Gypsum scale formation and inhibition kinetics with implications in membrane system.

Water desalination using membrane technology is one of the main technologies to resolve water pollution and scarcity issues. In the membrane treatment process, mineral scale deposition and fouling is a severe challenge that can lead to filtration efficiency decrease, permeate quality compromise, and even membrane damage. Multiple methods have been developed to resolve this problem, such as scale inhibitor addition, product recovery ratio adjustment, periodic membrane surface flushing. The performance of these methods largely depends on the ability to accurately predict the kinetics of mineral scale deposition and fouling with or without inhibitors. Gypsum is one of the most common and troublesome inorganic mineral scales in membrane systems, however, no mechanistic model is available to accurately predict the induction time of gypsum crystallization and inhibition. In this study, a new gypsum crystallization and inhibition model based on the classical nucleation theory and a Langmuir type adsorption isotherm has been developed. Through this model, it is believed that gypsum nucleation may gradually transit from homogeneous to heterogeneous nucleation when the gypsum saturation index (SI) decreases. Such transition is represented by a gradual decrease of surface tension at smaller SI values. This model assumes that the adsorption of inhibitors onto the gypsum nucleus can increase the nucleus superficial surface tension and prolong the induction time. Using the new model, this study accurately predicted the gypsum crystallization induction times with or without nine commonly used scale inhibitors over wide ranges of temperature (25-90 °C), SI (0.04-0.96), and background NaCl concentration (0-6 mol/L). The fitted affinity constants between scale inhibitors and gypsum show a good correlation with those between the same inhibitors and barite, indicating a similar inhibition mechanism via adsorption. Furthermore, by incorporating this model with the two-phase mineral deposition model our group developed previously, this study accurately predicts the gypsum deposition time on the membrane material surfaces reported in the literature. We believe that the model developed in this study can not only accurately predict the gypsum crystallization induction time with or without scale inhibitors, elucidate the gypsum crystallization and inhibition mechanisms, but also optimize the mineral scale control in the membrane filtration system.

A rapid experimental protocol to determine the desorption resistant fraction of sediment-sorbed hydrophobic organic contaminants.

Desorption of hydrophobic organic contaminants (HOCs) from sedimentary materials plays a vital role in dictating the fate and transport of HOCs in the environment. Desorption irreversibility is a commonly observed phenomenon in laboratory sorption/desorption studies of HOCs. A desorption-resistant fraction (DRF) typically exists during the desorption process. To correctly evaluate the DRF of HOCs can considerably contribute to the understanding of availability and bioavailability of HOCs. This can substantially benefit contaminant remediation and cleanup operations. Conventional batch method to measure the DRF replies on repetitive washing of the sediments, which is time-consuming and can be impractical. This study presents an experimental protocol to quantify the DRF of the sediment-sorbed organic contaminants in a rapid manner. This protocol utilizes cosolvent to expedite desorption kinetics and adopts an ultrafiltration/centrifugation combined method to achieve a complete separation of sediment and solution phases. This proposed experimental protocol can facilitate the quantification of the DRF of sorbed contaminants to understand and minimize the uncertainties associated with risk-based pollution remediation approach. This protocol has the potential to be widely used in environmental studies to characterize sorption and desorption properties of HOCs with soil and sedimentary materials.

Sorption and desorption characteristics of anionic surfactants to soil sediments.

Surfactants are important environmental chemicals due to their extensive domestic and industrial applications, such as subsurface organic pollution remediation and enhanced oil recovery. However, the interaction of surfactants with subsurface material particularly the desorption behavior of surfactants is less understood. Surfactant desorption is essential to control the fate and transport of surfactants as well as organic pollutants. In this study, the sorption and desorption of linear sodium dodecylbenzene sulfonate (SDBS) and sodium hexadecyl diphenyl oxide disulfonate (DPDS) with two types of soil sediment samples are compared. Sorption of surfactants can be modeled by hydrophobic sorption. Less DPDS sorption is observed at a higher aqueous concentration, which is attributed to the competition between surfactant micelles and sediment organic matter for DPDS sorption. A significant fraction of the sorbed surfactants resists desorption, and this is not a result of surfactant precipitation or desorption kinetics. Surfactant desorption behavior is similar to the irreversible desorption of hydrocarbons from soil with only half of the resistant phase surfactant being readily extracted by heated solvent extraction. The sorption/desorption data are interpreted with a molecular topology and irreversible sorption model. The knowledge of this study can be useful in understanding the environmental fate and transport of these common anionic surfactants. The methodology developed in this study can be expanded to study the sorptive nature of a wider range of surfactants in the environment.

Identification of a new high-molecular-weight Fe-citrate species at low citrate-to-Fe molar ratios: Impact on arsenic removal with ferric hydroxide.

Ferric hydroxide precipitation and flocculation is the most commonly used method for the removal of arsenic in water treatment. However, citrate often interrupts the precipitation of ferric hydroxides and thus affects arsenic removal. To date, the mechanisms controlling the effects of citrate on arsenic removal with ferric hydroxide flocculation and precipitation at very low citrate-to-Fe molar ratios are not well understood. Herein, we report a new mechanism by which citrate inhibits arsenic removal using ferric hydroxide. At a substoichiometric citrate-to-Fe molar ratio of 0.28, citrate forms a high-molecular-weight Fe-citrate (Fe4Cit) species. The optimized structure of the Fe4Cit species was obtained by the density functional theory calculation. To the best of our knowledge, this study is the first to report the formation and to identify the structure of dominant Fe-citrate species at a very low citrate-to-Fe molar ratio.

Mechanistic understanding of calcium-phosphonate solid dissolution and scale inhibitor return behavior in oilfield reservoir: formation of middle phase.

Phosphonates are an important class of mineral scale inhibitors used for oilfield scale control. By injecting the phosphonate into an oilfield reservoir, calcium-phosphonate precipitate will form and subsequently release the phosphonate into produced water for scale control. In this study, a systematic procedure is developed to mechanistically characterize an acidic calcium-phosphonate amorphous material that is later developed into a middle phase and eventually a crystalline phase. The phosphonate used in this study is diethylenetriamine pentakis (methylene phosphonic acid) (DTPMP). An amorphous calcium-DTPMP solid is precipitated by mixing a calcium-containing solution with a DTPMP solution. The stoichiometry of this initially formed solid can be experimentally confirmed via a static dissolution test. Following another dynamic development test, two additional Ca-DTPMP solid phases, i.e., a middle phase and a crystalline phase have been observed. Electron microscopy and X-ray diffraction were employed to characterize the morphology and crystallinity of different Ca-DTPMP solids of interest. Evidently, the dynamic brine flushing of the Ca-DTPMP solid developed the initially amorphous material into a middle phase solid with an amorphous/microcrystalline structure and eventually into a crystalline material. Furthermore, a dissolution characterization study was carried out to determine the solubility product of the middle phase solid at different conditions. The obtained mechanistic understanding of the Ca-DTPMP solid related to precipitation chemistry, dissolution behavior and phase transition is critical to elucidate oilfield DTPMP return data and more importantly, can optimize the oilfield scale squeeze design to achieve an extended squeeze lifetime.

Carbon-based nanoreporters designed for subsurface hydrogen sulfide detection.

Polyvinyl alcohol functionalized carbon black with H2S-sensor moieties can be pumped through oil and water in porous rock and the H2S content can be determined based on the fluorescent enhancement of the H2S-sensor addends.

Contaminant-mobilizing capability of fullerene nanoparticles (nC60): Effect of solvent-exchange process in nC60 formation.

Fullerene nanoparticles (nC(60)) in aqueous environments can significantly enhance the transport of hydrophobic organic contaminants by serving as a contaminant carrier. In the present study, the authors examine the effect of the solvent-exchange process on nC(60) aggregate formation and, subsequently, on nC(60) 's contaminant-mobilizing capability. A series of nC(60) samples were prepared using a modified toluene-water solvent-exchange method through the inclusion of a secondary organic solvent in the phase transfer of molecular C(60) in toluene to nC(60) in water. Two groups of solvents--a water-miscible group and a non-water-miscible group-of varied polarity were selected as secondary solvents. The involvement of a secondary solvent in the phase transfer process had only small effects on the particle size and distribution, ζ potential, and mobility of the nC(60) products but significantly influenced the capability of nC(60) to enhance the transport of 2,2',5,5'-polychlorinated biphenyl (PCB) in a saturated sandy soil column, regardless of whether the secondary solvent was water-miscible or non-water-miscible. The two groups of secondary solvents appear to affect the aggregation properties of nC(60) in water via different mechanisms. In general, nC(60) products made with a secondary water-miscible solvent have stronger capabilities to enhance PCB transport. Taken together, the results indicate that according to formation conditions and solvent constituents, nC(60) will vary significantly in its interactions with organic contaminants, specifically as related to adsorption or desorption as well as transport in porous media.

A priori prediction of thermodynamic properties of electrolytes in mixed aqueous-organic solvents to extreme temperatures.

The unified theory of electrolytes (J. Phys. Chem. B 2009, 113, 2398-2404) for predicting the standard state thermodynamic properties of aqueous electrolytes has been extended to include mixed solvent systems. The solubility of solid sodium chloride in mixed solvents (methanol/water concentration up to 75% w/w) was also measured up to 466 K and pressures near 7 MPa. The present model, together with a simple modification of Pitzer's thermodynamic treatment of aqueous solutions, allows a priori prediction of solubility of electrolytes in aqueous/organic systems to extreme temperatures and pressures. Solubility is predicted for sodium chloride and potassium chloride in mixed solvents (methanol/water, ethanol/water) over a wide range of temperatures and compositions from the extension of the unified theory of electrolytes to mixed solvents. Comparisons indicate good agreement in all cases to well within the uncertainties of the experimental data. The stoichiometric activity coefficients of saturated solution of sodium chloride in methanol/water mixed solvents were calculated up to 473.15 K. The stoichiometric activity coefficients, as a function of temperature at all concentrations (0 ≤ m ≤ m(sat)) and the entire range of mole fraction of methanol, were also calculated up to 473.15 K. The novelty of the present approach is that no additional parameters are required to account for the medium effect.

Transport of fullerene nanoparticles (nC60) in saturated sand and sandy soil: controlling factors and modeling.

Understanding subsurface transport of fullerene nanoparticles (nC(60)) is of critical importance for the benign use and risk management of C(60). We examined the effects of several important environmental factors on nC(60) transport in saturated porous media. Decreasing flow velocity from approximately 10 to 1 m/d had little effect on nC(60) transport in Ottawa sand (mainly pure quartz), but significantly inhibited the transport in Lula soil (a sandy, low-organic-matter soil). The difference was attributable to the smaller grain size, more irregular and rougher shape, and greater heterogeneity of Lula soil. Increasing ionic strength and switching background solution from NaCl to CaCl(2) enhanced the deposition of nC(60) in both sand and soil columns, but the effects were more significant for soil. This was likely because the clay minerals (and possibly soil organic matter) in soil responded to changes of ionic strength and species differently than quartz. Anions in the mobile phase had little effect on nC(60) transport, and fulvic acid in the mobile phase (5.0 mg/L) had a small effect in the presence of 0.5 mM Ca(2+). A two-site transport model that takes into account both the blocking-affected attachment process and straining effects can effectively model the breakthrough of nC(60).

Enhanced transport of 2,2',5,5'-polychlorinated biphenyl by natural organic matter (NOM) and surfactant-modified fullerene nanoparticles (nC60).

Stable colloidal suspensions of buckminsterfullerene (nC(60)) in aqueous environments can significantly affect the fate and transport of hydrophobic organic contaminants by serving as a contaminant carrier. In this study, we examined enhanced transport of 2,2',5,5'-polychlorinated biphenyl (PCB) in saturated sandy soil columns by a variety of nC(60) samples, including an nC(60) sample prepared by the typical solvent exchange method, as well as eight natural organic matter (NOM) or surfactant-modified nC(60) samples, prepared by phase-transferring C(60) from toluene to an NOM or a surfactant solution. Whereas the NOM- and surfactant-modified nC(60) samples have mobility similar to the unmodified nC(60), their contaminant-mobilizing capabilities are significantly greater: breakthrough of PCB increases by 47.2 to 227% with the surfactant-modified nC(60) samples and by 233 to 370% with the NOM-modified nC(60) samples. The significantly enhanced contaminant-mobilizing capability of the modified nC(60) is likely due to a combined effect of increased adsorption affinities and increased tendency of desorption nonequilibrium, likely caused by the changes of nC(60) aggregation properties induced by the presence of NOM or surfactant. Findings in this study indicate that nC(60) formed in different processes might have vastly different effects on contaminant fate and transport.

Mobilization of trace metals and inorganic compounds during resuspension of anoxic sediments from Trepangier Bayou, Louisiana.

The release of trace metals (Mn, Ni, Co, Cu, Zn, Pb, and Cd) and inorganic compounds (As) from initially anoxic Trepangier Bayou sediments, Louisiana and the sources of the released metals were investigated. After 1 to 2 d aeration, significant amounts of trace metals (Mn, Zn, Cd, Ni, and Co) were released to the aqueous phase with increased acidity, primarily due to the oxidation of acid-volatile sulfide and ferrous iron and iron sulfide minerals. The addition of a bacterial inhibitor, NaN,, to the Trepangier sediment during resuspension inhibited metal release, suggesting that microbial catalysis can regulate metal mobilization during sediment resuspension. In a well buffered system, oxidation of iron sulfides alone did not appear to induce trace metal release. Moreover, when Trepangier sediment was resuspended in anoxic conditions at neutral pH, <1% of the trace metal content was released, whereas a significant release of metal was observed under acidic anoxic conditions. Although oxidation of iron sulfide minerals is an essential prerequisite for the release of Zn, Co, Cd, and Ni, carbonates and oxides also play a role. The trace metals and inorganic compounds investigated could be classified into three groups according to their release characteristics: (i) Mn, Zn, Cd, Ni, and Co; (ii) Fe, Pb, and As; and (iii) Cu. The groupings appeared to depend on the sources of compounds and their relative affinity, after oxidation, to iron oxyhydroxides or organic matter.

Facilitated transport of 2,2',5,5'-polychlorinated biphenyl and phenanthrene by fullerene nanoparticles through sandy soil columns.

The potential environmental implications of buckminsterfullerene (C60) and its derivatives have received much attention. In this study, we investigated facilitated transport of 2,2',5,5'-polychlorinated biphenyl (PCB) and phenanthrene by nC60 (a stable aqueous-phase aggregate of C60) through two sandy soil columns. We found that low-level (from 1.55 to 12.8 mg/L) nC60 could significantly enhance the mobility of PCB and phenanthrene. However, none of the three model dissolved organic matters (DOMs)-a humic acid, a fulvic acid, and a bovine serum albumin-had a noticeable effect on the transport of PCB when these DOMs were present at concentrations equivalent to approximately 10-11 mg/L organic carbon. We propose that the contaminant-mobilizing ability of nC60 is a result of irreversible adsorption of a fraction of nC60-associated PCB/phenanthrene (whereas DOM-associated PCB is readily desorbable). Additionally, slow desorption kinetics of nC60-adsorbed PCB/phenanthrene is another possible mechanism. The findings in this study indicate that nC60 in the subsurface environment can greatly enhance the mobility of nonionic, highly hydrophobic organic contaminants, which typically exhibit very low mobility. Such effects should be taken into account when assessing the potential environmental risks of engineered carbonaceous nanomaterials.

pH-dependent effect of zinc on arsenic adsorption to magnetite nanoparticles.

UNLABELLED: The effect of Zn(2+) on both the kinetic and equilibrium aspects of arsenic adsorption to magnetite nanoparticles was investigated at pH 4.5-8.0. At pH 8.0, adsorption of both arsenate and arsenite to magnetite nanoparticles was significantly enhanced by the presence of small amount of Zn(2+) in the solution. With less than 3 mg/L of Zn(2+) added to the arsenic solution prior to the addition of magnetite nanoparticles, the percentage of arsenic removal by magnetite nanoparticles increased from 66% to over 99% for arsenate, and from 80% to 95% for arsenite from an initial concentration of ∼100 µg/L As at pH 8.0. Adsorption rate also increased significantly in the presence of Zn(2+). The adsorption-enhancement effect of Zn(2+) was not observed at pH 4.5-6.0, nor with ZnO nanoparticles, nor with surface-coated Zn-magnetite nanoparticles. The enhanced arsenic adsorption in the presence of Zn(2+) cannot be due to reduced negative charge of the magnetite nanoparticles surface by zinc adsorption. Other cations, such as Ca(2+) and Ag(+), failed to enhance arsenic adsorption. Several potential mechanisms that could have caused the enhanced adsorption of arsenic have been tested and ruled out. Formation of a ternary surface complex by zinc, arsenic and magnetite nanoparticles is a possible mechanism controlling the observed zinc effect. Zinc-facilitated adsorption provides further advantage for magnetite nanoparticle-enhanced arsenic removal over conventional treatment approaches. SYNOPSIS: Arsenic adsorption to magnetite nanoparticles at neutral or slightly basic pH can be significantly enhanced with trace amount of Zn(2+) due to the formation of a ternary complex.

A sorption kinetics model for arsenic adsorption to magnetite nanoparticles.

INTRODUCTION: Arsenic is a well known water contaminant that causes toxicological and carcinogenic effects. In this work magnetite nanoparticles were examined as possible arsenic sorbents. The objective of this work was to develop a sorption kinetics model, which could be used to predict the amount of arsenic adsorbed by magnetite nanoparticles in the presence of naturally occurring species using a first-order rate equation, modified to include adsorption, described by a Langmuir isotherm. DISCUSSION: Arsenate and arsenite adsorption to magnetite nanoparticles was studied, including the effect of naturally occurring species (sulfate, silica, calcium magnesium, dissolved organic matter, bicarbonate, iron, and phosphate) on adsorption. CONCLUSION: The model accurately predicts adsorption to magnetite nanoparticles used in a batch process to remove arsenic from spiked Houston, TX tap water, and contaminated Brownsville, TX groundwater.

Adsorption of arsenic to magnetite nanoparticles: effect of particle concentration, pH, ionic strength, and temperature.

Little work has been conducted on the adsorption of arsenic to the mixed iron [Fe(II)/(III)] oxide magnetite and the effect that environmental parameters, such as pH, ionic strength, and temperature, have on adsorption. Magnetite nanoparticles are unique because of their affinity for both arsenate and arsenite and increased adsorption capacity from their bulk counterparts. This article shows the effect of various magnetite nanoparticle concentrations on arsenic adsorption kinetics. The adsorption data show the ability of the magnetite nanoparticles to remove arsenate and arsenite from solution in both synthetic and natural waters, and the data fit a first-order rate equation. Because of the increased surface area of these particles, less than 1 g/L of magnetite nanoparticles was needed. The results suggest that arsenic adsorption to the nanoparticles was not significantly affected by the pH, ionic strength and temperature in the ranges tested, which are typical of most potable water sources.

Resistant desorption of hydrophobic organic contaminants in typical chinese soils: implications for long-term fate and soil quality standards.

Soil contamination is an enormous problem in China and severely threatens environmental quality and food safety. Establishing realistic soil quality standards is important to the management and remediation of contaminated sites and must be based on thorough understanding of contaminant desorption from soil. In the present study, we evaluated sorption and desorption behaviors of naphthalene, phenanthrene, atrazine, and lindane (four common soil contaminants in China) in two of the most common Chinese soils. The desorption of these compounds exhibited clear biphasic pattern-a fraction of contaminants in soil was much less available to desorption and persisted much longer than what was predicted with the conventional desorption models. The unique thermodynamic characteristics associated with the resistant-desorption fraction likely have important implications for the mechanism(s) controlling resistant desorption. Experimental observations in the present study are consistent with our previous work with chlorinated compounds and different adsorbents and could be well modeled with a biphasic desorption isotherm. We therefore suggest that more accurate biphasic desorption models should be used to replace the conventional linear sorption/desorption model that is still widely adopted worldwide in contaminant fate prediction and soil quality standard calculations.

Release of adsorbed polycyclic aromatic hydrocarbons under cosolvent treatment: implications for availability and fate.

During laboratory and field studies, a fraction of contaminants in soils or sediments often is observed to be highly resistant to desorption. This desorption-resistant fraction may have significant effects on long-term fate and exposure of soil/ sediment-bound contaminants in particular, causing much reduced availability and contaminant persistence. Previous work by many research groups has indicated that this nonideal desorption behavior could be better predicted with biphasic desorption models. The present study further investigated the release of naphthalene and phenanthrene from sediments during and after cosolvent treatment. Experimental results indicate that release of these two compounds under cosolvent conditions can be accurately predicted with a previously developed, biphasic desorption model when the solubility enhancement effect of cosolvent is accounted for using standard activity coefficient ratios. In addition, desorption of the residual contaminants after cosolvent treatment follows the original biphasic desorption model very well, suggesting that cosolvent treatment increases only the aqueous solubility and has little effect on the nature of the desorption-resistant fraction and that cosolvent desorption is a valuable analytical tool for quickly measuring the magnitude of the desorption-resistant fraction. The present findings might have important implications for the mechanisms controlling resistant desorption of hydrophobic organic compounds and for predicting the availability and long-term fate of contaminants in soils and sediments.

Adsorption and precipitation of an aminoalkylphosphonate onto calcite.

The mechanism of nitrilotris(methylenephosphonic acid) (H6NTMP)/calcite reaction was studied with a large number of batch experiments where phosphonic acid was neutralized with 0 to 5 equivalents of NaOH per phosphonic acid and the concentration ranged from about 10 nmol/L to 1 mol/L. It is proposed that the phosphonate/calcite reactions are characterized in three steps. At low phosphonate concentration (<1 micromol/L NTMP concentration), the phosphonate/calcite reaction can be characterized as a Langmuir isotherm. At saturation, only approximately 7% of the calcite surface is covered with phosphonate; presumably these are the kinks, step edges, or other imperfect sites. At higher phosphonate concentrations, the attachment is characterized by calcium phosphonate crystal growth to a maximum of four to five surface layer thick, with solid phase stoichiometry of Ca(2.5)HNTMP and a constant solubility product of 10(-24.11). After multiple layers of phosphonate are formed on the calcite surface, the solution is no longer at equilibrium with calcite. Further phosphonate retention is probably due to mixed calcium phosphonate solid phase formation at lower pH and depleted solution phase Ca conditions. The proposed mechanism is consistent with phosphate/calcite reaction and can be used to explain the fate of phosphonate in brines from oil producing wells and the results are compared with two oil wells.

A program for evaluating dual-equilibrium desorption effects on remediation.

Desorption is one of the most critical processes affecting the effectiveness of soil and ground water remediation. None of the currently adopted desorption models can accurately quantify desorption of low-hydrophobicity organic chemicals, and thus could potentially mislead remediation design and decision-making. A recently developed dual-equilibrium desorption (DED) model was found to be much more accurate in quantifying desorption. A screening-level transport model, DED-Transport, was developed to simulate the DED effect on behaviors of organic contaminant plumes during remediation. DED-Transport requires only simple parameters, but is applicable to many remediation scenarios. DED-Transport can be used as a decision-support tool in site remediation to more precisely predict the time required for cleanup.

Critical evaluation of desorption phenomena of heavy metals from natural sediments.

In natural sediments, the majority of heavy metal ions are generally associated with the solid phase. To become bioavailable, the metal ions must desorb from the solid. Numerous studies of heavy metals in sediments have suggested that sorption and desorption exhibit hysteresis (i.e., the two processes are not reversible), while other studies have suggested that desorption hysteresis does not exist. In this study, sorption/desorption hysteresis of lead (Pb) and cadmium (Cd) was evaluated over the following range of conditions: (i) desorption induced by replacing the supernatant liquid with contaminant-free electrolyte solution; (ii) desorption induced by lowering the solution pH with mineral acid; and (iii) desorption induced by sequestration with EDTA. Given the importance of dissolved organic and inorganic ligands in regulating heavy metal behavior in nature sediments, sorption/desorption experiments were conducted on both untreated and prewashed sediments. Prewashing treatment increases the sorption potential of Cd but not Pb. Desorption hysteresis is observed in both the untreated and the prewashed sediments using the replaced supernatant method, and the desorption hysteresis appears to increase with aging time. Hysteresis is not observed when desorption is initiated by lowering the solution pH. A large fraction of the sorbed heavy metal ions can be easily desorbed by EDTA; between 0.04 and 1.2 mmol/kg Cd and Pb ions are resistant to desorption.