Dysregulation of SOX17/NRF2 axis confers chemoradiotherapy resistance and emerges as a novel therapeutic target in esophageal squamous cell carcinoma.

BACKGROUND: Esophageal squamous cell carcinoma (ESCC) is the sixth leading cause of cancer-associated death worldwide with a dismal overall 5-year survival rate of less than 20%. The standard first-line therapy for advanced ESCC is concomitant chemo-radiation therapy (CCRT); however, patients usually develop resistance, resulting in unfavorable outcomes. Therefore, it is urgent to identify the mechanisms underlying CCRT resistance and develop effective treatment strategies. METHODS: Patients' endoscopic biopsy tumor tissues obtained before CCRT treatment were used to perform RNA-seq and GSEA analysis. Immunohistochemical (IHC) staining, chromatin immunoprecipitation (ChIP), and promoter reporter analyses were conducted to investigate the relationship between SOX17 and NRF2. Xenograft mouse models were used to study the role of SOX17/NRF2 axis in tumor growth and the efficacy of carboxymethyl cellulose-coated zero-valent-iron (ZVI@CMC). RESULTS: In this study, a notable gene expression signature associated with NRF2 activation was observed in the poor CCRT responders. Further, IHC staining of endoscopic biopsy of 164 ESCC patients revealed an inverse correlation between NRF2 and SOX17, a tumor-suppressive transcription factor with low expression in ESCC due to promoter hypermethylation. Using ChIP and promoter reporter analyses, we demonstrated that SOX17 was a novel upstream transcriptional suppressor of NRF2. In particular, SOX17low/NRF2high nuclear level significantly correlated with poor CCRT response and poor survival, indicating that the dysregulation of SOX17/NRF2 axis played a pivotal role in CCRT resistance and tumor progression. Notably, the in-house developed nanoparticle ZVI@CMC functioned as an inhibitor of DNA methyltransferases to restore expression of SOX17 that downregulated NRF2, thereby overcoming the resistance in ESCC. Additionally, the combination of ZVI@CMC with radiation treatment significantly augmented anticancer efficacy to inhibit tumor growth in CCRT resistant cancer. CONCLUSION: This study identifies a novel SOX17low/NRF2high signature in ESCC patients with poor prognosis, recognizes SOX17 as a transcriptional repressor of NRF2, and provides a promising strategy targeting SOX17/NRF2 axis to overcome resistance.

Rainfall Threshold Assessment Corresponding to the Maximum Allowable Turbidity for Source Water.

This study aims to assess the upstream rainfall thresholds corresponding to the maximum allowable turbidity of source water, using monitoring data and artificial neural network computation. The Taipei Water Source Domain was selected as the study area, and the upstream rainfall records were collected for statistical analysis. Using analysis of variance (ANOVA), the cumulative rainfall records of one-day Ping-lin, two-day Ping-lin, two-day Tong-hou, one-day Guie-shan, and one-day Tai-ping (rainfall in the previous 24 or 48 hours at the named weather stations) were found to be the five most significant parameters for downstream turbidity development. An artificial neural network model was constructed to predict the downstream turbidity in the area investigated. The observed and model-calculated turbidity data were applied to assess the rainfall thresholds in the studied area. By setting preselected turbidity criteria, the upstream rainfall thresholds for these statistically determined rain gauge stations were calculated.

BOTTLE MATERIAL AND CLEANSING PROCEDURES OF INFANT FEEDING BOTTLES.

The cleanliness of feeding bottles is vital for child health. Although machine cleansing of bottles in the food industry has been established, mechanical and manual cleansing methods are highly variable. This study was undertaken to determine the differences in the cleanliness of bottles that were cleaned using various combinations of bottle materials [glass and polypropylene (PP)], rinsing water volumes (1/3, 1/2, and 2/3 capacity of a bottle), and sustained shaking times (5 seconds and 20 seconds). Total organic carbon (TOC) and conductivity measurements were respectively used to evaluate the rinsed quantities of organic and inorganic formula residue from feeding bottles. The results indicated that glass bottles filled with rinsing water to 2/3 of their capacity showed the most efficient cleansing performance. However, the PP bottles exhibited a relatively poor cleansing result, particularly for organic cleanliness. The organic residue tends to accumulate on the PP bottle interior because of the aggregation of compounds with similar properties. The shaking time hardly influenced the cleanliness. The glass bottle was superior to the PP bottle in both organic and inorganic cleanliness, and organic constituents were more difficult to rinse from the bottle than the inorganic constituents were.

Degradation of antibiotic amoxicillin using 1 x 1 molecular sieve-structured manganese oxide.

The kinetics and mechanism ofamoxicillin (AMO) degradation using a 1 x 1 molecular sieve-structured manganese oxide (MnO2) was studied. The presence of the buffer solution (i.e., NaHCO3, NaH2PO4 and KH2PO4) diminished AMO binding to MnO2, thus reducing AMO degradation in the pretest; therefore, all other experiments in this study were conducted without the addition of a buffer. Third-order rate constants, second-order on AMO and first-order on MnO2 increased with elevating pH level (2.81-7.23) from 0.54 to 9.17 M(-2) s(-1), and it decreased to 4.27 M(-2) s(-1) at pH 8.53 beyond the pk(a2) of AMO (7.3). The dissolution of the MnO2 suspension with and without AMO exhibited a similar trend; that is, Mn2+ concentration increased with decreasing pH. However, the dissolution of MnO2 with AMO was greater than that without AMO, except for the reaction occurring at pH 8.53, partially indicating that MnO2 acts as an oxidant in AMO degradation. The preliminary chromatogram data display different products with varying pH reaction s, implying that AMO elimination using this 1 x 1 molecular sieve-structured MnO2 is by adsorption as well as oxidative degradation. A complementary experiment indicates that the amount of oxidatively degraded AMO increases substantially from 65.5% at 4 h to 95% at 48 h, whereas the AMO adsorbed onto MnO2 decreases slightly from 4.5% at4 h to 2.4% at 48 h. The oxidative degradation accounted for more AMO removal than adsorption over the whole reaction course, indicating that the oxidative reaction of AMO on MnO2 dominated the AMO removal.

Excretion of Ni, Pb, Cu, As, and Hg in Sweat under Two Sweating Conditions.

Physiologists have long regarded sweating as an effective and safe means of detoxification, and heavy metals are excreted through sweat to reduce the levels of such metals in the body. However, the body can sweat through many means. To elucidate the difference in the excretion of heavy metals among sweating methods, 12 healthy young university students were recruited as participants (6 men and 6 women). Sweat samples were collected from the participants while they were either running on a treadmill or sitting in a sauna cabinet. After they experienced continuous sweating for 20 min, a minimum of 7 mL of sweat was collected from each participant, and the concentrations of nickel (Ni), lead (Pb), copper (Cu), arsenic (As), and mercury (Hg) were analyzed. The results demonstrated that the sweating method affected the excretion of heavy metals in sweat, with the concentrations of Ni, Pb, Cu, and As being significantly higher during dynamic exercise than during sitting in the sauna (all p < 0.05). However, the concentrations of Hg were unaffected by the sweating method. This study suggests that the removal of heavy metals from the body through dynamic exercise may be more effective than removal through static exposure to a hot environment.

Comparative Study of the Composition of Sweat from Eccrine and Apocrine Sweat Glands during Exercise and in Heat.

This preliminarily study was made to examine the differences in sweat excretions from human eccrine and apocrine sweat glands in dynamic exercise and heat conditions. Sweat samples were collected from six young males while they were either running on a treadmill or sitting in a sauna cabinet. Sweat samples of at least 5 mL from the eccrine (upper-back) and apocrine (armpit) sweat glands were collected during a 20-min running (or inactive overheating) period. The samples were then analyzed for urea, uric acid, and electrolyte (Na+, Cl-, and K+) excretions. The results from a two-way repeated-measures analysis of variance (ANOVA) revealed that the secretions of urea and K+ were significantly higher during running than during inactive overheating for both glands, as were Na+ secretions for the apocrine glands (all P < 0.05). Under the same sweating conditions, urea and K+ excretions from the apocrine glands were also higher than those from the eccrine glands (all P < 0.05). Significant differences were observed between the Na+ secretions of the apocrine and eccrine glands under the running condition. The effects of various sweating methods and sweat glands on Cl- secretions were nonsignificant, and little uric acid was excreted. A higher urea excretion level during running rather than in hot conditions could be attributed to an elevated metabolic rate.

Effects of Surfactants on the Degradation of Diclofenac by Manganese Oxide.

Amine-containing pharmaceuticals are the most often detected pharmaceuticals in wastewater and ambient aquatic environments. They can usually be degraded by manganese oxide (MnO2), which is a common natural oxidant in soils. Surfactants often coexist with pharmaceuticals in wastewater. Some amine-containing pharmaceuticals, such as diclofenac (DIC), are acidic and are thus ionic compounds in neutral conditions. These compounds, therefore, have similar properties to surfactants. Surfactants, thus, may influence the adsorption and degradation processes of DIC by MnO2. The effect of the type of surfactant on the degradation of DIC by MnO2 was investigated in this study with the addition of two common biodegradable surfactants (cetyltrimethyl-ammonium bromide (CTAB) and sodium dodecylsulfate (SDS)). The results indicated that the cationic surfactant (CTAB) significantly increased the degradation rate in neutral and alkaline conditions. On the other hand, the anionic surfactant (SDS) slightly increased the DIC removal rate in an acidic condition but significantly decreased the removal in neutral and alkaline conditions. Coexisting cationic surfactants not only influenced the kinetics but also altered the transformation mechanism of DIC by MnO2. Decarboxylation is the main transformation mechanism of DIC in the presence of CTAB, while both decarboxylation and hydroxylation are the main transformation mechanisms in the absence of CTAB.

Dysregulated Kras/YY1/ZNF322A/Shh transcriptional axis enhances neo-angiogenesis to promote lung cancer progression.

Angiogenesis enhances cancer metastasis and progression, however, the roles of transcription regulation in angiogenesis are not fully defined. ZNF322A is an oncogenic zinc-finger transcription factor. Here, we demonstrate a new mechanism of Kras mutation-driven ZNF322A transcriptional activation and elucidate the interplay between ZNF322A and its upstream transcriptional regulators and downstream transcriptional targets in promoting neo-angiogenesis. Methods: Luciferase activity, RT-qPCR and ChIP-qPCR assays were used to examine transcription regulation in cell models. In vitro and in vivo angiogenesis assays were conducted. Immunohistochemistry, Kaplan-Meier method and multivariate Cox regression assays were performed to examine the clinical correlation in tumor specimens from lung cancer patients. Results: We validated that Yin Yang 1 (YY1) upregulated ZNF322A expression through targeting its promoter in the context of Kras mutation. Reconstitution experiments by knocking down YY1 under KrasG13V activation decreased KrasG13V-promoted cancer cell migration, proliferation and ZNF322A promoter activity. Knockdown of YY1 or ZNF322A attenuated angiogenesis in vitro and in vivo. Notably, we validated that ZNF322A upregulated the expression of sonic hedgehog (Shh) gene which encodes a secreted factor that activates pro-angiogenic responses in endothelial cells. Clinically, ZNF322A protein expression positively correlated with Shh and CD31, an endothelial cell marker, in 133 lung cancer patient samples determined using immunohistochemistry analysis. Notably, patients with concordantly high expression of ZNF322A, Shh and CD31 correlated with poor prognosis. Conclusions: These findings highlight the mechanism by which dysregulation of Kras/YY1/ZNF322/Shh transcriptional axis enhances neo-angiogenesis and cancer progression in lung cancer. Therapeutic strategies that target Kras/YY1/ZNF322A/Shh signaling axis may provide new insight on targeted therapy for lung cancer patients.

Thermal detoxification of hazardous metal sludge by applied electromagnetic energy.

Industrial wastewater sludge was treated by microwave processes to enhance the stabilization of laden copper. The effects of additives, processing time, microwave adsorbents, moisture content, reaction atmosphere, and cooling gas were investigated. The stabilization results were significantly enhanced by metal powder additives, prolonged microwave processing time, proper moisture content, the addition of carbonaceous materials, and a reaction environment with inert gas. It was also found that the moisture content would increase the homogeneity of applied microwave energy, and thus achieve a better overall efficiency between stabilizing agents and copper. The added metal powders may reduce Cu(II) to Cu(0) in the sludge or TCLP. The resulting thermal energy of microwave radiation, and microarcing process and the oxidation heat of Al powder may also assist the transformation of Cu(II) into CuO and CuAl2O4 phases. Part of the sludge was vitrified within inert gas environment when the processing time was longer than 18 min and active carbon dosage was more than 3g. Reduction reactions also occurred in the hybrid microwave processes, leading to the reduction of sulfates and metal ions, and the formation of Cu2S and FeS. Moreover, the microwave radiation can also enhance the feasibility of co-treating of inorganic and organic solid waste.

Simulation the kinetics of fluoride removal by electrocoagulation (EC) process using aluminum electrodes.

A variable order kinetic (VOK) model derived from the Langmuir equation was applied to specify the kinetics of the fluoride removal reaction for electrocoagulation (EC). Synthetic solutions were employed to elucidate the effects of the initial fluoride concentration, the applied current and the initial acidity on the simulation results of the model. The proposed model successfully describes the fluoride removal reaction, except in a system in which the initial concentration of the acid is less than the initial fluoride concentration. The violent change of pH companying with the appearance of equivalence point in the titration curves should be the main reason the VOK model fails to simulate the defluoridation in the systems with an initial acidity higher than initial fluoride concentration.

Microwave enhanced stabilization of heavy metal sludge.

A microwave process can be utilized to stabilize the copper ions in heavy metal sludge. The effects of microwave processing on stabilization of heavy metal sludge were studied as a function of additive, power, process time, reaction atmosphere, cooling gas, organic substance, and temperature. Copper leach resistance increased with addition of aluminum metal powder, with increased microwave power, increased processing time, and using a gaseous environment of nitrogen for processing and air for cooling [N2/air]. The organic in the sludge affected stabilization, whether or not the organic smoldered. During heating in conventional ovens, exothermic oxidation of the organic resulted in sludge temperatures of about 500 degrees C for oven control temperatures of 200-500 degrees C. After microwave heating dried the sludge, the sludge temperature rose to 500 degrees C. The reaction between copper ions and metal aluminum in the dried sludge should be regarded as a solid phase reaction. Adding aluminum metal powder and reaction temperature were the key parameters in stabilizing copper in the heavy metal sludge, whether heated by microwave radiation or conventional oven. The mass balance indicates insignificant volatization of the copper during heating.

The assistance of microwave process in sludge stabilization with sodium sulfide and sodium phosphate.

After industrial wastewater sludge passed through an acid-extraction process to reclaim most of the copper ions in it, the residue may still need to be treated by stabilization technologies. The common method for the stabilization of hazardous waste in Taiwan is by cement solidification. However, this method has the disadvantage of an increase in waste volume. In this study, it was tried to combine the advantages of sulfur anions and phosphate anions with the characteristics of microwave energy to offer a new method which can avoid the disadvantage of cement solidification. From the results, it was found that the assistance of heating in sludge stabilization with additives was effective. Huge amounts of additives were saved. Compared with the assistance of the traditional electrical-heating in sludge stabilization with additives, that of the microwave process saved much time and was more powerful. However, when the reaction time was longer, a re-leaching situation would occur. The hybrid microwave process, a procedure of leading an inert gas into the microwave process, could overcome the disadvantage of the microwave process with regard to the long reaction time. Finally, a modified hybrid microwave process which reduced the use of gas was performed and recommended.

Effect of precursor concentration on the characteristics of nanoscale zerovalent iron and its reactivity of nitrate.

Differing precursor concentrations, 1.0, 0.1, and 0.01 M FeCl(3) x 6H(2)O, were performed to produce nanoscale Fe(0) and the results were discussed in terms of the specific surface area, particle size and electrochemical properties. The results indicated that the nanoscale Fe(0) prepared by 0.01 M FeCl(3) had absolutely reduced in size (9-10nm) and possessed the greatest specific surface area (56.67 m(2) g(-1)). These synthesized nanoscale Fe(0) particles were attempted to enhance the removal of 40 mg-NL(-1) unbuffered nitrate solution. The first-order degradation rate constants (k(obs)) increased significantly (5.5-8.6 times) with nanoscale Fe(0) prepared by 0.01 M precursor solution (Fe(0.01 M)(0)). When normalized to iron surface area concentration, the specific rate constant (k(SA)) was increased by a factor of approximately 1.7-2.4 using Fe(0.01 M)(0) (6.84 x 10(-4) L min(-1) m(-2) for Fe(0.01 M)(0), 4.04 x 10(-4) L min(-1) m(-2) for Fe(0.1 M)(0) and 2.80 x 10(-4) L min(-1) m(-2) for Fe(1 M)(0)). The rise of reactivity of the reactive site on the Fe(0.01 M)(0) surface was indicated by the specific rate constant (k(SA)) calculation and the i(0) value of the electrochemical test.

Adsorption of copper ions onto microwave stabilized heavy metal sludge.

Microwave stabilized heavy metal sludge was used as an adsorbent to remove the copper ions from aqueous solution. The adsorption characteristics of copper on the stabilized-sludge were studied by various models, such as Freundlich and Langmuir isotherm equation. Results show that the pH(zpc) of stabilized-sludge was at 9.2-9.5. Moreover, the adsorption of copper ions onto the stabilized-sludge surface was mainly on account of the heterogeneous surface of the stabilized-sludge. In the dynamic study, the experimental data was fitted to the intraparticle diffusion model, pseudo-first order model and pseudo-second order model. However, the experimental data was only well correlated with pseudo-second order model with the correlation coefficient>0.995. Furthermore, both Freundlich and Langmuir isotherm equations were found to represent the measured adsorption data well. From the Langmuir equation, the adsorption capacity increased from 18 to 28 mg/g as the temperature rose from 15 to 55 degrees C, since this adsorption process was an endothermic reaction. After this adsorption process, copper ions can be concentrated on and in a small bead and recovery efficiently.

Factors Controlling Changes in Epilithic Algal Biomass in the Mountain Streams of Subtropical Taiwan.

In upstream reaches, epilithic algae are one of the major primary producers and their biomass may alter the energy flow of food webs in stream ecosystems. However, the overgrowth of epilithic algae may deteriorate water quality. In this study, the effects of environmental variables on epilithic algal biomass were examined at 5 monitoring sites in mountain streams of the Wuling basin of subtropical Taiwan over a 5-year period (2006-2011) by using a generalized additive model (GAM). Epilithic algal biomass and some variables observed at pristine sites obviously differed from those at the channelized stream with intensive agricultural activity. The results of the optimal GAM showed that water temperature, turbidity, current velocity, dissolved oxygen (DO), pH, and ammonium-N (NH4-N) were the main factors explaining seasonal variations of epilithic algal biomass in the streams. The change points of smoothing curves for velocity, DO, NH4-N, pH, turbidity, and water temperature were approximately 0.40 m s-1, 8.0 mg L-1, 0.01 mg L-1, 8.5, 0.60 NTU, and 15°C, respectively. When aforementioned variables were greater than relevant change points, epilithic algal biomass was increased with pH and water temperature, and decreased with water velocity, DO, turbidity, and NH4-N. These change points may serve as a framework for managing the growth of epilithic algae. Understanding the relationship between environmental variables and epilithic algal biomass can provide a useful approach for maintaining the functioning in stream ecosystems.

MS title: Catalytic oxidation and removal of arsenite in the presence of Fe ions and zero-valent Al metals.

Arsenic immobilization in acid mine drainage (AMD) is required prior to its discharge to safeguard aquatic organisms. Zero-valent aluminum (ZVAl) such as aluminum beverage cans (AlBC) was used to induce the oxidation of As(III) to As(V) and enhance the subsequent As removal from an artificially prepared AMD. While indiscernible As(III) oxidation was found in aerated ZVAl systems, the addition of 0.10-0.55mM Fe(II) or Fe(III) into the AMD significantly promoted the As(V) production. Reactions between Fe(II) and H2O2, which was produced through an oxidative reaction of ZVAl with dissolved oxygen, generated OH radicals. Such OH radicals subsequently induced the As(III) oxidation. Over the course of the Fenton like reaction, ZVAl not only directly generated the H2O2, but indirectly enhanced the OH radical production by replenishing Fe(II). Arsenite oxidation in the aerated ZVAl/Fe and AlBC/Fe systems followed zero- and first-order kinetics. Differences in the kinetic reactions of ZVAl and AlBC with respect to As(III) oxidation were attributed to higher productive efficiency of the oxidant in the AlBC systems. After the completion of As(III) oxidation, As(V) could be removed simultaneously with Al(III) and Fe(III) by increasing solution's pH to 6 to produce Al/Fe hydroxides as As(V) scavengers or to form Al/Fe/As co-precipitates.

Molecular Structures of Al/Si and Fe/Si Coprecipitates and the Implication for Selenite Removal.

Aluminum and iron oxides have been often used in the coagulation processes during water purification due to their unique surface properties toward anions. In the presence of silica, the coprecipitation of Al/Si or Fe/Si might decrease the efficiency of wastewater purification and reuse. In this study, surface properties and molecular structures of Al/Si and Fe/Si coprecipitates were characterized using spectroscopic techniques. Also, the selenite removal efficiency of Al/Si and Fe/Si coprecipitates in relation to their surface and structural properties was investigated. While dissolved silicate increased with increasing pH from Fe/Si coprecipitates, less than 7% of silicate was discernible from Al/Si samples over the range from acidic to alkaline conditions. Our spectroscopic results showed that the associations between Al and Si were relatively stronger than that between Fe and Si in coprecipitates. In Al/Si coprecipitates, core-shell structures were developed with AlO6/AlO4 domains as the shells and Si frameworks polymerized from the SiO2 as the cores. However, Si framework remained relatively unchanged upon coprecipitation with Fe hydroxides in Fe/Si samples. The Si core with Al shell structure of Al/Si coprecipitates shielded the negative charges from SiO2 and thereby resulted in a higher adsorption capacity of selenite than Fe/Si coprecipitates.

Effect of citric acid on aluminum hydrolytic speciation.

The mechanisms of the influence of organics on Al transformation were not fully understood. This study investigated the effect of citric acid on Al speciation in partially neutralized aluminum solution. The partially neutralized solution was prepared with 20 mmol L(-1) AlCl3 without citrate (citrate/Al molar ratio of 0, control) or with citrate (citrate to Al molar ratios between 0.1 and 3.0) at pH between 3.0 and 7.0. The nature of aluminum hydrolytic products as influenced by citrate complexation was investigated by turbidity measurement, ferron kinetic color development, peak line width in 27Al nuclear magnetic resonance (NMR) deconvolution demodule quantitative methods, and the MinteqA2 chemical speciation program. Sulfate precipitates from Al solution as influenced by citrate were examined by X-ray diffraction (XRD) analysis and atomic force microscopy (AFM). The turbidity of the Al solution increased with increasing pH values. Increases in citrate/Al molar ratio from 0 to 0.1 decreased dramatically the turbidity due to citrate complexation. The 27Al NMR peak at 6 ppm of the Al solution at a citrate/Al molar ratio of 0.5 shifted to 8 and 10 ppm in the solutions at citrate/Al molar ratio of 1.0 and 3.0, respectively. Comparison of 27Al NMR data and the data obtained from the MinteqA2 chemical speciation program, indicate that the Al-citrate complexes as revealed by 27Al NMR data are largely Al(citrate), AlH(citrate)+, and Al(citrate)(2)3- complexes (99-112%) in the pH range of 4.5-6.5. The non-detected Al fractions by the MinteqA2 program account for 82-99% of the non-detected Al fractions by NMR quantitation in the same pH range. The AFM of sulfate precipitates from solutions with low citrate/Al molar ratios (i.e., 0.01, pH 4.5, aged 40 days) shows that Al13 sulfate precipitates were ellipse-shaped. These ellipse-shaped precipitates were aggregated when solution pH increased from 4.5 to 7.0 (aged 40 days), indicating the fast hydrolytic rate of Al at high pH. The sulfate precipitates from solution with a high citrate/Al molar ratio (i.e., 0.05, pH 4.5, aged 40 days) also shows aggregate of particles, and XRD non-crystallized precipitates the hampering effect of citrate on Al precipitates.

Chemical reduction of an unbuffered nitrate solution using catalyzed and uncatalyzed nanoscale iron particles.

Uncatalyzed and catalyzed nanoscale Fe(0) systems were employed for the denitrification of unbuffered 40 mgN L(-1) nitrate solutions at initial neutral pH. Compared to microscale Fe(0) (<100 mesh), the efficiency and rate of nitrate removal using uncatalyzed and catalyzed nano-Fe(0) were highly promoted, in which the maximum promoted rate was obtained using copper-catalyzed nano-Fe(0) (nano-Cu/Fe). Nitrate first-order degradation rate constants (k(obs)) decreased significantly (>70%) with aged nano-Fe(0) and aged nano-Cu/Fe, and were recovered with NaBH(4) as reductants at levels of about 85 and 75%, respectively. Activation energies (E(a)) of nitrate reduction over the temperature range of 10-60 degrees C were 42.5 kJ mol(-1) for microscale Fe(0), 25.8 kJ mol(-1) for nano-Fe(0) and 16.8 kJ mol(-1) for nano-Cu/Fe. Unlike microscale Fe(0), the kinetics of denitrification by nano-Fe(0) and nano-Cu/Fe began to show characteristics of mass transport in addition to chemical reaction control. Ammonium was the predominant end product in all the systems. However, as for nitrite, 40% of the degraded nitrate persisted in the nano-Cu/Fe system. Thus, relative to nano-Cu/Fe, nano-Fe(0) is a potential reductant for denitrification of groundwater as far as toxic nitrite generation is concern.

Effects of iron surface pretreatment on kinetics of aqueous nitrate reduction.

Using hydrogen gas at 400 degrees C to activate iron surface was proposed to remove nitrate (40 mg NL(-1)) in a HEPES buffer solution at pH value between 6.5 and 7.5. Compared with the nonpretreated iron, the first-order reaction rate constant (kobs) was increased 4.7 times by pretreated iron, and the lag of the early period disappeared. Normalized to iron surface area concentration, the specific rate constant (kSA) was increased approximately by a factor of 6 using hydrogen reduction (0.0020 min(-1)m(-2)L for nonpretreated iron and 0.0128 min(-1)m(-2)L for pretreated iron). The reactivity of aged iron covered by a complex mixture of iron oxides (soaking in nitrate solution for 60 days) were restored by hydrogen gas at 400 degrees C. Scanning electron microscopy (SEM) and temperature-programmed reduction (TPR) exhibited visibly cleaner without pitting and cracking and less oxygen fraction on pretreated iron surface relative to nonpretreated iron. Activation energies (Ea) of nitrate reduction over the temperature range of 10-45 degrees C were 46.0 kJ mol(-1) for nonpretreated iron, and 32.0 kJ mol(-1) for pretreated iron, indicating chemical reaction control, rather than diffusion. The results indicated that this enhancement was attributed to the increase in active site concentration on iron surface by hydrogen reduction.