Novel, bio-based, photoactive arsenic sorbent: TiO2-impregnated chitosan bead

A novel sorbent for arsenic, TiO₂-impregnated chitosan bead (TICB), has been synthesized and successfully tested. Kinetic plots, pH dependence, isotherm data, and bead morphology are reported. Equilibrium is achieved after 185 h in batch experiments with exposure to UV light. The TICB system performs similarly to the mass equivalent of neat TiO₂ nanopowder. The point of zero charge (pzc) for TICB was determined to be 7.25, and as with other TiO₂-based arsenic removal technologies, the optimal pH range for sorption is below this pH_pzc. Without exposure to UV light, TICB removes 2198 μg As(III)/g TICB and 2050 μg As(V)/g TICB. With exposure to UV light, TICB achieves photo-oxidation of As(III) to As(V), the less toxic and more easily sequestered arsenic form. UV irradiation also results in enhanced arsenic removal, reaching sorption capacities of 6400 μg As/g TICB and 4925 μg As/g TICB, where arsenic is initially added as As(III) and As(V), respectively. Because the TICB system obviates filtration post-treatment, TICB is superior to TiO₂ nanopowder from the perspective of implementation for decentralized water treatment.     

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

The effect of Zn²⁺ 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 Zn²⁺ in the solution. With less than 3 mg/L of Zn²⁺ 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 Zn²⁺. The adsorption-enhancement effect of Zn²⁺ 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 Zn²⁺ cannot be due to reduced negative charge of the magnetite nanoparticles surface by zinc adsorption. Other cations, such as Ca²⁺ 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 Zn²⁺ due to the formation of a ternary complex.     

Anchorage of iron hydro(oxide) nanoparticles onto activated carbon to remove As(V) from water

The adsorption of arsenic (V) by granular iron hydro(oxides) has been proven to be a reliable technique. However, due to the low mechanical properties of this material, it is difficult to apply it in full scale water treatment. Hence, the aim of this research is to develop a methodology to anchor iron hydro(oxide) nanoparticles onto activated carbon, in which the iron hydro(oxide) nanoparticles will give the activated carbon an elevated active surface area for arsenic adsorption and also help avoid the blockage of the activated carbon pores. Three activated carbons were modified by employing the thermal hydrolysis of iron as the anchorage procedure. The effects of hydrolysis temperature (60-120 °C), hydrolysis time (4-16 h), and FeCl₃ concentration (0.4-3 mol Fe/L) were studied by the surface response methodology. The iron content of the modified samples ranged from 0.73 to 5.27%, with the higher end of the range pertaining to the carbons with high oxygen content. The materials containing smaller iron hydro(oxide) particles exhibited an enhanced arsenic adsorption capacity. The best adsorbent material reported an arsenic adsorption capacity of 4.56 mg As/g at 1.5 ppm As at equilibrium and pH 7.     

Removal of arsenic from water: Effects of competing anions on As(III) removal in KMnO4–Fe(II) process

Effects of sulfate, phosphate, silicate and humic acid (HA) on the removal of As(III) in the KMnO₄–Fe(II) process were investigated in the pH range of 4–9 with permanganate and ferrous sulfate applied at selected dosage. Sulfate decreased the removal of arsenic by 6.5–36.0% at pH 6–9 and the decrease in adsorption did not increase with increasing concentration of sulfate from 50 to 100 mg/L. In the presence of 1 mg/L phosphate, arsenic removal decreased gradually as pH increased from 4 to 6, and a sharp drop occurred at pH 7–9. The presence of 10 mg/L silicate had negligible effect on arsenic removal at pH 4–5 whereas decreased the arsenic removal at pH 6–9 and the decrease was more significant at higher pH. The presence of HA dramatically decreased the arsenic removal over the pH range of 6–9 and HA of higher concentration resulted in greater drop in arsenic removal. The effects of the competing anions on arsenic removal in the KMnO₄–Fe(II) process were highly dependent on pH and the degree of these four anions influencing As(III) removal decreased in the following order, phosphate > humic acid > silicate > sulfate. Sulfate differed from the other three anions because sulfate decreased the removal of arsenic mainly by competitive adsorption while phosphate, silicate and HA decreased the removal of As(III) by competitive adsorption and sequestering the formation of ferric hydroxide derived from Fe(II).     

Removal of arsenic from water: Effect of calcium ions on As(III) removal in the KMnO4–Fe(II) process

A novel KMnO₄–Fe(II) process was developed in this study for As(III) removal. The optimum As(III) removal was achieved at a permanganate dosage of 18.6 μM. At the optimum dosage of permanganate, the KMnO₄–Fe(II) process was much more efficient than the KMnO₄–Fe(III) process for As(III) removal by 15–38% at pH 5–9. The great difference in As(III) removal in these two processes was not ascribed to the uptake of arsenic by the MnO₂ formed in situ but to the different properties of conventional Fe(III) and the Fe(III) formed in situ. It was found that the presence of Ca²⁺ had limited effects on As(III) removal under acidic conditions but resulted in a significant increase in As(III) removal under neutral and alkaline conditions in the KMnO₄–Fe(II) process. Moreover, the effects of Ca²⁺ on As(III) removal in the KMnO₄–Fe(II) process were greater at lower permanganate dosage when Fe(II) was not completely oxidized by permanganate. This study revealed that the improvement of As(III) removal at pH 7–9 in the KMnO₄–Fe(II) process by Ca²⁺ was associated with three reasons: (1) the specific adsorption of Ca²⁺ increased the surface charge; (2) the formation of amorphous calcium carbonate and calcite precipitate that could co-precipitate arsenate; (3) the introduction of calcium resulted in more precipitated ferrous hydroxide or ferric hydroxide. On the other hand, the enhancement of arsenic removal by Ca²⁺ under acidic conditions was ascribed to the increase of Fe retained in the precipitate. FTIR tests demonstrated that As(III) was removed as arsenate by forming monodentate complex with Fe(III) formed in situ in the KMnO₄–Fe(II) process when KMnO₄ was applied at 18.6 μM. The strength of the “non-surface complexed” As–O bonds of the precipitated arsenate species was enhanced by the presence of Ca²⁺ and the complexation reactions of arsenate with Fe(III) formed in situ in the presence or absence of Ca²⁺ were proposed.     

Adsorption of arsenic from a Nova Scotia groundwater onto water treatment residual solids

Water treatment residual solids were examined in batch adsorption and column adsorption experiments using a groundwater from Halifax Regional Municipality that had an average arsenic concentration of 43 μg/L (±4.2 μg/L) and a pH of 8.1. The residual solids studied in this paper were from five water treatment plants, four surface water treatment plants that utilized either alum, ferric, or lime in their treatment systems, and one iron removal plant. In batch adsorption experiments, iron-based residual solids and lime-based residual solids pre-formed similarly to GFH, a commercially-available adsorbent, while alum-based residual solids performed poorly. Langmuir isotherm modeling showed that ferric residuals had the highest adsorptive capacity for arsenic (Q_max = 2230 mg/kg and 42,910 mg/kg), followed by GFH (Q_max = 640 mg/kg), lime (Q_max = 160 mg/kg) and alum (Q_max = <1 mg/kg and 3 mg/kg). Similarly, the maximum arsenic removal was >93% for the ferric and lime residuals and GFH, while the maximum arsenic removal was <49% for the alum residuals under the same conditions. In a column adsorption experiment, ferric residual solids achieved arsenic removal of >26,000 bed volumes before breakthrough past 10 μg As/L, whereas the effluent arsenic concentration from the GFH column was under the method detection limit at 28,000 bed volumes. Overall, ferric and lime water treatment residuals were promising adsorbents for arsenic adsorption from the groundwater, and alum water treatment residuals did not achieve high levels of arsenic adsorption.     

As(III) removal by hydrous titanium dioxide prepared from one-step hydrolysis of aqueous TiCl4 solution

Hydrous titanium dioxide (TiO₂·xH₂O) nanoparticles were synthesized by a low-cost one-step hydrolysis process with aqueous TiCl₄ solution. These TiO₂·xH₂O nanoparticles ranged from 3 to 8 nm and formed aggregates with a highly porous structure, resulting in a large surface area and easy removal capability from aqueous environment after the treatment. Their effectiveness on the removal of As(III) (arsenite) from water was investigated in both laboratory and natural water samples. The adsorption capacity on As(III) of these TiO₂·xH₂O nanoparticles reached over 83 mg/g at near neutral pH environment, and over 96 mg/g at pH 9.0. Testing with a As(III) contaminated natural lake water sample confirmed the effectiveness of these TiO₂·xH₂O nanoparticles in removing As(III) from natural water. The high adsorption capacity of the TiO₂·xH₂O nanoparticles is related to the high surface area, large pore volume, and the presence of high affinity surface hydroxyl groups.     

Arsenic sorption on TiO2 nanoparticles: Size and crystallinity effects

Single solute As (III) and As (V) sorption on nano-sized amorphous and crystalline TiO₂ was investigated to determine: size and crystallinity effects on arsenic sorption capacities, possible As (III) oxidation, and the nature of surface complexes. Amorphous and crystalline nanoparticles were prepared using sol-gel synthesis techniques. For amorphous TiO₂, solute pH in the range of 4-9 had a profound impact on only As (V) sorption. As (III) and As (V) sorption isotherms indicated that sorption capacities of the different TiO₂ polymorphs were dependent on the sorption site density, surface area (particle size) and crystalline structure. When normalized to surface area, As (III) surface coverage on the TiO₂ surface remained almost constant for particles between 5 and 20 nm. However, As (V) surface coverage increased with the degree of crystallinity. X-ray absorption spectroscopic analysis provided evidence of partial As (III) oxidation on amorphous TiO₂ rather than crystalline TiO₂. The data also indicated that As (III) and As (V) form binuclear bidentate inner-sphere complexes with amorphous TiO₂ at neutral pH.     

Occurrence of arsenic in core sediments and groundwater in the Chapai-Nawabganj District, northwestern Bangladesh

Groundwater and core sediments of two boreholes (to a depth of 50 m) from the Chapai-Nawabganj area in northwestern Bangladesh were collected for arsenic concentration and geochemical analysis. Groundwater arsenic concentrations in the uppermost aquifer (10-40 m of depth) range from 2.8 μg L⁻¹ to 462.3 μg L⁻¹. Groundwater geochemical conditions change from oxidized to successively more reduced, higher As concentration with depth. Higher sediment arsenic levels (55 mg kg⁻¹) were found within the upper 40 m of the drilled core samples. X-ray absorption near-edge structure spectroscopy was employed to elucidate the arsenic speciation of sediments collected from two boreholes. Environmental scanning electron microscopy and transmission X-ray microscopy were used to investigate the characteristics of FeOOH in sediments which adsorb arsenic. In addition, a pH-Eh diagram was drawn using the Geochemist's Workbench (GWB) software to elucidate the arsenic speciation in groundwater. The dominant groundwater type is Ca-HCO₃ with high concentrations of As, Fe and Mn but low levels of NO₃⁻ and SO₄²⁻. Sequential extraction analysis reveals that Mn and Fe hydroxides and organic matter are the major leachable solids carrying As. High levels of arsenic concentration in aquifers are associated with fine-grained sediments. Fluorescent intensities of humic substances indicate that both groundwater and sediments in this arsenic hotspot area contain less organic matter compared to other parts of Bengal basin. Statistical analysis clearly shows that As is closely associated with Fe and Mn in sediments while As is better correlated with Mn in groundwater. These correlations along with results of sequential leaching experiments suggest that reductive dissolution of MnOOH and FeOOH mediated by anaerobic bacteria represents an important mechanism for releasing arsenic into the groundwater.     

Efficient removal of microcystin-LR by UV-C/H₂O₂ in synthetic and natural water samples

The destruction of the commonly found cyanobacterial toxin, microcystin-LR (MC-LR), in surface waters by UV-C/H₂O₂ advanced oxidation process (AOP) was studied. Experiments were carried out in a bench scale photochemical apparatus with low pressure mercury vapor germicidal lamps emitting at 253.7 nm. The degradation of MC-LR was a function of UV fluence. A 93.9% removal with an initial MC-LR concentration of 1 μM was achieved with a UV fluence of 80 mJ/cm² and an initial H₂O₂ concentration of 882 μM. When increasing the concentration of MC-LR only, the UV fluence-based pseudo-first order reaction rate constant generally decreased, which was probably due to the competition between by-products and MC-LR for hydroxyl radicals. An increase in H₂O₂ concentration led to higher removal efficiency; however, the effect of HO scavenging by H₂O₂ became significant for high H₂O₂ concentrations. The impact of water quality parameters, such as pH, alkalinity and the presence of natural organic matter (NOM), was also studied. Field water samples from Lake Erie, Michigan and St. Johns River, Florida were employed to evaluate the potential application of this process for the degradation of MC-LR. Results showed that the presence of both alkalinity (as 89.6-117.8 mg CaCO₃/L) and NOM (as ∼2 to ∼9.5 mg/L TOC) contributed to a significant decrease in the destruction rate of MC-LR. However, a final concentration of MC-LR bellow the guideline value of 1 μg/L was still achievable under current experimental conditions when an initial MC-LR concentration of 2.5 μg/L was spiked into those real water samples.     

Splitting tensile strength of concrete using ground granulated blast furnace slag and SiO2 nanoparticles as binder

In the present study, split tensile strength together with pore structure, thermal behavior and microstructure of concrete containing ground granulated blast furnace slag and SiO₂ nanoparticles have been investigated. Portland cement was replaced by different amounts of ground granulated blast furnace slag and the properties of concrete specimens were measured. Although it negatively impacts the properties of concrete at early ages, ground granulated blast furnace slag was found to improve the physical and mechanical properties of concrete up to 45 wt% at later ages. SiO₂ nanoparticles with the average particle size of 15 nm were partially added to concrete with the optimum content of ground granulated blast furnace slag and physical and mechanical properties of the specimens were studied. SiO₂ nanoparticle as a partial replacement of cement up to 3 wt% could accelerate C-S-H gel formation as a result of increased crystalline Ca(OH)₂ amount at the early age of hydration and hence increase split tensile strength of concrete specimens. The increased the SiO₂ nanoparticles’ content more than 3 wt% causes the reduced the split tensile strength because of the decreased crystalline Ca(OH)₂ content required for C-S-H gel formation. SiO₂ nanoparticles could improve the pore structure of concrete and shift the distributed pores to harmless and few-harm pores.     

Al2O3 nanoparticles in concrete and different curing media

In the present study, the effect of limewater on strength and percentage of water absorption of Al₂O₃ nanoparticles blended concrete has been investigated. Portland cement was partially replaced by Al₂O₃ nanoparticles with the average particle size of 15 nm with different amount and the specimens were cured in water and saturated limewater for specific ages. Utilizing up to 2.0 wt% Al₂O₃ nanoparticles could produce concrete with improved strength and water permeability when the specimens cured in saturated limewater while this content is 1.0 wt% for the specimens cured in tap water. The high action of fine nanoparticles substantially increases the quantity of C-S-H gel. Although the limewater reduces the strength of concrete without nanoparticles when compared with that cured in water, curing the specimens in saturated limewater results in more strengthening gel formation around Al₂O₃ nanoparticles and causes improved permeability together with high strength. In addition, Al₂O₃ nanoparticles are able to act as nanofillers and recover the pore structure of the specimens by decreasing harmful pores. Accelerated peak appearance in conduction calorimetry tests, more weight loss in thermogravimetric analysis and more rapid appearance of peaks related to hydrated products in X-ray diffraction results, all indicate that Al₂O₃ nanoparticles could improve mechanical and physical properties of the specimens.     

Mobilization of arsenic and other naturally occurring contaminants in groundwater of the Main Ethiopian Rift aquifers

This study investigates the mechanisms of arsenic (As) and other naturally occurring contaminants (F⁻, U, V, B, and Mo) mobilization from Quaternary sedimentary aquifers of the Main Ethiopian Rift (MER) and their enrichment in the local groundwater. The study is based on systematic measurements of major and trace elements as well as stable oxygen and hydrogen isotopes in groundwater, coupled with geochemical and mineralogical analyses of the aquifer rocks. The Rift Valley aquifer is composed of rhyolitic volcanics and Quaternary lacustrine sediments. X-ray fluorescence (XRF) results revealed that MER rhyolites (ash, tuff, pumice and ignimbrite) and sediments contain on average 72 wt. % and 65 wt. % SiO₂, respectively. Petrographic studies of the rhyolites indicate predominance of volcanic glass, sanidine, pyroxene, Fe-oxides and plagioclase. The As content in the lacustrine sediments (mean = 6.6 mg/kg) was higher than that of the rhyolites (mean: 2.5 mg/kg). The lacustrine aquifers of the Ziway-Shala basin in the northern part of MER were identified as high As risk zones, where mean As concentration in groundwater was 22.4 ± 33.5 (range of 0.60–190 μg/L) and 54% of samples had As above the WHO drinking water guideline value of 10 μg/L. Field As speciation measurements showed that most of the groundwater samples contain predominantly (∼80%) arsenate-As(V) over arsenite-As(III) species. The As speciation together with field data of redox potential (mean Eh = +73 ± 65 mV) and dissolved-O₂ (6.6 ± 2.2 mg/L) suggest that the aquifer is predominantly oxidative. Water-rock interactions, including the dissolution of volcanic glass produces groundwater with near-neutral to alkaline pH (range 6.9–8.9), predominance of Na–HCO₃ ions, and high concentration of SiO₂ (mean: 85.8 ± 11.3 mg/L). The groundwater data show high positive correlation of As with Na, HCO₃¯, U, B, V, and Mo (R² > 0.5; p < 0.001). Chemical modeling of the groundwater indicates that Fe-oxides and oxyhydroxides minerals were saturated in the groundwater, suggesting that the As reactivity is controlled by adsorption/desorption processes with these minerals. The data show that As and other oxyanion-forming elements such as U, B, Mo, and V had typically higher concentrations at pH > ∼8, reflecting the pH-dependence of their mobilization. Based on the geochemical and stable isotope variations we have established a conceptual model for the occurrence of naturally occurring contaminants in MER groundwater: 1) regional groundwater recharge from the Highland, along the Rift margins, followed by lateral flow and water–rock interactions with the aquifer rocks resulted in a gradual increase of the salinity and naturally occurring contaminants towards the center of the valley; and (2) local δ¹⁸O-rich lake water recharge into adjacent shallow aquifers, followed by additional mobilization of As and other oxyanion-forming elements from the aquifer rocks. We posit that the combined physical-chemical conditions of the aquifers such as oxidizing state, Na–HCO₃ composition, and pH>∼8 lead to enhanced mobilization of oxyanion-forming elements from Fe-oxides and consequently contamination of local groundwater. These geochemical conditions characterize groundwater resources along the Eastern African Rift and thus constitute a potential threat to the quality of groundwater in larger areas of Eastern Africa.     

Electrochemical degradation of chlortetracycline using N-doped Ti/TiO2 photoanode under sunlight irradiations

The appearance and the persistence of pharmaceutical products in the aquatic environment urgently call for the development of an innovative and practical water treatment technology. This study deals with the development of nanostructured nitrogen-doped TiO₂ photoanodes and their subsequent use for chlortetracycline (CTC) photoelectrocatalytic oxidation under visible light. The N-doped TiO₂ photoanodes with different nitrogen contents were prepared by means of a radiofrequency magnetron sputtering (RF-MS) process, with the objective to tune shift their optical absorption from the UV towards the visible. The N-doped TiO₂ consist of nanostructured anatase phase with average TiO₂ nanocrystallite size of 29 nm. The nitrogen doping is clearly shown to produce the desired red shift of the absorption onset of the TiO₂ coatings (from ∼380 nm to ∼550 nm). Likewise, the N-doped TiO₂ are found to be highly photo-electroactive not only under the UV light but most interestingly under the visible light as well. Using the optimal N-doped photoanodes, 99.6% of CTC (100 μg/L) was successfully degraded after 180 min of treatment time with a current intensity of 0.6 A. Under these conditions, a relatively high mineralization of CTC (92.5% ± 0.26% of TOC removal and 90.3% ± 1.1% of TN removal) was achieved.     

Characterization of microstructural features of Tamusu mudstone

Tamusu mudstone formation, located in the Alxa area in western Inner Mongolia, is considered a potential host formation for high-level radioactive waste (HLW) underground disposal in China. In this study, complementary analyses with X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), mercury intrusion porosimetry (MIP), and N₂ physisorption isotherm were conducted on the Tamusu mudstone to characterize its physical characteristics and microstructural features, such as mineral compositions and pore structure. Several minerals, including carbonates, feldspar, clays and analcime, were identified in Tamusu mudstone by XRD. Images from FE-SEM show that pores in the Tamusu mudstone were dominantly on nanometer scale and generally located within their mineral matrix or at the interface with non-porous minerals. The combination of the MIP and N₂ physisorption curves indicated that the Tamusu mudstone has diverse pore sizes, a porosity varying from 2.34% to 2.84%, and a total pore volume in the range of 0.0065–0.0222 cm³/g with the average pore diameter ranging from 9.6 nm to 19.23 nm. The specific surface area measured by MIP (2.572–5.861 m²/g) was generally higher than that by N₂ physisorption (1.29–3.04 m²/g), due to the pore network effect, pore shape (e.g. ink-bottle shape), or technique limits. The results related to pore information can be applied as an input in the future to model single- or multi-phase fluid flow and the transport of radionuclides in porous geomedium by migration and diffusion.     

Increasing arsenic concentrations in runoff from 12 small forested catchments (Czech Republic, Central Europe): Patterns and controls

The 40-year long period of heavy industrialization in Central Europe (1950-1990) was accompanied by burning of arsenic-rich lignite in thermal power plants, and accumulation of anthropogenic arsenic in forest soils. There are fears that retreating acidification may lead to arsenic mobilization into drinking water, caused by competitive ligand exchange. We present monthly arsenic concentrations in surface runoff from 12 headwater catchments in the Czech Republic for a period of 13 years (1996-2008). The studied area was characterized by a north-south gradient of decreasing pollution. Acidification, caused mainly by SO_x and NO_x emissions from power plants, has been retreating since 1987. Between 1996 and 2003, maximum arsenic concentrations in runoff did not change, and were < 1 ppb in the rural south and < 2 ppb in the industrial north. During the subsequent two years, 2004-2005, maximum arsenic concentrations in runoff increased, reaching 60% of the drinking water limit (10 ppb). Starting in 2006, maximum arsenic concentrations returned to lower values at most sites. We discuss three possible causes of the recent arsenic concentration maximum in runoff. We rule out retreating acidification and a pulse of high industrial emission rates as possible controls. The pH of runoff has not changed since 1996, and is still too low (< 6.5) at most sites for an As-OH⁻ ligand exchange to become significant. Elevated arsenic concentrations in runoff in 2004-2005 may reflect climate change through changing hydrological conditions at some, but not all sites. Dry conditions may result in elevated production of DOC and sulfur oxidation in the soil. Subsequent wet conditions may be accompanied by acidification leading to faster dissolution of arsenic-bearing sulfides, dissolution of arsenic-bearing Fe-oxyhydroxides, and elevated transport of arsenic sorbed on organic matter. Anaerobic domains exist in normally well-aerated upland soils for hours-to-days following precipitation events.     

Performance of granular zirconium-iron oxide in the removal of fluoride from drinking water

In this study, a granular zirconium-iron oxide (GZI) was successfully prepared using the extrusion method, and its defluoridation performance was systematically evaluated. The GZI was composed of amorphous and nano-scale oxide particles. The Zr and Fe were evenly distributed on its surface, with a Zr/Fe molar ratio of ∼2.3. The granular adsorbent was porous with high permeability potential. Moreover, it had excellent mechanical stability and high crushing strength, which ensured less material breakage and mass loss in practical use. In batch tests, the GZI showed a high adsorption capacity of 9.80 mg/g under an equilibrium concentration of 10 mg/L at pH 7.0, which outperformed many other reported granular adsorbents. The GZI performed well over a wide pH range, of 3.5-8.0, and especially well at pH 6.0-8.0, which was the preferred range for actual application. Fluoride adsorption on GZI followed pseudo-second-order kinetics and could be well described by the Freundlich equilibrium model. With the exception of HCO₃⁻, other co-existing anions and HA did not evidently inhibit fluoride removal by GZI when considering their real concentrations in natural groundwater, which showed that GZI had a high selectivity for fluoride. In column tests using real groundwater as influent, about 370, 239 and 128 bed volumes (BVs) of groundwater were treated before breakthrough was reached under space velocities (SVs) of 0.5, 1 and 3 h⁻¹, respectively. Additionally, the toxicity characteristic leaching procedure (TCLP) results suggested that the spent GZI was inert and could be safely disposed of in landfill. In conclusion, this granular adsorbent showed high potential for fluoride removal from real groundwater, due to its high performance and physical-chemical properties.     

Traffic-related air pollution and cardiovascular mortality in central Taiwan

In this study, the relationship between cardiovascular mortality and traffic-related air pollutants (NO₂, CO, PM₁₀, and six volatile organic compounds (VOCs), propane, iso-butane, propylene, benzene, meta-, para-, and ortho-xylenes) was investigated. The concentrations of NO₂, PM₁₀ and CO from 1993 to 2006 were measured at a fixed-site air monitoring station, and VOC data from 2003 to 2006 were obtained from a photochemical assessment monitoring site in an urban area in central Taiwan. Outcome variables were data on mortality due to cardiovascular diseases (ICD-9-CM 410-411, 414, 430-437) from 1993 to 2006. Cardiovascular mortality averaged 1.5 cases, ranging between 0 and 9 cases per day. Daily air pollution levels ranged from 0.5 to 80.5 ppb for NO₂ and from 0.1 to 3.8 ppm for CO. From the subset of data from 2003 to 2006, daily average values ranged from 0.6 to 17.5 ppb for propane, 0.3 to 6.7 ppb for iso-butane, 0.3 to 6.7 ppb for propylene, 0.2 to 3.8 ppb for benzene, 0.3 to 26.0 ppb for m,p-xylene, and 0.02 to 7.6 ppb for o-xylene. Poisson generalized additive model was used to estimate the effects of elevated air pollutant levels on daily mortality, adjusting for meteorological conditions and temporal trends. Single-pollutant model showed that cardiovascular mortality was significantly associated with NO₂ lagged 2 days, and with propane, iso-butane, and benzene lagged 0 day. The relative risk for an interquartile range increase in air pollutant levels was 1.053 for NO₂, 1.064 for propane, 1.055 for iso-butane, and 1.055 for benzene. In conclusion, daily cardiovascular mortality showed association with data on acute exposure to traffic air pollutants in Taichung, which is an important factor to consider in studying cardiovascular mortality in urban environments.     

Removing low ppb level perchlorate, RDX, and HMX from groundwater with cetyltrimethylammonium chloride (CTAC) pre-loaded activated carbon

Perchlorate contaminates vast amounts of groundwater throughout the United States which could potentially be used as potable water. Activated carbon pre-loaded with cetyltrimethylammonium chloride has been shown in this research to be an effective adsorbent for removing perchlorate from three low conductivity (50-66 microS/cm) groundwaters containing perchlorate (ClO(4)(-)) concentrations of 0.85, 1.0, and 5.6 parts per billion (ppb), respectively. In rapid small-scale column tests (RSSCTs), the virgin granular activated carbon (GAC) (used as a control) treated between 20,000 and 40,000 bed volumes (BV) of water. In contrast, the activated carbon that was pre-loaded with CTAC processed 170,000-270,000 BV before perchlorate was detected above 0.25 ppb in the effluent. Though this pre-loading significantly increased the capacity for perchlorate, it also diminished the GAC's capacity to remove organics. The groundwater containing 1 ppb ClO(4)(-) also contained the nitro-organics HMX (0.6 ppb) and RDX (5.5-6.6 ppb). RDX was detected in the effluent from the CTAC-pre-loaded bed after only 8000 BV had been processed whereas 308,000 BV could be processed through the virgin bed before RDX was detected. Likewise, HMX breakthrough was observed after 116,000 BV in the CTAC-pre-loaded bed while the virgin RSSCT exhibited no breakthrough of HMX during a test that was operated for 309,000 BV. However, by combining a CTAC-pre-loaded bed followed by a virgin GAC bed in series, both perchlorate and RDX could be removed for the same length of time.     

Transport and deposition of CeO2 nanoparticles in water-saturated porous media

Ceria nanoparticles are used for fuel cell, metal polishing and automobile exhaust catalyst; however, little is known about the impact of their release to the environment. The stability, transport and deposition of engineered CeO₂ nanoparticles through water-saturated column packed with sand were studied by monitoring effluent CeO₂ concentration. The influence of solution chemistry such as ionic strength (1-10 mM) and pH (3-9) on the mobility and deposition of CeO₂ nanoparticles was investigated by using a three-phase (deposition-rinse-reentrainment) procedure in packed bed columns. The results show that water chemistry governs the transport and deposition of CeO₂ nanoparticles. Transport is significantly hindered at acidic conditions (pH 3) and high ionic strengths (10 mM and above), and the deposited CeO₂ particles may not be re-entrained by increasing the pH or lowering the ionic strength of water. At neutral and alkaline conditions (pH6 and 9), and lower ionic strengths (below 10 mM), partial breakthrough of CeO₂ nanoparticles was observed and particles can be partially detached and re-entrained from porous media by changing the solution chemistry. A mathematical model was developed based on advection-dispersion-adsorption equations and it successfully predicts the transport, deposition and re-entrainment of CeO₂ nanoparticles through a packed bed. There is strong agreement between the deposition rate coefficients calculated from experimental data and predicted by the model. The successful prediction for attachment and detachment of nanoparticles during the deposition and re-entrainment phases is unique addition in this study. This work can be applied to access the risk of CeO₂ nanoparticles transport in contaminated ground water.