Low Surface Loading Research Articles

Face-dependent phosphate speciation on goethite: CD-MUSIC modeling and ATR-FTIR/2D-COS study

Understanding the face-dependent phosphate adsorption mechanisms and their variations with environmental conditions is of great significance for revealing phosphate adsorption mechanisms on various goethites and predicting phosphorus speciation in iron-rich soils. In this study, micro- (MicroGoe) and nano-sized goethite (NanoGoe) were synthesized and used to investigate the face-dependent adsorption behaviors of proton and phosphate on goethite by combining the charge distribution-multisite surface complexation (CD-MUSIC) model and attenuated total reflectance Fourier transform infrared (ATR-FTIR). The results demonstrated that MicroGoe had a higher charge density and phosphate adsorption capacity than NanoGoe, which could be attributed to the higher site density of ≡FeOH−0.5 and inner-layer capacitance arising from a higher proportion of capping face and rougher surface of MicroGoe. The logKH of ≡FeOH−0.5 on the main and capping face was 8.2 and 8.9, respectively. Three types of monodentate mononuclear phosphate complexes in different protonated states were identified, along with the non-protonated bidentate complex. Protonated monodentate complexes were formed at relatively low pH and high surface loadings, whereas non-protonated complexes were the predominant species at intermediate to high pH. MicroGoe had a higher percentage of monodentate complexes than NanoGoe, and both goethites had considerably lower phosphate adsorption on the capping face than on the main face. The results provide valuable insights into the interfacial reactivity of goethite prepared with various methods and facilitate further prediction of phosphorus speciation and availability in iron-rich soils.

Evaluation and sizing of proprietary sedimentation devices for decentralised stormwater treatment.

Suspended solids removal is a key performance measure for proprietary stormwater treatment devices. Various technologies are available, with manufacturers claiming hydrodynamic separators offer performance advantages. However, it is important to assess manufacturers' claims. Accordingly, this study seeks to compare the performance of proprietary devices, by applying dimensional analysis to third-party certification data and experimental data from uncertified devices, and to determine the accuracy of a single parameter estimation (Hazen or Péclet number) of removal efficiency. Statistical analysis indicates that device performance is well described by a single parameter estimation transitioning from Hazen (Nash-Sutcliffe coefficient = 0.81 and root mean square error = 5.1%) at low surface loading rates (SLR) in all technology types (high removal efficiency) to Péclet (Nash-Sutcliffe coefficient = 0.5 to 0.61 and root mean square error = 5.9% to 4.3%) at higher SLR (low removal efficiency) for hydrodynamic separators. This indicates that performance at low SLR is well explained by gravity separation in all technology types, whilst in hydrodynamic separators removal at high SLR is better explained by gravity separation plus advection. Consequently, when high (>80%) removal efficiency is required there is no performance advantage between technology types. However, when low (<50%) removal efficiency is required hydrodynamic separators offer a 33% increase in treatment area.

Impact of immobilization strategies on the activity and recyclability of lipases in nanomagnetic supports

The use of enzymes immobilized on nanomagnetic supports has produced surprising results in catalysis, mainly due to the increase in surface area and the potential for recovery and reuse. However, the meticulous control of the process and difficulties in reproducibility have made industrial-scale applications unfeasible. Furthermore, the role of conjugation strategies in the catalytic activity and recycling of catalysts is unclear. Therefore, the objective of this study was to compare the conjugation of enzymes on nanomagnetic supports through physical adsorption (naked) or covalent bonding with mercaptopropyltrimethoxysilane (MPTS) and aminopropyltriethoxysilane (APTS) ligands. The free lipase obtained from Rhizomucor miehei was used as a model enzyme. Total protein and enzyme activity were determined using spectrophotometry (UV–Vis) and the p-nitrophenyl palmitate (p-NPP) hydrolysis method. The results indicated that a more significant enzyme surface loading does not always mean better immobilization success. The physical adsorption binding strategy had higher surface loading and low catalytic activity. On the other hand, covalent coupling with free NH2 had an excellent catalytic activity with very low surface loading. Finally, we show that recyclability can be improved with conjugation mediated by disulfide bonds. The findings presented here are essential for developing nanoconjugates with high enzymatic activity, which can guarantee the success of several industrial applications.

The role of clay content and mineral surface area for soil organic carbon storage in an arable toposequence

Correlations between organic carbon (OC) and fine mineral particles corroborate the important role of the abundance of soil minerals with reactive surfaces to bind and increase the persistence of organic matter (OM). The storage of OM broadly consists of particulate and mineral-associated forms. Correlative studies on the impact of fine mineral soil particles on OM storage mostly combined data from differing sites potentially confounded by other environmental factors. Here, we analyzed OM storage in a soil clay content gradient of 5–37% with similar farm management and mineral composition. Throughout the clay gradient, soils contained 14 mg OC g−1 on average in the bulk soil without showing any systematic increase. Density fractionation revealed that a greater proportion of OC was stored as occluded particulate OM in the high clay soils (18–37% clay). In low clay soils (5–18% clay), the fine mineral-associated fractions had up to two times higher OC contents than high clay soils. Specific surface area measurements revealed that more mineral-associated OM was related to higher OC loading. This suggests that there is a potentially thicker accrual of more OM at the same mineral surface area within fine fractions of the low clay soils. With increasing clay content, OM storage forms contained more particulate OC and mineral-associated OC with a lower surface loading. This implies that fine mineral-associated OC storage in the studied agricultural soils was driven by thicker accrual of OM and decoupled from clay content limitations.

Hausmannite as potential As(V) filter. Macroscopic and spectroscopic study of As(V) adsorption and desorption by citric acid

Arsenic (As) is a toxic element that leads the list of human health threats and is one of the priority contaminants in soil and water. In order to remove As(V) and/or reduce its mobility, filters and amendments with high affinity for As(V) adsorption are used in drinking water treatment or directly applied to the soil, thereby promoting its immobilization. Hausmannite and hematite were compared by in-situ Attenuated Total Reflection - Fourier Transform Infrared (ATR-FTIR) spectroscopy and batch experiments for evaluating As(V) adsorption and sequential desorption by citrate. The pH and contact time were used as variables. Hausmanite adsorbed more As(V) than hematite. As(V) was adsorbed on the mineral surface of simultaneously inner- and outer-sphere species. Inner-sphere bidentate complex form preferentially at high pH, early adsorption time and low surface loading, while the monodentate species should be responsible to increase total As(V) adsorption at low pH, later adsorption kinetics and higher As(V) surface loading. Citrate was effective in causing As(V) desorption at higher citric acid concentrations and higher pH values. After a long time of incubation, the neogenesis of a manganite by hausmnannite oxidation was observed. Concomitantly, less As(V) was desorbed by citrate desorption, even in the presence of high citric acid concentrations. Hausmannite was an efficient mineral for As(V) removal and immobilization.

Adsorption mechanism of alkyl hydroxamic acid onto bastnäsite: Fundamental steps toward rational collector design for rare earth elements

Rare earth element (REE) production is limited in part by inefficient strategies for beneficiation. Hydroxamic acid ligands are promising reagents for the selective flotation of bastnäsite [(Ce,La)FCO3], a major REE ore mineral, but the mechanism and energetics of adsorption are not understood, interfering with the design of new, more efficient reagents. Here, the adsorption of octyl hydroxamic acid onto bastnäsite was measured using a combination of experimental and computational methods. In-situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy revealed changes in the hydroxamate functional group vibrational frequencies, corresponding to chelation with cerium cations at the bastnäsite surface. The results indicate a monodentate chemisorption mechanism at low surface loading that changes to bidentate chemisorption at higher concentrations. This interpretation is supported by molecular vibrational frequency shifts calculated using density functional theory (DFT), and orientation of the hydrocarbon chain measured by sum frequency generation (SFG) vibrational spectroscopy. The binding enthalpies of octyl hydroxamic acid interacting with La and Ce-bastnäsite surfaces were measured using isothermal titration calorimetry (ITC) revealing a stronger coordinating ability with bastnäsite than with a common gangue mineral, calcite (CaCO3). Because octyl hydroxamate favors monodentate adsorption at low surface coverages, the relative chelating strength of metal ions could be a poor predictor for selectivity under monolayer adsorption conditions. At higher surface loadings, where the bidentate mode of adsorption is active, selectivity is likely to be limited by increased flotation of gangue ores.

Enzyme immobilization on protein-resistant PNIPAAm brushes: impact of biotin linker length on enzyme amount and catalytic activity.

Thermoresponsive poly(N-isopropylacrylamide) (PNIPAAm) brushes with terminal click functionality can be used to selectively immobilize enzymes. Exploiting their inherent protein-repellent and thus non-fouling properties, surfaces with specific bioactivity can be created in this way. This report describes the functionalization of alkyne-PNIPAAm brushes with two biotin linkers of different poly(ethylene glycol) (PEG) spacer length via click chemistry and the subsequent immobilization of streptavidin-conjugated horseradish peroxidase (SA-HRP) by the strong interaction between biotin and streptavidin. Spectroscopic ellipsometry is used to quantify the biotin and the SA-HRP amount on the PNIPAAm brushes. Enzyme activities are determined by UV‑vis spectroscopy. A better accessibility to the alkyne-functionalized chain ends for the short biotin-PEG3 linker leads to a higher biotin amount on these PNIPAAm brushes, which in turn results in higher SA‑HRP amounts on biotin-PEG3-modified brushes in the swollen (20 °C) and collapsed state (37 °C) compared to biotin-PEG23-modified ones. For both linkers, an increased immobilization temperature leads to higher SA-HRP amounts due to an enhanced reaction kinetics and mobility. All immobilized SA-HRP amounts are in range of 81-98% monolayer coverage, except for SA-HRP immobilized on biotin-PEG23-modified PNIPAAm brushes at 20 °C, exhibiting only 43% monolayer coverage. A high mobility of the biotin linker combined with a low surface loading of SA-HRP is found to be beneficial for the activity of SA-HRP. Hence, the highest specific activity as measured by HRP-catalyzed 3,3´,5,5´‑tetramethylbenzidine (TMB) oxidation is found for a low SA-HRP amount on biotin-PEG23-modified brushes.

Recovery of particulate matter from a high-rate moving bed biofilm reactor by high-rate dissolved air flotation

Abstract High-rate biological wastewater treatment processes for carbon recovery are able to improve the energy balance and carbon footprint of water resource recovery facilities. Combination of a high-rate moving bed biofilm reactor (HR-MBBR) with a rapid flotation (HR-DAF), as a replacement for the ‘A stage’ of the A-B process, can achieve this objective. The main goal of this study was to maximize the capture of biodegradable particulate matter from an HR-MBBR effluent by an HR-DAF. A pilot-scale HR-DAF process was operated downstream of an HR-MBBR treating screened municipal wastewater. The particulate biodegradable matter recovery was evaluated by determining the total suspended solids (TSS) removal efficiency. TSS recovery in experiments without chemicals at low surface loading rates (&amp;lt;15 m/h) and high recycle ratio (&amp;gt;25%) was 94 ± 1%. By using a tannin-based polymer, the solids capture efficiency of the HR-DAF was slightly improved with TSS recovery reaching 96 ± 1% at a high SLR (at least 22 m/h) and low recycle ratio (14%). The anaerobic biodegradability of the tannin tested was determined to be 17%. The HR-DAF process downstream of an HR-MBBR gave a very good particulate matter recovery that offers a promising alternative to the A-B process for carbon recovery.

Identification of Bernalite Transformation and Tridentate Arsenate Complex at Nano-goethite under Effects of Drying, pH and Surface Loading

The structural configuration of arsenate on iron (hydr)oxide determines its leachability and bioavailability in the soil environment. It is important to understand how the stability of iron hydroxide and the structural configuration of arsenate complexes vary in response to changes in environmental conditions. Therefore, we investigated the effects of drying, pH and surface loadings on the stability of goethite and the structural configuration of arsenate through batch experiments and TEM and XAS measurements with DFT calculation. As a result, we observed no significant transformation of goethite under most conditions, but TEM confirmed the partial formation of bernalite in the presence of arsenate at a pH of 10, and the bernalite showed 2.18 times higher arsenate sorption than the goethite. The linear combination fitting of the EXAFS spectra with DFT calculations revealed that tridentate and bidentate complexes were dominant under low surface loading and pH conditions in the sedimented samples, while monodentate complexes were abundant under high surface loading and pH conditions. Based on our results, we conclude that the formation of arsenic-rich colloids could account for mobilization in the soil environment, and the density of available sorption sites combined with the concentration of solute could cause the change in structural configuration.

The effect of electron competition on chromate reduction using methane as electron donor.

We studied the effect of electron competition on chromate (Cr(VI)) reduction in a methane (CH4)-based membrane biofilm reactor (MBfR), since the reduction rate was usually limited by electron supply. A low surface loading of SO42- promoted Cr(VI) reduction. The Cr(VI) removal percentage increased from 60 to 70% when the SO42- loading increased from 0 to 4.7mgSO42-/m2-d. After the SO42- loading decreased back to zero, the Cr(VI) removal further increased to 90%, suggesting that some sulfate-reducing bacteria (SRB) stayed in the reactor to reduce Cr(VI). However, a high surface loading of SO42- (26.6mgSO42-/m2-d) significantly slowed down the Cr(VI) reduction to 40% removal, which was probably due to competition between Cr(VI) and SO42- reduction. Similarly, when 0.5mg/L of Se(VI) was introduced into the MBfR, Cr(VI) removal percentage slightly decreased to 60% and then increased to 80% when input Se(VI) was removed again. The microbial community strongly depended on the loadings of Cr(VI) and SO42-. In the sulfate effect experiment, three genera were dominant. Based on the correlation between the abundances of the three genera and the loadings of Cr(VI) and SO42-, we conclude that Methylocystis, a type II methanotroph, reduced both Cr(VI) and sulfate, Meiothermus only reduced Cr(VI), and Ferruginibacter only reduced SO42-.

Irreversibility of sorption of cobalt to goethite (α-FeOOH) and disparities in dissolution of aged synthetic Co-goethite

The behaviours of incorporated cobalt in goethite during desorption and dissolution is fundamental to our understanding of the best extraction techniques for maximum cobalt recovery. Here, Surface Complexation Modelling, desorption and dissolution of aged synthetic Co-goethite was investigated to demonstrate the transition between surface complexion, surface precipitation and structural incorporation in goethite with different amounts of cobalt found in oxic laterites. Surface Complexation Modelling of cobalt sorption on goethite reveals existence of both surface complexation and polynuclear complexes. Surface complexation starts at a low surface loading (≥0.004wt% Co) to form Fe(OH)2Co, and as uptake (0.03 to 0.2wt% Co) increases, two surfaces complexes, Fe(OH)2Co and (>FeOH)2Co, are formed. Additional increases in concentration (0.45 to 1.7wt%) leads to the formation of poly-nuclear complexes (e.g., (>FeOH)3Co2) co-existing with other complexes. Structural incorporation would be manifest if Co sorption was irreversible. We find that after four weeks of sorption about 55 to 70% of cobalt is reversible and the retention capacity increases with decreasing concentration. Samples formed at low loading show strong evidence of structural incorporation relative to those formed at high loading. In particular, the sample with 0.004wt% Co needs a 20% dissolution of goethite before 64% of its incorporated cobalt is released while samples with 1.74wt% Co requires a dissolution of 7.8% of goethite before liberating 66% of adsorbed cobalt. All the grades of Co-goethite dissolves incongruently with iron, however, the mode of formation should be considered when determining the leaching conditions for maximum recovery. In addition, the mixed Co-goethite grades show strong deviation from congruent dissolution and have a negative effect on the amount of cobalt and iron released during extraction.

Effects of surface structural disorder and surface coverage on isotopic fractionation during Zn(II) adsorption onto quartz and amorphous silica surfaces

Metal ion-mineral surface interactions and the attendant isotopic fractionation depend on the properties of the mineral surface and the local atomic-level chemical environment. However, these factors have not been systematically examined for phases of the same composition with different levels of surface disorder. We present pH-dependent adsorption edges, X-ray absorption spectra, and isotopic measurements to illustrate the effects of surface structural disorder and surface coverage on zinc(II) (Zn(II)) surface complexation and isotope fractionation. Our results demonstrate that Zn(II) surface complexes on quartz and amorphous silica (SiO2(am)) transition from octahedral to tetrahedral coordination by oxygen as surface coverage increases. In low ionic strength solutions (I=0.004M) and at low surface loadings (Γ<0.6μmolm−2), Zn(II) adsorbs to the quartz surface predominantly as outer-sphere octahedral complexes (RZn-O=2.05Å) with no significant isotopic fractionation (Δ66/64Znaqueous-sorbed=−0.01±0.06‰) from aqueous Zn(II). In contrast, under similar chemical conditions and surface loading, outer-sphere Zn(II) adsorption complexes are not observed on SiO2(am) surfaces. At high ionic strength (I=0.1M) and low surface loading (Γ<0.2μmolm−2), inner-sphere, monodentate octahedral Zn(II) complexes (RZn-O=2.05–2.07Å) are observed on both quartz and SiO2(am) surfaces. At the same ionic strength (I=0.1M) and higher surface loading (Γ=0.6–1.4μmolm−2), Zn(II) forms inner-sphere, monodentate tetrahedral complexes (RZn-O=1.98Å) at the quartz surface. On the SiO2(am) surface under similar chemical conditions and surface loading, Zn(II) forms dominantly inner-sphere, monodentate tetrahedral complexes with shorter ZnO bond distances (RZn-O=1.94Å). Despite different coordination numbers, the measured equilibrium isotope fractionation factors for inner-sphere octahedral and tetrahedral complexes versus dissolved Zn, under the same conditions and on the same silica substrate, are not distinguishable beyond uncertainties. However, there is a larger measured equilibrium isotope fractionation with preferential sorption of heavy Zn as inner-sphere complexes on SiO2(am) (Δ66/64Znaqueous-sorbed=−0.94±0.11‰) than on quartz (Δ66/64Znaqueous-sorbed=−0.60±0.11‰).The propensity for Zn(II) to occur in tetrahedral and octahedral coordination with oxygen may help explain these observations. We posit that the low energetic difference between octahedral and tetrahedral Zn(II) may be why changes in inner-sphere Zn(II) coordination numbers with increasing coverage do not manifest as distinguishable isotope fractionations or asan observable alteration to the macroscopic sorption edges. Thus, we attribute the larger magnitude of Zn isotope fractionation on SiO2(am) compared to quartz to differences in the bonding environments on the two types of silica surfaces rather than to a change in the coordination number of Zn(II).

Characteristic comparison of heavy metal contamination between road-deposited and roof-deposited sediments in suburban area.

Surface-deposited sediment in urban area is an essential environmental medium for assessing heavy metal contamination. A total of 10 sampling trips were conducted to collect road-deposited and roof-deposited sediments for the comparison of nickel (Ni), copper (Cu), cadmium (Cd), lead (Pb), zinc (Zn), and chromium (Cr) contamination characteristics. Results indicated that roof sediment appeared to have a finer size distribution than road sediments. Roof sediment indicated higher metal concentration and lower surface loading than road sediment. The impact of particle size on heavy metal contamination was quantified by using the developed pioneering term of finer particle effect factor; it differed according to surface types and grain size fraction. Particles in individual grain size fraction showed different contribution to the surface loading for bulk sediments. No consistent trend was found for the grain size fraction loading along with grain size for the studied heavy metals for road sediments. In contrast, an asymmetric "W" trend was observed for the roof sediments, and it had the following results: Fraction of <63 and 250-500μm showed higher loading, while fraction of 90-125 and >850μm indicated the smaller loading. Findings above facilitated the appropriate management practice selection for the treatment of surface-deposited sediments.

Energy and Electron Transfer Cascade in Self-Assembled Bilayer Dye-Sensitized Solar Cells.

Current high efficiency dye-sensitized solar cells (DSSCs) rely on the incorporation of multiple chromophores, via either codeposition or preformed assemblies, as a means of increasing broad band light absorption. These strategies have some inherent limitations including decreased total light absorption by each of the dyes, low surface loadings, and complex synthetic procedures. In this report, we introduce an alternative strategy, self-assembled bilayers, as a simple, stepwise method of incorporating two complementary chromophores into a DSSC. The bilayer devices exhibit a 10% increase in Jsc, Voc, and η over the monolayer devices due to increased incident photon-to-electron conversion efficiency across the entire visible spectrum and slowed recombination losses at the interface. Directional energy and electron transfer toward the metal oxide surface are key steps in the bilayer photon-to-current generation process. These results are important as they open the door to a new architecture for harnessing broadband light in dye-sensitized devices.

Hairpin DNA-functionalized gold nanorods for mRNA detection in homogenous solution.

We report a fluorescent probe for mRNA detection. It consists of a gold nanorod (GNR) functionalized with fluorophore-labeled hairpin oligonucleotides (hpDNA) that are complementary to the mRNA of a target gene. This nanoprobe was found to be sensitive to a complementary oligonucleotide, as indicated by significant changes in both fluorescence intensity and lifetime. The influence of the surface density of hpDNA on the performance of this nanoprobe was investigated, suggesting that high hybridization efficiency could be achieved at a relatively low surface loading density of hpDNA. However, steady-state fluorescence spectroscopy revealed better overall performance, in terms of sensitivity and detection range, for nanoprobes with higher hairpin coverage. Time-resolved fluorescence lifetime spectroscopy revealed significant lifetime changes of the fluorophore upon hybridization of hpDNA with targets, providing further insight on the hybridization kinetics of the probe as well as the quenching efficiency of GNRs.

Adsorption characteristics of Direct Red 23 azo dye onto powdered tourmaline

The high electric field on the surface of tourmaline particles has a potential of enhancing electrostatic reactions during adsorption. However, information concerning the adsorption characteristics of dyes onto tourmaline is currently unavailable. In the present study, the behavior and efficiency of powdered tourmaline (PT) in removing the diazo Direct Red 23 (DR23) dye from aqueous solution were investigated. The observations from batch adsorption experiments indicated that the adsorption was more favorable under low adsorbate surface loading, low pH, high temperature, and low ionic strength conditions. A homogeneous particle diffusion model (HPDM) was used to characterize the process, and the rate of adsorption was found to be controlled by intra-particle diffusion. An activation energy of 4.54kcal/mol was calculated, suggesting that the adsorption proceeded with a low energy barrier and that a physisorption was involved. The functional groups binding anionic DR23 on the PT particles were also identified. A maximum adsorption capacity of 153mg/g was determined according to the Langmuir isotherm. The PT was subjected to a total of 5 regeneration runs without losing much of its dye-adsorption capacities. Due to its low price, abundant availability, and superb adsorption capacity, PT has a great potential for use as an effective adsorbent in removing DR23 from aqueous solutions.

Effect of plants and surface loading rate on the treatment efficiency of shallow subsurface constructed wetlands

The aim of this research was to study the influence of the presence of plants and of plant species on the treatment efficiency of shallow (0.3m effective depth) horizontal subsurface flow constructed wetlands (CWs) treating diluted municipal wastewater. The pilot plant was situated in A Coruña (Spain) and constituted of five CW units in parallel: CW1 (unplanted), CW2 (Juncus effusus) CW3 (Iris pseudacorus), CW4 (Typha latifolia L.) and CW5 (Phragmites australis). A long term study (from October 2009 to March 2012) was carried out with five monitoring campaigns during the two first years of operation at low surface loading rate (SLR, 2.5g BOD5/m2d on average) and two monitoring campaigns during the third year at design SLR (4.7g BOD5/m2d on average). At low SLR rate, significant differences between units were not found for TSS (89–93%), COD (83–88%) or BOD5 (90–95%) percentage removal which, in turn, appeared at design SLR, when BOD5 removal decreased to 78% (CW1), 69% (CW4), 87% (CW2), 86% (CW3) and 94% (CW5). Thus, the effect of plants on the removal efficiency of organic matter (COD, BOD5) appeared to be dependent on the loading rate. CW2 reached the highest nitrogen removal, followed by CW4, CW5 and CW3 at a similar level and, finally, by CW1. Results indicate that the additional nitrogen removal rate in planted units increased with plant biomass productivity which also determined evapotranspiration variability between units. Typha latifolia L. appeared to be the most sensitive species to adverse conditions.

Fe-Impregnated Mineral Colloids for Peroxide Activation: Effects of Mineral Substrate and Fe Precursor

Heterogeneous iron species at the mineral/water interface are important catalysts for the generation of reactive oxygen species at circumneutral pH. One significant pathway leading to the formation of such species arises from deposition of dissolved iron onto mineral colloids due to changes in redox conditions. This study investigates the catalytic properties of Fe impregnated on silica, alumina, and titania nanoparticles (as prototypical mineral colloids). Fe impregnation was carried out by immersing the mineral nanoparticles in dilute Fe(II) or Fe(III) solutions at pH 6 and 3, respectively, in an aerobic environment. The uptake of iron per unit surface area follows the order of nTiO2 > nAl2O3 > nSiO2 for both types of Fe precursors. Impregnation of mineral particles in Fe(II) solutions results in predominantly Fe(III) species due to efficient surface-mediated oxidation. The catalytic activity of the impregnated solids to produce hydroxyl radical (·OH) from H2O2 decomposition was evaluated using benzoic acid as a probe compound under dark conditions. Invariably, the rates of benzoic acid oxidation with different Fe-laden particles increase with the surface density of Fe until a critical density above which the catalytic activity approaches a plateau, suggesting active Fe species are formed predominantly at low surface loadings. The critical surface density of Fe varies with the mineral substrate as well as the aqueous Fe precursor. Fe impregnated on TiO2 exhibits markedly higher activity than its Al2O3 and SiO2 counterparts. The speciation of interfacial Fe is analyzed with diffuse reflectance UV-vis analysis and interpretation of the data in the context of benzoic oxidation rates suggests that the surface activity of the solids for ·OH generation correlates strongly with the isolated (i.e., mononuclear) Fe species. Therefore, iron dispersed on mineral colloids is a significant form of reactive iron surfaces in the aquatic environment.

A novel solid-state NMR method for the investigation of trivalent lanthanide sorption on amorphous silica at low surface loadings.

The modelling of radionuclide transport in the subsurface depends on a comprehensive understanding of their interactions with mineral surfaces. Spectroscopic techniques provide important insight into these processes directly, but at high concentrations are sometimes hindered by safety concerns and limited solubilities of many radionuclides, especially the actinides. Here we use Eu(iii) as a surrogate for trivalent actinide species, and study Eu(iii) sorption on the silica surface at pH 5 where sorption is fairly limited. We have applied a novel, surface selective solid-state nuclear magnetic resonance (NMR) technique to provide information about Eu binding at the silica surface at estimated surface loadings ranging from 0.1 to 3 nmol m(-2) (<0.1% surface loading). The NMR results show that inner sphere Eu(iii) complexes are evenly distributed across the silica surface at all concentrations, but that at the highest surface loadings there are indications that precipitates may form. These results illustrate that this NMR technique may be applied in solubility-limited systems to differentiate between adsorption and precipitation to better understand the interactions of radionuclides at solid surfaces.

The impact of particle size on the adsorption of citrate to hematite

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.