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.

Understanding the electrode reaction process of dechlorination of 2,4-dichlorophenol over Ni/Fe nanoparticles: Effect of pH and 2,4-dichlorophenol concentration.

Herein, with the exploitation of iron and nickel electrodes, the 2,4-dichlorophenol (2,4-DCP) dechlorinating processes at the anode and cathode, respectively, were separately studied via various electrochemical techniques (e.g., Tafel polarization, linear polarization, electrochemical impedance spectroscopy). With this in mind, Ni/Fe nanoparticles were prepared by chemical solution deposition, and utilized to test the dechlorination activities of 2,4-DCP over a bimetallic system. For the iron anode, the results showed that higher 2,4-DCP concentration and solution acidity aggravated the corrosion within the electrode. The charge transfer resistance (Rct) values of the iron electrode were 703, 473, 444, and 437 Ω∙cm2 for the initial 2,4-DCP concentrations of 0, 20, 50, and 80 mg/L, respectively. When the bulk pH of the 2,4-DCP solution varied from 3.0, 5.0 to 7.0, the corresponding Rct values were 315, 376, and 444 Ω∙cm2, respectively. For the nickel cathode, the reduction current densities on the electrode at -0.75 V (vs. saturated calomel electrode) were 80, 106, and 111 µA/cm2, for initial 2,4-DCP concentrations of 40, 80, and 125 mg/L. The dechlorination experiments demonstrated that when the initial pH of the solution was 7.0, 5.0, and 3.0, the dechlorination percentage of 2,4-DCP by Ni/Fe nanoparticles was 62%, 69%, and 74%, respectively, which was in line with the electrochemical experiments. 10 wt.% Ni loading into Ni/Fe bimetal was affordable and gave a good dechlorination efficiency of 2,4-DCP, and fortunately the Ni/Fe nanoparticles remained comparatively stable in the dechlorination processes at pH 3.0.

Full simulation of disinfection stage in a water recycling plant using low-cost, hybrid 3-dimensional computational fluid dynamics.

Water purification is a crucial process in the operation of a municipality. Ensuring that water treatment plants are meeting regulatory requirements is a vital, but complicated and costly process. Because water treatment plant influent and effluent rates are demand driven, and vary both diurnally and seasonally, controlling flow rates for the disinfection stage can be challenging both operationally and economically. Thus, performing large-scale field experiments to verify water quality regulatory criteria such as modal transport time of conservative tracers in a chlorine disinfection contact tank under extreme operating conditions can range from difficult and costly to impossible. In this paper, a computational fluid dynamics (CFD) approach is used to verify the compliance of a water reclamation plant disinfection stage with respect to modal time. CFD allows a large parameter space to be tested without the need to build large physical models or taking functioning systems in a treatment plant offline. This can save facilities large amounts of time and money when designing, optimizing, and developing plants or checking compliance. This paper introduces a hybrid approach of computational analysis of a water reclamation plant's chlorine contact tank in Southern California. The method uses a hybrid approach which combines three-dimensional CFD with hydraulic grade line analysis of the open water surface. Verification cases were compared to experimental measurements at a functioning, full-scale plant with modal contact time differences below 15%. The method was then used to predict residence time distributions (RTDs) for cases which could not be artificially induced at the plant, but represented peak flow conditions that could be expected. PRACTITIONER POINTS: The hybrid 3-dimensional CFD method allows low cost simulation of the disinfection stage. By using head loss calculations to properly define the water level at each section, a steady-state single phase flow simulation can be run in 3D without the need to scale down geometries. This allows for more accurate transport results and parameter studies.

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.

Fe-Ti/Fe (II)-loading on ceramic filter materials for residual chlorine removal from drinking water.

Ceramic filter material was prepared with silicon dioxide (SiO2), which was recovered from red mud and then modified with Fe (II) and Fe-Ti bimetal oxide. Ceramic filter material can be used to reduce the content of residual chlorine from drinking water. The results showed that after a two-step leaching process with 3 M hydrochloric acid (HCl) and 90% sulfuric acid (H2SO4), the recovery of SiO2 exceeded 80%. Fe (II)/Fe-Ti bimetal oxide, with a high adsorption capacity of residual chlorine, was prepared using a 3:1 M ratio of Fe/Ti and a concentration of 0.4 mol/L Fe2+. According to the zeta-potential, scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) analysis, Fe (II) and Fe-Ti bimetal oxide altered the zeta potential and structural properties of the ceramic filter material. There was a synergistic interaction between Fe and Ti in which FeOTi bonds on the material surface and hydroxyl groups provided the active sites for adsorption. Through a redox reaction, Fe (II) transfers hypochlorite to chloride, and FeOTiCl bonds were formed after adsorption.

Dechlorination of three tetrachlorobenzene isomers by contaminated harbor sludge-derived enrichment cultures follows thermodynamically favorable reactions.

Dechlorination patterns of three tetrachlorobenzene isomers, 1,2,3,4-, 1,2,3,5-, and 1,2,4,5-TeCB, were studied in anoxic microcosms derived from contaminated harbor sludge. The removal of doubly, singly, and un-flanked chlorine atoms was noted in 1,2,3,4- and 1,2,3,5-TeCB fed microcosms, whereas only singly flanked chlorine was removed in 1,2,4,5-TeCB microcosms. The thermodynamically more favorable reactions were selectively followed by the enriched cultures with di- and/or mono-chlorobenzene as the main end products of the reductive dechlorination of all three isomers. Based on quantitative PCR analysis targeting 16S rRNA genes of known organohalide-respiring bacteria, the growth of Dehalococcoides was found to be associated with the reductive dechlorination of all three isomers, while growth of Dehalobacter, another known TeCB dechlorinator, was only observed in one 1,2,3,5-TeCB enriched microcosm among biological triplicates. Numbers of Desulfitobacterium and Geobacter as facultative dechlorinators were rather stable suggesting that they were not (directly) involved in the observed TeCB dechlorination. Bacterial community profiling suggested bacteria belonging to the phylum Bacteroidetes and the order Clostridiales as well as sulfate-reducing members of the class Deltaproteobacteria as putative stimulating guilds that provide electron donor and/or organic cofactors to fastidious dechlorinators. Our results provide a better understanding of thermodynamically preferred TeCB dechlorinating pathways in harbor environments and microbial guilds enriched and active in anoxic TeCB dechlorinating microcosms.

Analysis of Small Ions with Capillary Electrophoresis.

Small inorganic ions are easily separated through capillary electrophoresis because they have a high charge-to-mass ratio and suffer little from some of the undesired phenomenon affecting higher molecular weight species like adsorption to the capillary wall, decomposition, and precipitation. This chapter is focused on the analysis of small ions other than metal ions using capillary electrophoresis. Methods are described for the determination of ions of nitrogen, phosphorus, sulfur, fluorine, chlorine, bromine, and iodine.

Diverse Reductive Dehalogenases Are Associated with Clostridiales-Enriched Microcosms Dechlorinating 1,2-Dichloroethane.

The achievement of successful biostimulation of active microbiomes for the cleanup of a polluted site is strictly dependent on the knowledge of the key microorganisms equipped with the relevant catabolic genes responsible for the degradation process. In this work, we present the characterization of the bacterial community developed in anaerobic microcosms after biostimulation with the electron donor lactate of groundwater polluted with 1,2-dichloroethane (1,2-DCA). Through a multilevel analysis, we have assessed (i) the structural analysis of the bacterial community; (ii) the identification of putative dehalorespiring bacteria; (iii) the characterization of functional genes encoding for putative 1,2-DCA reductive dehalogenases (RDs). Following the biostimulation treatment, the structure of the bacterial community underwent a notable change of the main phylotypes, with the enrichment of representatives of the order Clostridiales. Through PCR targeting conserved regions within known RD genes, four novel variants of RDs previously associated with the reductive dechlorination of 1,2-DCA were identified in the metagenome of the Clostridiales-dominated bacterial community.

Evaluation of the formation of oxidants and by-products using Pt/Ti, RuO2/Ti, and IrO2/Ti electrodes in the electrochemical process.

The aim of this study was to evaluate the formation of oxidants and by-products by using different electrode materials, such as Pt/Ti, RuO2/Ti, and IrO2/Ti, in the electrochemical process. The harmful by-products ClO3- and ClO4- were formed during the electrolysis of a Cl- electrolyte solution, as well as active chlorine, which is the most common water disinfectant. With regard to drinking water treatment, the most efficient electrode was defined as that leading to a higher formation of active chlorine and a lower formation of hazardous by-products. Overall, it was found that the Pt/Ti electrode should not be used for drinking water treatment applications, while the IrO2/Ti and RuO2/Ti electrodes are ideal for use.

Carbon and chlorine isotope fractionation during Fenton-like degradation of trichloroethene.

Dual isotope approach has been proposed as a viable tool for characterizing and assessing in situ contaminant transformation, however, little data is currently available on its applicability to chlorinated ethenes. This study determined carbon and chlorine isotope fractionation during Fenton-like degradation of trichloroethene (TCE). Carbon and chlorine isotope enrichment factors were εC=-2.9 ± 0.3‰ and εCl=-0.9 ± 0.1‰, respectively. An observed small secondary chlorine isotope effect (AKIECl=1.001) was consistent with an initial transformation by adding hydroxyl radicals (OH) to CC bonds without cleavage of CCl bonds. The relative change in carbon and chlorine isotope ratios (Δ=Δδ(13)C/Δδ(37)Cl) was calculated to be 3.1 ± 0.2, approximately equal to the ratio of chlorine and carbon isotope enrichment factors (εC/εCl=3.2). The similarity of the Δ (or εC/εCl) values between Fenton-like degradation and microbial reductive dechlorination of TCE was observed, indicating that application of solely dual isotope approach may be limited in distinguishing the two transformation pathways.

New and effective multi-element alpha-hematite systems for reduction of trichloroethylene.

The reactivity of different alpha-hematite (alpha-Fe203) systems for dechlorination of trichloroethylene (TCE) in the presence of Fe(II) and CaO was investigated. Initially different experiments were conducted to investigate the reactivity of pure and doped alpha-Fe203. It was found that the presence of elements such as Si, Cu, and Mn in alpha-Fe203 had a significant effect on TCE reduction potential of alpha-Fe203; however, the reduction potential was less than that of alpha-Fe203 (Bayferrox- 110 M, used in a previous study). Further studies were carried out and alpha-Fe203 was synthesized in a manner similar to that of Bayferrox-110 M. This synthetic alpha-Fe203 showed improved reactivity and was found to follow pseudo-first-order kinetics when used in TCE reduction experiments. The preliminary end products analysis showed that TCE degradation was probably via beta-elimination pathway. Detailed investigations ofa-Fe203 systems were carried out using X-ray diffraction, X-ray fluorescence, and scanning electron microscopy with energy-dispersive spectrometry. The results demonstrated that the TCE reduction capacity of alpha-Fe203 was strongly dependent on the other elements present in iron powder used to synthesize alpha-Fe203. It was suspected that these multi-elements in alpha-Fe203 helped to improve its conduction property. Current findings suggest that alpha-Fe203 not in the pure but combined with other elements could be thought as a potential system for TCE reduction.

Influences of dissolved organic matter characteristics on trihalomethanes formation during chlorine disinfection of membrane bioreactor effluents.

Dissolved organic matter (DOM) in MBR-treated municipal wastewater intended for reuse was fractionated through ultrafiltration and XAD-8 resin adsorption and characterized by fluorescence spectroscopy. To probe the influences of DOM characteristics on trihalomethanes (THMs) formation reactivity during chlorination, THMs yield and speciation of DOM fractions was investigated. It was found that chlorine reactivity of DOM decreased with the decrease of molecular weight (MW), and MW>30kDa fractions produced over 55% of total THMs in chlorinated MBR effluent. Hydrophobic organics had much higher THMs formation reactivity than hydrophilic substances. Particularly, hydrophobic acids exhibited the highest chlorine reactivity and contributed up to 71% of total THMs formation. Meanwhile, low-MW and hydrophilic DOM were susceptible to produce bromine-containing THMs. Of the fluorescent DOM in MBR effluent, aromatic moieties and humic acid-like had higher chlorine reactivity. Conclusively, macromolecular and hydrophobic organics containing aromatic moieties and humic acid-like must be removed to reduce THMs formation.

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.

Application of activated carbons from coal and coconut shell for removing free residual chlorine.

This study investigated the removal of free residual chlorine by activated carbon (AC). ACs were prepared from coal (AC1) and coconut shell (AC2). The specific surface area of AC1 was larger than that of AC2. The removal of free residual chlorine increased with elapsed time and amount of adsorbent. The removal mechanism of free residual chlorine was the dechlorination reaction between hypochlorous acid or hypochlorite ion and AC. Moreover, AC1 was useful in the removal of free residual chlorine in tap water. The optimum condition for the removal of free residual chlorine using a column is space velocity 306 1/h; liner velocity 6.1 m/h.

Low and high acetate amendments are equally as effective at promoting complete dechlorination of trichloroethylene (TCE).

Experiments with trichloroethylene-contaminated aquifer material demonstrated that TCE, cis-DCE, and VC were completely degraded with concurrent Fe(III) or Fe(III) and sulfate reduction when acetate was amended at stoichiometric concentration; competing TEAPs did not inhibit ethene production. Adding 10× more acetate did not increase the rate or extent of TCE reduction, but only increased methane production. Enrichment cultures demonstrated that ~90 µM TCE or ~22 µM VC was degraded primarily to ethene within 20 days with concurrent Fe(III) or Fe(III) + sulfate reduction. The dechlorination rates were comparable between the low and high acetate concentrations (0.36 vs 0.34 day(-1), respectively), with a slightly slower rate in the 10× acetate amended incubations. Methane accumulated to 13.5 (±0.5) µmol/tube in the TCE-degrading incubations with 10× acetate, and only 1.4 (±0.1) µmol/tube with low acetate concentration. Methane accumulated to 16 (±1.5) µmol/tube in VC-degrading enrichment with 10× acetate and 2 (±0.1) µmol/tube with stoichiometric acetate. The estimated fraction of electrons distributed to methanogenesis increased substantially when excessive acetate was added. Quantitative PCR analysis indicated that 10× acetate did not enhance Dehalococcoides biomass but rather increased the methanogen abundance by nearly one order of magnitude compared to that with stoichiometric acetate. The data suggest that adding low levels of substrate may be equally if not more effective as high concentrations, without producing excessive methane. This has implications for field remediation efforts, in that adding excess electron donor may not benefit the reactions of interest, which in turn will increase treatment costs without direct benefit to the stakeholders.

Use of Cl and C isotopic fractionation to identify degradation and sources of polychlorinated phenols: mechanistic study and field application.

The widespread use of chlorinated phenols (CPs) as a wood preservative has led to numerous contaminated sawmill sites. However, it remains challenging to assess the extent of in situ degradation of CPs. We evaluated the use of compound-specific chlorine and carbon isotope analysis (Cl- and C-CSIA) to assess CP biotransformation. In a laboratory system, we measured isotopic fractionation during oxidative 2,4,6-trichlorophenol dechlorination by representative soil enzymes (C. fumago chloroperoxidase, horseradish peroxidase, and laccase from T. versicolor). Using a mathematical model, the validity of the Rayleigh approach to evaluate apparent kinetic isotope effects (AKIE) was confirmed. A small but significant Cl-AKIE of 1.0022 ± 0.0006 was observed for all three enzymes, consistent with a reaction pathway via a cationic radical species. For carbon, a slight inverse isotope effect was observed (C-AKIE = 0.9945 ± 0.0019). This fractionation behavior is clearly distinguishable from reported reductive dechlorination mechanisms. Based on these results we then assessed degradation and apportioned different types of technical CP mixtures used at two former sawmill sites. To our knowledge, this is the first study that makes use of two-element CSIA to study sources and transformation of CPs in the environment.

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.

Control of disinfection by-product formation using ozone-based advanced oxidation processes.

The effects of ozone dosage, water temperature and catalyst addition in an ozonation-fluidized bed reactor (O3/FBR) on treated water quality and on the control of chlorinated and ozonated disinfection by-products (DBPs) were investigated. A biofiltration column was used to evaluate its removal efficiency on biodegradable organic matter and to reduce DBP formation. The Dong-Gang River, polluted by agricultural and domestic wastewater in Pingtung, Taiwan, was used as the water source. The treated water quality in terms of dissolved organic carbon (DOC), biodegradable DOC, ultraviolet absorbance at 254 nm (UV254) and specific UV absorbance (SUVA) improved with increasing ozone and catalyst dosages. Catalytic ozonation was more effective than ozonation alone at reducing the formation of DBPs at a given dosage. Experimental results show that water temperature had little effect on the treated water quality with the O3/FBR system used in this study (p > 0.05). The combination of O3/FBR and the biofiltration process effectively decreased the amount ofDBP precursors. The concentration of total trihalomethanes (TTHMs) was less than the maximum contaminant level (MCL) requirement, which is 80 microg/L, for all treated waters and the concentration of five haloacetic acids (HAA5) fell below 60 microg/L with an ozone dosage higher than 2.5 mg/L.