Effect of dissolved metal ions on PCE decomposition by gamma-rays

This study investigates the effect of initial tetrachloroethylene (PCE) concentration, irradiation dose and dissolved metal ions such as Cr3+, Mn2+, Fe3+, Co2+, Ni2+, Cu2+ and Zn2+ on removal of PCE by gamma irradiation. The amount of removed PCE decreased with increase in initial PCE concentration and increased with increase in irradiation dose. PCE removal reached a maximum in the presence of Fe3+, while Cu2+ strongly hindered PCE decomposition. Except for Cu2+, the amount of removed PCE in the presence of metal ions was linearly dependent on the standard reduction potential of the metal ions. The extraordinary inhibition of Cu2+ in PCE removal was caused by the action of Cu2+ as a strong *OH scavenger, that was directly confirmed by electron paramagnetic resonance spectroscopy.     

EPR characterization of the catalytic activity of clays for PCE removal by gamma-radiation induced by acid and thermal treatments

Clays from tidal flat sediments showed efficient catalytic activity in the decomposition of PCE by gamma-radiation. The highest PCE removal of 98.6% was obtained with clays heated to 700 degrees C after acid treatment. The improved catalytic activity was identified by electron paramagnetic resonance (EPR) spectroscopy. The EPR spectra of clays were significantly changed by the acid and thermal treatments. The intensity of a narrow signal at g=2 (signal III) was decreased with increasing thermal treatment temperature and this increased the PCE removal efficiency. The acid treatment completely removed a broad signal at g=2 (signal II), decreased the intensity of signal III, and improved the gamma-radiation treatment of PCE.     

Reductive dechlorination of chlorinated methanes in cement slurries containing Fe(II)

Degradative solidification/stabilization (DS/S) is a novel remediation technology that combines chemical degradation with conventional solidification/stabilization. The applicability of the Fe(II)-based DS/S to treating chlorinated alkanes was tested by characterizing degradation reactions of carbon tetrachloride (CT) and its daughter products in cement slurries containing Fe(II). Degradation kinetics of CT and chloroform (CF) were generally very rapid with reaction rates comparable to rates that can be obtained with zero-valent iron. Dechlorination reactions of CT proceeded primarily via a hydrogenolysis pathway, which yielded CF and methylene chloride (MC) as major products and chloromethane and methane as minor products. However, reaction pathways other than hydrogenolysis also appeared to be important at very high pH conditions. MC apparently was resistant to dechlorination reactions over a period of about two months. Kinetics of CT and CF transformation were strongly dependent on pH with an optimal value around 13, which was higher than found previously for PCE. When the initial CF concentration varied between 0.01 and 1 mM, and the Fe(II) dose was 104 mM, pseudo-first-order kinetics generally described the degradation reactions of CF. However, there was also some indication of substrate saturation kinetics in these experiments. This suggests that a saturation model would better describe the kinetics in systems with higher concentration of substrates or lower concentration of the reactive surfaces.     

Laboratory-scale in situ chemical oxidation of a perchloroethylene pool using permanganate

In situ chemical oxidation (ISCO) is an emerging technology for the destruction of some chlorinated solvents present in subsurface environments. A laboratory investigation using a physical model was designed to assess the effectiveness of using permanganate as an oxidant to reduce the mass of a perchloroethylene (PCE) pool. The physical model was filled with silica sand overlying a silica flour base, simulating a two-dimensional saturated sand zone overlying a capillary barrier. PCE was introduced into the model so that it rested on top of the silica flour base, forming a dense nonaqueous phase liquid pool. The experimental methodology involved flushing the model with a permanganate solution for 146 days. During this period, measurements of chloride were used to assess the extent of pool oxidation. Before and after the oxidant flush, the quasi-steady state dissolution from the PCE pool was evaluated. Additionally, tracer studies were completed to assess changes in the flow field due to the oxidation process. At the termination of the experiment nine soil cores extracted from the model were used to detect the presence of MnO2 deposits and to quantify the mass of PCE remaining in the system. Excavation of the remaining material in the model revealed that the MnO2 distribution throughout the model was consistent with that observed in the cores. The oxidant flush was concluded before all of the pure phase PCE had been completely oxidized; however, approximately 45% of the PCE mass was removed, resulting in a fourfold decrease in the quasi-steady state aqueous phase mass loading of PCE from the pool. Measurements of chloride during the oxidant flush and of PCE in the soil cores suggested that the oxidation reaction occurred primarily at the upgradient edge of the PCE pool. MnO2 deposits within the model aquifer decreased the velocity of water directly above the pool, and the overall mass transfer from the remaining PCE pool. The results of this experimental study indicate that ISCO using permanganate is capable of removing substantial mass from a DNAPL pool; however, the performance of ISCO as a pool removal technology will be limited by the formation and precipitation of hydrous MnO2 that occurs during the oxidation process.     

Sorption of Zn(II) in aqueous solutions by scoria

We conducted kinetic and equilibrium sorption experiments on removal of Zn(II) from aqueous solutions by scoria (a vesicular pyroclastic rock with basaltic composition) from Jeju Island, Korea, in order to examine its potential use as an efficient sorbent. The batch-type kinetic sorption tests under variable conditions indicated that the percentage of Zn(II) removal by scoria increases with decreasing initial Zn(II) concentration, particle size, and sorbate/sorbent ratio. However, the sorption capacity decreases with the decrease of the initial Zn(II) concentration and sorbate/sorbent ratio. Equilibrium sorption tests show that Jeju scoria has a larger capacity and affinity for Zn(II) sorption than commercial powdered activated carbon (PAC); at initial Zn(II) concentrations of more than 10mM, the sorption capacity of Jeju scoria is about 1.5 times higher than that of PAC. The acquired sorption data are better fitted to the Langmuir isotherm than the Freundlich isotherm. Careful examination of ionic concentrations in sorption batches suggests that the sorption behavior is mainly controlled by cation exchange and typically displays characteristics of 'cation sorption'. The Zn(II) removal capacity decreases when solution pH decreases because of the competition with hydrogen ions for sorption sites, while the Zn(II) removal capacity increases under higher pH conditions, likely due to hydroxide precipitation. At an initial Zn(II) concentration of 5.0mM, the removal increases from 70% to 96% with the increase of initial pH from 3.0 to 7.0. We recommend Jeju scoria as an economic and efficient sorbent for Zn(II) in contaminated water.     

PCE dissolution and simultaneous dechlorination by nanoscale zero-valent iron particles in a DNAPL source zone

While the capability of nanoscale zero-valent iron (NZVI) to dechlorinate organic compounds in aqueous solutions has been demonstrated, the ability of NZVI to remove dense non-aqueous phase liquid (DNAPL) from source zones under flow-through conditions similar to a field scale application has not yet been thoroughly investigated. To gain insight on simultaneous DNAPL dissolution and NZVI-mediated dechlorination reactions after direct placement of NZVI into a DNAPL source zone, a combined experimental and modeling study was performed. First, a DNAPL tetrachloroethene (PCE) source zone with emplaced NZVI was built inside a small custom-made flow cell and the effluent PCE and dechlorination byproducts were monitored over time. Second, a model for rate-limited DNAPL dissolution and NZVI-mediated dechlorination of PCE to its three main reaction byproducts with a possibility for partitioning of these byproducts back into the DNAPL was formulated. The coupled processes occurring in the flow cell were simulated and analyzed using a detailed three-dimensional numerical model. It was found that subsurface emplacement of NZVI did not markedly accelerate DNAPL dissolution or the DNAPL mass-depletion rate, when NZVI at a particle concentration of 10g/L was directly emplaced in the DNAPL source zone. To react with NZVI the DNAPL PCE must first dissolve into the groundwater and the rate of dissolution controls the longevity of the DNAPL source. The modeling study further indicated that faster reacting particles would decrease aqueous contaminant concentrations but there is a limit to how much the mass removal rate can be increased by increasing the dechlorination reaction rate. To ensure reduction of aqueous contaminant concentrations, remediation of DNAPL contaminants with NZVI should include emplacement in a capture zone down-gradient of the DNAPL source.     

Nanoscale zero-valent iron (nZVI): aspects of the core-shell structure and reactions with inorganic species in water

Aspects of the core-shell model of nanoscale zero-valent iron (nZVI) and their environmental implications were examined in this work. The structure and elemental distribution of nZVI were characterized by X-ray energy-dispersive spectroscopy (XEDS) with nanometer-scale spatial resolution in an aberration-corrected scanning transmission electron microscope (STEM). The analysis provides unequivocal evidence of a layered structure of nZVI consisting of a metallic iron core encapsulated by a thin amorphous oxide shell. Three aqueous environmental contaminants, namely Hg(II), Zn(II) and hydrogen sulfide, were studied to probe the reactive properties and the surface chemistry of nZVI. High-resolution X-ray photoelectron spectroscopy (HR-XPS) analysis of the reacted particles indicated that Hg(II) was sequestrated via chemical reduction to elemental mercury. On the other hand, Zn(II) removal was achieved via sorption to the iron oxide shell followed by zinc hydroxide precipitation. Hydrogen sulfide was immobilized on the nZVI surface as disulfide (S(2)(2-)) and monosulfide (S(2-)) species. Their relative abundance in the final products suggests that the retention of hydrogen sulfide occurs via reactions with the oxide shell to form iron sulfide (FeS) and subsequent conversion to iron disulfide (FeS(2)). The results presented herein highlight the multiple reactive pathways permissible with nZVI owing to its two functional constituents. The core-shell structure imparts nZVI with manifold functional properties previously unexamined and grants the material with potentially new applications.     

Laboratory evaluation of zero-valent iron to treat water impacted by acid mine drainage

This study examines the applicability and limitations of granular zero-valent iron for the treatment of water impacted by mine wastes. Rates of acid-neutralization and of metal (Cu, Cd, Ni, Zn, Hg, Al, and Mn) and metalloid (As) uptake were determined in batch systems using simulated mine drainage (initial pH 2.3-4.5; total dissolved solids 14000-16000 mgl(-1)). Metal removal from solution and acid-neutralization occurred simultaneously and were most rapid during the initial 24 h of reaction. Reaction half-lives ranged from 1.50+/-0.09 h for Al to 8.15+/-0.36 h for Zn. Geochemical model results indicate that metal removal is most effective in solutions that are highly undersaturated with respect to pure-metal hydroxides suggesting that adsorption is the initial and most rapid metal uptake mechanism. Continued adsorption onto or co-precipitation with iron corrosion products are secondary metal uptake processes. Sulfate green rust was identified as the primary iron corrosion product, which is shown to be the result of elevated [SO(4)(2-)]/[HCO(3)(-)] ratios in solution. Reversibility studies indicate that zero-valent iron will retain metals after shifts in redox states are imposed, but that remobilization of metals may occur after the acid-neutralization capacity of the material is exhausted.     

High-level arsenite removal from groundwater by zero-valent iron

The objectives of this study were to conduct batch and column studies to (i) assess the effectiveness of zero-valent iron for arsenic remediation in groundwater, (ii) determine removal mechanisms of arsenic, and (iii) evaluate implications of these processes with regard to the stability of arsenic and long-term remedial performance of the permeable reactive barrier (PRB) technology. A high concentration arsenic solution (50 mg l(-1)) was prepared by using sodium arsenite (arsenic (III)) to simulate groundwater at a heavily contaminated Superfund site in the USA. Batch studies indicate that the removal of arsenic is a two-step reaction with fast initial disappearance of arsenite followed by a slow subsequent removal process. Flow-through columns were conducted at a flow rate of 17 ml h(-1) under reducing conditions for 6.6 mo. Kinetic analysis suggested that arsenic removal behaves as a zero-order reaction at high arsenic concentrations. Arsenic removal rate constants decreased with time and arsenic breakthrough was observed in the column study. Arsenic removal capacity of zero-valent iron was determined to be approximately 7.5 mg As/g Fe. Carbonate green rust was identified from the analysis of surface precipitates; arsenite uptake by green rust may be a major mechanism responsible for arsenic remediation by zero-valent iron. Analysis of HCl-extractable arsenic from iron samples indicated that approximately 28% of arsenic was in the form of arsenate suggesting that a surface oxidation process was involved in the arsenic removal with zero-valent iron.     

Controlled release, blind test of DNAPL remediation by ethanol flushing

A dense nonaqueous phase liquid (DNAPL) source zone was established within a sheet-pile isolated cell through a controlled release of perchloroethylene (PCE) to evaluate DNAPL remediation by in-situ cosolvent flushing. Ethanol was used as the cosolvent, and the main remedial mechanism was enhanced dissolution based on the phase behavior of the water-ethanol-PCE system. Based on the knowledge of the actual PCE volume introduced into the cell, it was estimated that 83 L of PCE were present at the start of the test. Over a 40-day period, 64% of the PCE was removed by flushing the cell with an alcohol solution of approximately 70% ethanol and 30% water. High removal efficiencies at the end of the test indicated that more PCE could have been removed had it been possible to continue the demonstration. The ethanol solution extracted from the cell was recycled during the test using activated carbon and air stripping treatment. Both of these treatment processes were successful in removing PCE for recycling purposes, with minimal impact on the ethanol content in the treated fluids. Results from pre- and post-flushing partitioning tracer tests overestimated the treatment performance. However, both of these tracer tests missed significant amounts of the PCE present, likely due to inaccessibility of the PCE. The tracer results suggest that some PCE was inaccessible to the ethanol solution which led to the inefficient PCE removal rates observed. The flux-averaged aqueous PCE concentrations measured in the post-flushing tracer test were reduced by a factor of 3 to 4 in the extraction wells that showed the highest PCE removal compared to those concentrations in the pre-flushing tracer test.     

Microwave-induced nanoscale zero-valent iron degradation of perchloroethylene and pentachlorophenol

Microwave (MW) is applied to enhance perchloroethylene (PCE) or pentachlorophenol (PCP) removal using zero-valent iron (ZVI; Fe⁰) as the dielectric medium. ZVI has a much higher dielectric loss factor (39.5) than other media; it is capable of absorbing MW radiation rapidly to speed up the release of electrons, leading to rises of the ZVI particle surface temperature. If the MW power is continued, excessive electricity will accumulated inside ZVI particles, resulting in sparks. The results show that during the initial 5 sec (700 W), the linear aliphatic PCE has a faster decomposing rate than the ringed PCP (82.0% vs. 4.8%) because less energy is required for decomposing the linear-chlorine bond (90 kcal mol^?1) than ring-chlorine bonds (95 kcal mol^?1). Later, the removal rate for either PCE or PCP remains the same when the exposure time is between 5 and 60 sec. Without MW irradiation, linear PCE molecules have larger surface area to contact ZVI, and hence they have better removal efficiencies than PCP molecules. Using Fe⁰ as a microwave dielectric medium to treat PCE or PCP is a new and worthwhile treatment technology; it is environmentally friendly, and its use will eliminate the secondary pollution.

Implications Nanoscale iron particles are characterized by high surface-area-to-volume ratios, high specific surface area, and high surface reactivity. With a much higher dielectric loss factor, it is capable of absorbing MW radiation rapidly to speed up the release of electrons, leading to rise in temperature. The time needed to achieve a satisfactory treatment is also reduced, leading to significant saving of energy consumption to make this method cost-effective and also environmentally friendly for the industry to pursuit sustainable development.     

Dechlorination of PCE in the presence of Fe0 enhanced by a mixed culture containing two Dehalococcoides strains

A mixed culture capable of supplying its energy requirements by the oxidation of zero-valent iron (Fe0) and concomitant reduction of chlorinated ethenes was established. The culture contained Dehalococcoides species as determined by polymerase chain reaction (PCR) with genus specific primers. The use of a newly designed ARDRA procedure and subsequent sequencing revealed the presence of two Dehalococcoides strains, one closely related to Dehalococcoides ethenogenes strain 195, a bacterium respiring with chlorinated ethenes, and one closely related to strain CBDB1 a chlorobenzene and dioxin dehalogenating anaerobe. The mixed culture was used to study dechlorination of tetrachloroethene (PCE) to ethene in the presence of Fe0. Whereas abiotic transformation of PCE by Fe0 led to incomplete dechlorination, the mixed culture mediated fast and complete dechlorination of PCE to ethene with Fe0 as electron donor. Compared to cultures with hydrogen added as electron donor, cultures with Fe0 as electron donor showed the same or higher rates of PCE dechlorination. Growth of the Dehalococcoides strains in the mixed culture is linked to the presence of Fe0 as electron donor and PCE as electron acceptor demonstrating that Dehalococcoides spp. play a pivotal role in the dechlorination of chlorinated ethenes in Fe0 systems.     

Field demonstration of surfactant-enhanced solubilization of DNAPL at Dover Air Force Base, Delaware

This study reports on a surfactant-based flood for tetrachloroethylene (PCE) removal from a control test cell at the Dover National Test Site. The surfactant formulation (sodium dihexyl sulfosuccinate (Aerosol-MA or AMA), isopropanol and calcium chloride) was able to achieve a high concentration of PCE in swollen micelles (supersolubilization) without vertical PCE migration. The hydraulic system included eight screened wells that were operated in both vertical circulation and line drive configurations. After 10 pore volumes of flushing, the overall PCE removal was 68% (65% of which corresponded to the surfactant flooding alone). In addition, the residual PCE saturation was reduced from 0.7% to 0.2%, and the concentration of PCE in the groundwater was reduced from 37-190 mg/L before the flushing to 7.3 mg/L after flooding. Recycling the surfactant solution reduced the required surfactant mass (and thus cost, and waste) by 90%. Close to 80% of the total PCE removal was obtained during the first five pore volumes which were operated in an upward vertical circulation flow scheme. No free oil phase was observed during the test. Further analysis of multilevel sampler data suggests that most of the trapped oil remaining in the cell was likely localized in secluded regions of the aquifer, which helps explain the lower PCE groundwater concentration after remedial activities. In summary, this field study demonstrated the feasibility of surfactant-enhanced remediation to reduce the mass in the source zone and significantly reduce the PCE aqueous concentration and therefore the risk associated with the contaminant plume.     

Ferrate(VI) oxidation of zinc-cyanide complex

Zinc-cyanide complexes are found in gold mining effluents and in metal finishing rinse water. The effect of Zn(II) on the oxidation of cyanide by ferrate(VI) (Fe(VI)O(4)(2-), Fe(VI)) was thus investigated by studying the kinetics of the reaction of Fe(VI) with cyanide present in a potassium salt of a zinc cyanide complex (K(2)Zn(CN)(4)) and in a mixture of Zn(II) and cyanide solutions as a function of pH (9.0-11.0). The rate-law for the oxidation of Zn(CN)(4)(2-) by Fe(VI) was found to be -d[Fe(VI)]/dt=k[Fe(VI)][Zn(CN)(4)(2-)](0.5). The rate constant, k, decreased with an increase in pH. The effect of temperature (15-45 degrees C) on the oxidation was studied at pH 9.0, which gave an activation energy of 45.7+/-1.5kJmol(-1). The cyanide oxidation rate decreased in the presence of the Zn(II) ions. However, Zn(II) ions had no effect on the cyanide removal efficiency by Fe(VI) and the stoichiometry of Fe(VI) to cyanide was approximately 1:1; similar to the stoichiometry in absence of Zn(II) ions. The destruction of cyanide by Fe(VI) resulted in cyanate. The experiments on removal of cyanide from rinse water using Fe(VI) demonstrated complete conversion of cyanide to cyanate.     

Removal of chromium from synthetic plating waste by zero-valent iron and sulfate-reducing bacteria.

Experiments were conducted to evaluate the potential of zero-valent iron and sulfate-reducing bacteria (SRB) for reduction and removal of chromium from synthetic electroplating waste. The zero-valent iron shows promising results as a reductant of hexavalent chromium (Cr+6) to trivalent chromium (Cr+3), capable of 100% reduction. The required iron concentration was a function of chromium concentration in the waste stream. Removal of Cr+3 by adsorption or precipitation on iron leads to complete removal of chromium from the waste and was a slower process than the reduction of Cr+6. Presence SRB in a completely mixed batch reactor inhibited the reduction of Cr+6. In a fixed-bed column reactor, SRB enhanced chromium removal and showed promising results for the treatment of wastes with low chromium concentrations. It is proposed that, for waste with high chromium concentration, zero-valent iron is an efficient reductant and can be used for reduction of Cr+6. For low chromium concentrations, a SRB augmented zero-valent iron and sand column is capable of removing chromium completely.     

Retention of Cd, Zn and Co on hydroxyapatite filters

This study qualifies and quantifies the immobilization of Cd, Zn and Co, (used as models of bivalent metal ions due to their relevant toxicity) in filters of synthetic hydroxyapatite (HAP) [Ca5(PO4)3OH]. They were flushed with solutions containing Cd (1 x 10(-5)M), Zn and Co (1 x 10(-4)M) at constant pH (8.6) and ionic strength (0.01 M). The concentration of these metal ions in the outlet was measured by ICP-OEM spectroscopy. The software PHREEQC (version 2.4.2) was used to model sorption process and the potential effect of salinity (KCl), pH, alkalinity (NaHCO3) and hardness (CaCl2) over the efficiency of the treatment. Results showed an excellent retention capacity of HAP for Cd, Zn and Co. Sorption data were successfully described considering a mix model of surface complexation onto phosphate surface groups, ionic exchange in surface calcium sites and the precipitation of ZnO. Co exchange and surface complexation constants (Kex and Kc) were taken from previous experiments, while KexCd=0.32 and KcCd=0.63 were estimated from our modeling results. Predictive values of metal ion sorption show that: (a) an increase in hardness does not play a significant role in the retention capacity of these metals on HAP; (b) an increase in alkalinity promotes the precipitation of MeCO3 which could alter the hydrodynamic of the column; (c) a decrease in pH and an increase in salinity inhibit ZnO precipitation enhancing Zn and Cd adsorption and decreasing Co retention on HAP.     

Sorption and reduction of tetrachloroethylene with zero valent iron and amphiphilic molecules

Effects of surfactants and natural organic matter (NOM) on the sorption and reduction of tetrachloroethylene (PCE) with zero valent iron (ZVI) were examined in this study. PCE reduction by ZVI depended on the ionic type of the surfactants. The removal of PCE and production of TCE with non-ionic Triton X-100 and cationic hexadecyltrimethyl-ammonium (HDTMA) at one-half and two times the critical micelle concentration (CMC) were 1.2-1.8 times higher than without surfactants because of the enhanced PCE partitioning and surface concentration by the sorbed surfactants. When anionic sodium dodecyl benzene sulfonate (SDDBS) at one-half and two times CMC and NOM at 20 mg l(-1) and 50 mg l(-1) concentrations were used, the removal of PCE doubled and TCE production decreased. In the presence of SDDBS, TCE production by ZVI was lower than with HDTMA and Triton X-100 while PCE removal was higher than with the other surfactants.     

Comparative study of H(2)O(2) and O3 effects on radiation treatment of TCE and PCE

The effects of H(2)O(2) and O(3) on the decomposition of trichloroethylene (TCE) and perchloroethylene (PCE) by gamma-rays (gamma-rays) were investigated in this work. The combined gamma-rays/O(3) process showed a synergistic effect and enhanced the removal of TCE and PCE compared with gamma-rays alone, but, the gamma-rays/H(2)O(2) process did not increase the removal. This interesting result was successfully identified by an electron paramagnetic resonance spectroscopy/spin-trapping method that can quantify hydroxyl radicals, which is directly related to the efficiency of TCE and PCE decomposition. For gamma-rays/H(2)O(2) system, there was no difference of hydroxyl radical production between gamma-rays alone and gamma-rays/H(2)O(2). This indicates gamma-rays cannot activate H(2)O(2) to produce hydroxyl radicals and this causes no increase of TCE and PCE removals. To the contrary, the production of hydroxyl radicals was obviously increased in the case of gamma-rays/O(3) process. This suggests additional hydroxyl radicals are produced from the reaction of O(3) with the irradiation products of water such as hydrated electrons, hydrogen atoms, etc. and this accelerates the removal of TCE and PCE.     

Effect of metal ions and humic acid on the dechlorination of tetrachloroethylene by zerovalent iron

The dechlorination of tetrachloroethylene (PCE) by zerovalent iron (Fe(0)) in the presence of metal ions and humic acid was investigated. In the absence of metal ion and humic acid, 64% of the initial PCE was dechlorinated after 125 h with the production of ethane and ethene as the major end products. The dechlorination followed pseudo-first-order kinetics and the normalized surface rate constant (k(SA)) for PCE dechlorination was (3.43+/-0.61)x10(-3)lm(-2)h(-1). Addition of metal ions enhanced the dechlorination efficiency and rate of PCE, and the enhancement effect followed the order Ni(II)>Cu(II)>Co(II). The k(SA) for PCE dechlorination in the presence of metal ions were 2-84 times higher than that in the absence of metal ions. X-ray photoelectron spectroscopy (XPS) showed that Cu(II) and Ni(II) were reduced by Fe(0) to zerovalent metals, and resulted in the formation of bimetallic system to accelerate the dechlorination reaction. On the contrary, humic acid out-competed the reactive sites on iron surface with PCE, and subsequently decreased the dechlorination efficiency and rate of PCE by Fe(0). However, the reactivity of Fe(0) for PCE dechlorination in the presence of metal ions and humic acid increased by a factor of 3-161 when compared to the iron system containing humic acid alone. Since humic acid and metal ions are the most often found co-existing compounds in the contaminated aquifers with chlorinated hydrocarbons, results obtained in this study is useful to better understand the feasibility of using Fe(0) for long-term application to the remediation of contaminated sites.     

Mechanisms of phosphorus removal by cement-bound ochre pellets

Hydrous ferric oxide (here termed ‘ochre’) sludge, an abundant waste product produced from the treatment of acid mine drainage (AMD), was used in this study for the removal of phosphorus (in the form of phosphate ions) from contaminated waters. The phosphorus uptake capacities of both raw and pelletized AMD solids were compared using batch and column tests. Addition of a cement binder to the AMD solids during pellet production led to significantly increased P-loading of the resultant solids compared to the raw sludge. Additionally, the pellets were found to continue to remove P in tests up to 7 d in duration whereas the unbound AMD sludge appeared to approach equilibrium with phosphate solution after approximately 60 min of contact time. In line with previous studies P uptake by the AMD solids was found to be primarily via adsorption. By contrast calcium phosphate precipitation was found to be the dominant removal mechanism for the cement-bound ochre pellets with a relatively small proportion of removal attributable to the AMD solids. SEM–EDX analysis of the surface of used pellets showed a Ca:P molar ratio close to that of hydroxyapatite (HAP). Continuous column tests on these pellets showed a rapid decrease in P removal capacity by the pellets over time, attributable to the formation of a passivating HAP surface layer.