Preliminary Large Scale Mitigation of 3-Monochloropropane-1, 2-diol (3-MCPD) Esters and Glycidyl Esters in Palm Oil.

Approximately 900 tonne of crude palm oil (CPO) underwent washing using 5 to 10% hot water (90 to 95°C) at a palm oil mill. The aim of the CPO washing was to eliminate and/or reduce total chlorine content present in the conventional CPO, as it is known as the main precursor for the formation of 3-monochloropropane-1, 2-diol esters (3-MCPDE). By a simple hot water washing, more than 85% of the total chlorine was removed. However, washing did not have significant (p > 0.05) effect on other oil quality parameters such as the deterioration of bleachability index (DOBI), free fatty acid (FFA) content and diacylglycerol (DAG) content of the oil. The latter has been established as the main precursor for glycidyl esters (GE) formation. The treated CPO was then transported using tankers and further refined at a commercial refinery. Refining of washed CPO resulted in significantly (p < 0.05) lower formation of 3-MCPDE, but GE content remained slightly high. Post-treatment of refined oil significantly reduced the GE content (p < 0.05) to an acceptable level whilst almost maintaining the low 3-MCPDE level. The study has proven that water washing of CPO prior to refining and subsequent post-refining is so far the most effective way to produce good quality refined oil with considerably low 3-MCPDE and GE contents. Dry fractionation of refined palm oil showed these contaminants partitioned more into the liquid olein fraction compared to the stearin fraction.

Removal of phenol and chlorine from wastewater using steam activated biomass soot and tire carbon black.

This study aims to demonstrate a novel method for removing toxic chemicals using soot produced from wood and herbaceous biomass pyrolyzed in a drop tube reactor and tire pyrolytic carbon black. The influence of ash content, nanostructure, particle size, and porosity on the filter efficiency of steam activated carbon materials was studied. It has been shown for the first time that steam activated soot and carbon black can remove phenol and chloride with filter efficiencies as high as 95%. The correlation of filter efficiency to material properties showed that the presence of alkali and steam activation time were the key parameters affecting filter efficiencies. This study shows that steam activated biomass soot and tire carbon black are promising alternatives for the cleaning of wastewater.

Effect of silver or copper middle layer on the performance of palladium modified nickel foam electrodes in the 2-chlorobiphenyl dechlorination.

To enhance the activity of chemi-deposited palladium/nickel foam (Pd/Ni) electrodes used for an electrochemical dechlorination process, silver or copper was deposited electrochemically onto the nickel foam substrate (to give Ag/Ni or Cu/Ni) before the chemical deposition of palladium. The physicochemical properties of the resulting materials (Pd/Ni, Pd/Ag/Ni and Pd/Cu/Ni) were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), and their electrochemical catalytic activities were evaluated by monitoring the electrochemical dechlorination of 2-chlorobiphenyl (2-CB) in strongly alkaline methanol/water solution. The results show that the Pd/Ag/Ni and Pd/Cu/Ni electrodes had consistently higher electrocatalytic activities and current efficiencies (CEs) compared with the untreated Pd/Ni electrode. The Pd/Ag/Ni electrode exhibited the highest activity. The dechlorination was also studied as a function of Pd loading, the Ag or Cu interlayer loadings, and the current density. The Pd loading and the interlayer loadings both had positive effects on the dechlorination reaction. Increasing the current density increased the reaction rate but reduced the CE. The improvement of the electrocatalytic activities of the Pd/Ni electrode by applying the interlayer of Ag or Cu resulted from the enlargement of the effective surface area of the electrode and the adjustment of the metal-H bond energy to the appropriate value, as well as the effective adsorption of 2-CB on Ag. Moreover, the high catalytic activity of the Pd/Ag/Ni electrode was maintained after six successive cyclic experiments, whereas Pd/Cu/Ni electrodes deactivate severely under the same conditions.

Dechlorination of short chain chlorinated paraffins by nanoscale zero-valent iron.

In this study, nanoscale zero-valent iron (NZVI) particles were synthesized and used for the reductive dehalogenation of short chain chlorinated paraffins (SCCPs) in the laboratory. The results show that the dechlorination rate of chlorinated n-decane (CP(10)) by NZVI increased with decreased solution pH. Increasing the loading of NZVI enhanced the dechlorination rate of CP(10). With an increase in temperature, the degradation rate increased. The reduction of CP(10) by NZVI was accelerated with increasing the concentration of humic acid up to 15 mg/L but then was inhibited. The dechlorination of CP(10) within the initial 18 h followed pseudo-first order rate model. The formation of intermediate products indicates a stepwise dechlorination pathway of SCCPs by NZVI. The carbon chain length and chlorination degree of SCCPs have a polynominal impact on dechlorination reactions.

A field comparison of two reductive dechlorination (zero-valent iron and lactate) methods.

Two parallel pilot experiments were performed at Kurivody (Czech Republic) in order to compare two reductive remedial technologies for chlorinated ethenes - microbial dehalogenation assisted by lactate and chemical dehalogenation with zero-valent iron (nZVI) nanoparticles. The methods were applied at a site contaminated by tetrachlorethylene (PCE) and trichlorethylene (TCE), with total concentrations from 10 to 50 mg/l. Concentrations of chlorinated ethenes, inorganic components of interest, pH and oxidation reduction potential (ORP) were monitored at the site for a period up to 650 days. The method of biological reductive dechlorination supported by lactate showed a considerable removal of PCE and TCE, but temporary accumulation of transient reaction product 1,2-cis-dihloroethene. Reductive dechlorination with nZVI showed a significant reduction in the concentration of chlorinated ethenes without a formation of intermediate products. The development of pH showed only small changes due to the high buffering capacity of the aquifer. Both methods differ in the initial development of ORP, but over the long term showed similar values around 100 mV. Significant differences were observed for chemical oxygen demand, where groundwater after the application of nZVI showed no change in comparison to the application of lactate. The reductive effects of both agents were verified by changes in inorganic compound concentrations.

Ecotoxicological screening of reclaimed disinfected wastewater by Vibrio fischeri bioassay after a chlorination-dechlorination process.

It is well known that different substances can react with chlorine in a water disinfection process to produce disinfection by-products (DBPs). Some of these substances have proven to be carcinogenic in humans and animals. Because it is not possible to detect all DBPs produced in chlorinated wastewater, toxicity tests have been proposed as a useful tool for screening toxic chemicals in treated wastewater. In this study, the Microtox bioassay with Vibrio fischeri was used to evaluate the formation of toxic by-products in wastewater, after a chlorination-dechlorination disinfection treatment. All the variables were found to be normally distributed, so analysis of variance could be directly applied without transformation of variables. Significant correlations were obtained between toxicity values and total carbon, total inorganic carbon, total nitrogen, chlorine, and pH. In contrast, total organic carbon, chemical oxygen demand, electrical conductivity and turbidity had no effect on toxicity formation. Toxicity increased with the Cl2:NH4+ ratio at a higher chlorine concentration released from combined chlorine. Regression models provided a good fit for effective concentration (EC50) as a function of total carbon and total nitrogen, after 5, 10, and 15 min of exposure. These models had greater multiple determination coefficients than previously reported for similar studies, without autocorrelation in the residuals as indicated by the Durbin-Watson statistic test. The measured and predicted ecotoxicity values were strongly correlated.

Recycling of transformer oil contaminated by polychlorinated biphenyls (PCBs) using catalytic hydrodechlorination.

Catalytic hydrodechlorination of polychlorinated biphenyls (PCBs) in the presence of transformer oil was carried out in a batch mode to detoxify PCBs and to recycle the treated oil. Various metal supported catalysts, including 0.98 wt% Pt, 0.79 wt% Pd and 12.8 wt% Ni on gamma -alumina (gamma -Al(2)O(3)) support, and 57.6 wt% Ni on silicon oxide-aluminum oxide (SiO(2)-Al(2)O(3)) support were used for the hydrodechlorination. Metal particle size of the Pt catalyst was 2.0 nm and metal particle sizes of the Pd and Ni catalysts were in the range of 6.4-6.9 nm. Various supercritical fluids, supercritical carbon dioxide (scCO(2)), supercritical propane (scPropane), supercritical dimethyl ether (scDME) and supercritical isobutane (scIsobutane) were used as reaction media. PCBs conversion, dechlorination degree of PCBs, was measured using gas chromatograph (GC) with an electron capture detector (ECD). The hydrodechorination degree increased in the order Ni > Pd > Pt, possibly due to higher metal loading and larger metal size of the Ni catalysts. At temperatures below 175 degrees C, scCO(2) was effective as the reaction media for the catalytic hydrodechlorination of PCBs in the presence of the transformer oil. However, PCBs conversion decreased significantly when the hydrodechlorination was carried out in a homogeneous phase with using scPropane, scDME or scIsobutane as a reaction medium. This was attributed to dilution effect of the supercritical fluids. Molecular weights of the transformer oils before and after the catalytic hydrodechlorination were analyzed using high-performance size exclusion chromatography (HPSEC). The molecular weight of the treated oil with 100 % PCBs conversion did not change after the catalytic hydrodechlorination at 200 degrees C. This process has proven to be effective to detoxify PCBs containing transformer oil and to recycle the treated oil.

Poly(ethylene glycol) enhanced dehydrochlorination of poly(vinyl chloride).

Poly(ethylene glycol) (PEG), an environment-friendly reaction medium, has been adopted to accelerate the dehydrochlorination of poly(vinyl chloride) (PVC). Experimental results demonstrated that at 210 degrees C for 1h the dechlorination degree was as high as 74.2% for PVC/PEG, while for PVC only 50.0%. Moreover, from thermogravimetric analysis, it was found that for PVC/PEG the decomposition of PVC corresponding to the dehydrochlorination stage shifted to lower temperatures compared with that of pure PVC, suggesting some interactions exist between PEG and PVC that caused the faster dehydrochlorination rate. In addition, during this process, no waste byproducts such as KCl have been produced, and satisfactory recyclability of PEG (10 cycles) has been obtained.

Reductive dechlorination of trichloroethylene by combining autotrophic hydrogen-bacteria and zero-valent iron particles.

The objective of this study was to evaluate the dechlorination rate (from an initial concentration of 180 micromol l(-1)) and synergistic effect of combining commercial Fe(0) and autotrophic hydrogen-bacteria in the presence of hydrogen, during TCE degradation process. In the batch test, the treatment using Fe(0) in the presence of hydrogen (Fe(0)/H(2)), showed more effective dechlorination and less iron consumption than Fe(0) utilized only (Fe(0)/N(2)), meaning that catalytic degradation had promoted transformation of TCE, and the iron was protected by cathodic hydrogen. The combined use of Fe(0) and autotrophic hydrogen-bacteria was found to be more effective than did the individual exercise even though the hydrogen was insufficient during the batch test. By the analysis of XRPD, the crystal of FeS transformed by sulfate reducing bacteria (SRB) was detected on the surface of iron after the combined treatment. The synergistic impact was caused by FeS precipitates, which enhanced TCE degradation through catalytic dechlorination. Additionally, the dechlorination rate coefficient of the combined method in MFSB was 3.2-fold higher than that of iron particles individual use. Results from batch and MFSB experiments revealed that, the proposed combined method has the potential to become a cost-effective remediation technology for chlorinated-solvent contaminated site.

Manipulating the size and dispersibility of zerovalent iron nanoparticles by use of carboxymethyl cellulose stabilizers.

Zerovalent iron (ZVI) nanoparticles of various sizes were synthesized by applying various types of carboxymethyl cellulose (CMC) as a stabilizer. At an initial Fe2+ concentration of 0.1 g/L and with 0.2% (w/w) of CMC (Mr = 90 000), nanoparticles with a hydrodynamic diameter of 18.6 nm were obtained. Smaller nanoparticles were obtained as the CMC/Fe2+ molar ratio was increased. When the initial Fe2+ concentration was increased to 1 g/L, only 1/4 of the CMC was needed to obtain similar nanoparticles. On an equal weight basis, CMC with a greater Mr or higher D.S. (degree of substitution) gave smaller nanoparticles, and lower the synthesizing temperature favored the formation of smaller nanoparticles. It is proposed that CMC stabilizes the nanoparticles through the accelerating nucleation of Fe atoms during the formation of ZVI nanoparticles and, subsequently, forms a bulky and negatively charged layer via sorption of CMC molecules on the ZVI nanoparticles, thereby preventing the nanoparticles from agglomeration through electrosteric stabilization. In agreement with the classical coagulation theory, the presence of high concentrations of cations (Na+ and Ca2+) promoted agglomeration of the nanoparticles. The strategy for manipulating the size of the ZVI nanoparticles may facilitate more effective applications of ZVI nanoparticles for in situ dechlorination in soils and groundwater.

Effects of carbonate precipitates on long-term performance of granular iron for reductive dechlorination of TCE.

Long-term column experiments were conducted to evaluate the effects of secondary carbonate minerals on permeability and reactivity of commercial granular iron treating trichloroethene (TCE). The results showed that carbonate precipitates caused a decrease in reactivity of the iron, and spatially and temporally varying reactivity loss resulted in migration of mineral precipitation fronts, as well as profiles of TCE, pH, alkalinity, calcium, and dissolved iron. In the columns receiving solutions of dissolved calcium carbonate, porosity gradually decreased in proportion to the source concentrations, as carbonate minerals accumulated. However, the rate of porosity loss slowed over time because of the declining reactivity of the iron. Thus, secondary minerals are not likely to accumulate to the extent that there is a substantial reduction in hydraulic conductivity. The reactivity of the iron was found to decrease as an exponential function of the carbonate mineral volume fraction. This changing reactivity of iron should be incorporated into predictive models for improved designs of iron permeable reactive barriers (PRBs).

Effects of the electrode arrangements on reductive dechlorination of trichloroethylene in an electro-enhanced iron wall.

This study examined the factors that influence the reductive dechlorination of trichloroethylene (TCE) when direct current is externally supplied to a laboratory scale iron wall. Experimental results indicated that an anode electrode was placed in contact with the iron filling near the inlet of the column, and then a cathode was located on the top of the column. Excellent TCE degradation efficiency was displayed. The surface of the iron particles was acid-washed by H+, owing to water oxidation around the anode, and large quantities of Fe2+ were produced as a reductant which enhanced the TCE degradation, due to iron corrosion caused by the supply of external electrons. The cathode should be placed in sand fill atop the iron filling in order to avoid the formation of iron (hydr) oxide precipitates on the surface of the iron particles when the pH increases as a result of the release of OH+ around the cathode. Due to more H+ being released, which benefited the acid-washing of the iron filling, the TCE removal efficiency increased from 32% to 100% when the electric potential increased to 60V. However, black precipitates of iron (hydr) oxide were observed coated on the iron surface, causing the blocking of pores in the iron wall with the increase in the electric potential application. The efficiency of TCE degradation was almost equal regardless of groundwater velocity when direct current was applied to the iron wall. Based on observations of TCE degradation during long-term operations, the TCE removal efficiency in the effluent reached 100% after seven days of operation and maintained this high level after 25 days of operation. Thus, iron wall by electroremediation displayed excellent potential for development in long-term operations.

Enhanced reductive dechlorination in columns treated with edible oil emulsion.

The effect of edible oil emulsion treatment on enhanced reductive dechlorination was evaluated in a 14 month laboratory column study. Experimental treatments included: (1) emulsified soybean oil and dilute HCl to inhibit biological activity; (2) emulsified oil only; (3) emulsified oil and anaerobic digester sludge; and (4) continuously feeding soluble substrate. A single application of emulsified oil was effective in generating strongly reducing, anaerobic conditions for over 14 months. PCE was rapidly reduced to cis-DCE in all three live columns. Bioaugmentation with a halorespiring enrichment culture resulted in complete dechlorination of PCE to ethene in the soluble substrate column (yeast extract and lactate). However, an additional treatment with a pulse of yeast extract and bioaugmentation culture was required to stimulate complete dechlorination in the emulsion treated columns. Once the dechlorinating population was established, the emulsion only column degraded PCE from 90-120 microM to below detection with concurrent ethene production in a 33 day contact time. The lower biodegradation rates in the emulsion treated columns compared to the soluble substrate column suggest that emulsified oil barriers may require a somewhat longer contact time for effective treatment. In the HCl inhibited column, partitioning of PCE to the retained oil substantially delayed PCE breakthrough. However, reduction of PCE to more soluble degradation products (cis-DCE, VC and ethene) greatly reduced the impact of oil-water partitioning in live columns. There was only a small decline in the hydraulic conductivity (K) of column #1 (low pH+emulsion, K(final)/K(initial)=0.57) and column #2 (live+emulsion, K(final)/K(initial)=0.73) indicating emulsion injection did not result in appreciable clogging of the clayey sand. However, K loss was greater in column #3 (sludge+emulsion, K(final)/K(initial)=0.12) and column #4 (soluble substrate, K(final)/K(initial)=0.03) indicating clogging due to biomass and/or gas production can be significant.

Comparison of pulsed and continuous addition of H2 gas via membranes for stimulating PCE biodegradation in soil columns.

Column experiments were performed to investigate a technology for remediating aquifers contaminated with chlorinated solvents. The technology involves installation of hollow-fiber membranes in the subsurface to supply hydrogen gas (H2) to groundwater to support biological reductive dechlorination in situ. Three laboratory-scale columns [control (N2 only), continuous H2, and pulsed H2] were packed with aquifer material from a trichloroethene (TCE)-contaminated wetland in Minnesota and supplied with perchloroethene (PCE)-contaminated synthetic groundwater. The main goals of the research were: (1) evaluate the long-term performance of the H2 supply system and (2) compare the effects of pulsed (4 h on, 20 h off) versus continuous H2 supply (lumen partial pressure approximately 1.2 atm) on PCE dechlorination and production of by-products (i.e. methane and acetate). The silicone-coated fiberglass membranes employed in these experiments were robust, delivering H2 steadily over the entire 349-day experiment. Methane production decreased when H2 was added in a pulsed manner. Nevertheless, the percentage of added H2 used to support methanogenesis was similar in both H2-fed columns (92-93%). For much of the experiment, PCE dechlorination (observed end product = dichloroethene) in the continuous and pulsed H2 columns was comparable, and enhanced in comparison to the natural attenuation observed in the control column. Dechlorination began to decline in the pulsed H2 column after 210 days, however, while dechlorination in the continuous H2 column was sustained. Acetate was detected only in the continuous H2 column, at concentrations of up to 36 microM. The results of this research suggest that in situ stimulation of PCE dechlorination by direct H2 addition requires the continuous application of H2 at high partial pressures, favoring the production of bioavailable organic matter such as acetate to provide a carbon source, electron donor, or both for dechlorinators. Unfortunately, this strategy has proven to be inefficient, with the bulk of the added H2 used to support methanogenesis.

Congener-specific dechlorination of dissolved PCBs by microscale and nanoscale zerovalent iron in a water/methanol solution.

Polychlorinated biphenyl (PCB)-contaminated sediments remain a significantthreatto humans and aquatic ecosystems. Dredging and disposal is costly, so viable in situ technologies to dechlorinate PCBs are needed. This study demonstrates that nanoscale zerovalent iron (ZVI) dechlorinates PCBs to lower-chlorinated products under ambient conditions, provides insight into structure-activity relationships between PCB isomers, and compares the reactivity of nanoscale ZVI to that of palladized microscale ZVI. Six PCB congeners were studied (22', 34', 234, 22'35', 22'45', and 33'44') to compare the initial rate of dechlorination of each and to monitor the order in which chlorines are removed. Using 200 g/L of nanoscale ZVI in a 30% MeOH/water mixture, observed surface-area-normalized pseudo-first-order PCB dechlorination rate constants ranged from 1 x 10(-6) to 5.5 x 10(-4) L yr(-1) m(-2) depending on the PCB congener tested. Using 200 g/L of palladized (0.05 wt %) microscale ZVI, surface-area-normalized pseudo-first-order PCB dechlorination rate constants were significantly faster and ranged from 3.8 x 10(-2) to 1.7 x 10(-1) L yr(-1) m(-2), but these rates were not sustainable. For nanoscale ZVI, nonorthosubstituted congeners had faster initial dechlorination rates than orthosubstituted congeners in the same homologue group. Chlorines in the para and meta position were predominantly removed over chlorines in the ortho position, which suggests that more-toxic coplanar PCB congeners are not likely to form from less-toxic noncoplanar, orthosubstituted congeners. Complete dechlorination was not observed over the course of the experiments. PCB dechlorination is rapid enough that nanoscale ZVI may offer novel in situ remedial alternatives for PCB-contaminated sediments.

Understanding reduction of carbon tetrachloride at nickel surfaces.

Nickel has been found to be an effective cathode material and catalyst for reductive destruction of chlorinated solvents in contaminated water. This study investigated reductive dechlorination of carbon tetrachloride (CT) at a nickel rotating disk electrode using chronoamperometry and electrochemical impedance spectroscopy. Chronoamperometry experiments were performed to determine rates of CT reduction as a function of the electrode potential, pH, CT concentration, and temperature. The reaction products of CT dechlorination were 95 +/- 4% methane and 4.1 +/- 2.5% chloroform. Only trace levels of methylene chloride and chloromethane were produced, indicating that sequential hydrogenolysis was not the predominant pathway for methane production. Electrochemical impedance spectroscopy showed that the rate-limiting step for methane production was the transfer of the first electron to a physically adsorbed CT molecule. The temperature independence of the electron transfer coefficient and the decreasing activation energy with decreasing electrode potential indicated that the rate-limiting step involved an outer-sphere electron transfer. At neutral pH values, oxides inactivated much of the electrode surface for both CT reduction and hydrogen evolution. At lower pH values, oxide dissolution served to increase the electroactive surface area of the disk electrode. Anson analysis and kinetic modeling showed that CT adsorption to electroactive sites was a nonlinear function of the CT concentration and was in equilibrium with the bulk solution. CT dechlorination rates on nickel electrodes were 16 times slower than those on iron electrodes under similar conditions. However, CT reactions at nickel surfaces produced predominantly methane as the first detectable product, while reduction at iron surfaces produced chloroform. These results suggest that, although nickel is not a catalyst for the rate-limiting step for CT dechlorination, it may serve a catalytic role in subsequent reaction steps.