. Divalent cations (Mg2+ and Ca2+) in tap water induce the formation of settleable QD flocs such that 70-80% of the QGDs by mass settle out.     

Sorption of aromatic organic contaminants by biopolymers: effects of pH, copper (II) complexation, and cellulose coating

Sorption of hydrophobic organic compounds (HOCs) (i.e., pyrene, phenanthrene, naphthalene, and 1-naphthol) by original and coated biopolymers was examined. Lignin yielded nonlinear isotherms due to its glassy character. Except for pyrene, cellulose showed linear isotherms for other compounds, indicating a partitioning dominant mechanism. Sorption of 1-naphthol by lignin decreased with increasing pH, attributed to both the increased pi e theta-pi e theta repulsion and weakened hydrogen bonds, while the affinity reduction of cellulose for 1-naphthol with increasing pH resulted from only the decrease in H-bonding due to its absence of benzene ring. Complexation of lignin with Cu2+ increased the sorption affinity for phenanthrene (2.6 times) and slightly enhanced its isotherm nonlinearity. For 1-naphthol, lignin-Cu2+ complex had a much higher sorption capacity (7 times)than the original lignin, accompanied bythe increased isotherm nonlinearity. Cellulose-coated lignin showed increased sorption affinity and more pronounced nonlinearity for 1-naphthol than the lignin-Cu2+ complex. In comparison, cellulose coating exhibited little effect on sorption affinity for phenanthrene relative to the lignin-Cu2+ complex. Isotherm nonlinearity of coated lignins increased with increasing cellulose coating, indicating more condensed domains produced, supported by an increase (from 68.9 degrees C for the original lignin to 82.4 degrees C for the highest cellulose coating level) in glass transition temperature (Tg). Results of this study highlightthe importance of structure, polarity, surface O-containing functional groups, and surface charges of biopolymers in controlling HOC sorption.     

Np(V) and Pu(v) ion exchange and surface-mediated reduction mechanisms on montmorillonite

Due to their ubiquity and chemical reactivity, aluminosilicate clays play an important role in actinide retardation and colloid-facilitated transport in the environment. In this work, Pu(V) and Np(V) sorption to Na-montmorillonite was examined as a function of ionic strength, pH, and time. Np(V) sorption equilibrium was reached within 2 h. Sorption was relatively weak and showed a pH and ionic strength dependence. An approximate NpO(2)(+) → Na(+) Vanselow ion exchange coefficient (Kv) was determined on the basis of Np(V) sorption in 0.01 and 1.0 M NaCl solutions at pH < 5 (Kv ~ 0.3). In contrast to Np(V), Pu(V) sorption equilibrium was not achieved on the time-scale of weeks. Pu(V) sorption was much stronger than Np(V), and sorption rates exhibited both a pH and ionic strength dependence. Differences in Np(V) and Pu(V) sorption behavior are indicative of surface-mediated transformation of Pu(V) to Pu(IV) which has been reported for a number of redox-active and redox-inactive minerals. A model of the pH and ionic strength dependence of Pu(V) sorption rates suggests that H(+) exchangeable cations facilitate Pu(V) reduction. While surface complexation may play a dominant role in Pu sorption and colloid-facilitated transport under alkaline conditions, results from this study suggest that Pu(V) ion exchange and surface-mediated reduction to Pu(IV) can immobilize Pu or enhance its colloid-facilitated transport in the environment at neutral to mildly acidic pHs.     

Linear adsorption of nonionic organic compounds from water onto hydrophilic minerals: silica and alumina

To characterize the linear adsorption phenomena in aqueous nonionic organic solute-mineral systems, the adsorption isotherms of some low-molecular-weight nonpolar nonionic solutes (1,2,3-trichlorobenzene, lindane, phenanthrene, and pyrene) and polar nonionic solutes (1,3-dinitrobenzene and 2,4-dinitrotoluene) from single- and binary-solute solutions on hydrophilic silica and alumina were established. Toward this objective, the influences of temperature, ionic strength, and pH on adsorption were also determined. It is found that linear adsorption exhibits low exothermic heats and practically no adsorptive competition. The solute-solid configuration and the adsorptive force consistent with these effects were hypothesized. For nonpolar solutes, the adsorption occurs presumably by London (dispersion) forces onto a water film above the mineral surface. For polar solutes, the adsorption is also assisted by polar-group interactions. The reduced adsorptive forces of solutes with hydrophilic minerals due to physical separation by the water film and the low fractions of the water-film surface covered by solutes offer a theoretical basis for linear solute adsorption, low exothermic heats, and no adsorptive competition. The postulated adsorptive forces are supported by observations that ionic strength or pH poses no effect on the adsorption of nonpolar solutes while it exhibits a significant effect on the uptake of polar solutes.     

Solubility of Salmon Myosin as Affected by Conformational Changes at Various Ionic Strengths and pH

The relationship between solubility and conformational changes of salmon ( Oncorhynchus tshawytscha ) myofibrillar proteins at various ionic strengths and pH was investigated using myosin as a model system. Solubility of myosin increased with increased KCl concentration up to 0.5M. Further increasing salt concentration resulted in a gradually reduced solubility. In the absence of salt, myosin was slightly soluble at pH>7 or <4. The increased solubility correlated with the increased surface hydrophobicity and relative sulfhydryl content as well as the decreased α-helicity. At KCl >1.0M, myosin regained its helix structure with a concomitant loss of solubility due to the dominant hydrophobic interaction among nonpolar amino acid residues.