Enhancing the Biological Oxidation of H2S in a Sewer Pipe with Highly Conductive Concrete and Electricity-Producing Bacteria.

Hydrogen sulfide (H2S) generated in sewer systems is problematic to public health and the environment, owing to its corrosive consequences, odor concerns, and poison control issues. In a previous work, conductive concrete, based on amorphous carbon with a mechanism that operates as a microbial fuel cell was investigated. The objective of the present study is to develop additional materials for highly conductive concrete, to mitigate the concentration of H2S in sewer pipes. Adsorption experiments were conducted to elucidate the role of the H2S reduction. Additionally, electricity-producing bacteria (EPB), isolated from a municipal wastewater treatment plant, were inoculated to improve the H2S reduction. The experimental results showed that inoculation with EPB could decrease the concentration of H2S, indicating that H2S was biologically oxidized by EPB. Several types of new materials containing acetylene black, or magnetite were discovered for use as conductive concrete, and their abilities to enhance the biological oxidation of H2S were evaluated. These conductive concretes were more effective than the commercial conductive concrete, based on amorphous carbon, in decreasing the H2S concentration in sewer pipes.

Preferential adsorption and surface precipitation of lead(II) ions onto anatase in artificially contaminated Dixie clay.

During TEM-EDS (transmission electron microscopy coupled with an X-ray energy dispersive spectrometer) analysis of Dixie clay artificially contaminated with Pb(II), we observed that Pb(II) was preferentially adsorbed and precipitated on the surface of TiO2. To deepen the understanding of the mechanism and importance of this phenomenon, batch sorption experiments, XANES (X-ray absorption near edge spectroscopy) analysis, and sequential extraction analysis were performed. The TiO2 in Dixie clay was found to be anatase, and anatase showed a higher Pb(II) sorption propensity than rutile, α-FeOOH, and one of two MnO2 investigated in this study. Our experimental results indicated that the Pb precipitates preferentially formed on the surface of anatase was Pb(II) hydroxide or Pb(II) oxide. Additionally, sequential extraction analysis showed that at least 32% and 42% of Pb(II) was sorbed onto anatase in the Dixie clay contaminated with a Pb content of 736mg Pb/kg and 1,958mg Pb/kg, respectively. These results demonstrated that in addition to Fe and Mn oxides that are well-known metal oxides that serve as sinks for Pb(II) in the soil environment, TiO2 is also a metal oxide that controls the behavior and fate of Pb(II) in soils.

Relationship between performance deterioration of a polyamide reverse osmosis membrane used in a seawater desalination plant and changes in its physicochemical properties.

While it is known that the performance of reverse osmosis membranes is dependent on their physicochemical properties, the existing literature studying membranes used in treatment facilities generally focuses on foulant layers or performance changes due to fouling, not on the performance and physicochemical changes that occur to the membranes themselves. In this study, the performance and physicochemical properties of a polyamide reverse osmosis membrane used for three years in a seawater desalination plant were compared to those of a corresponding unused membrane. The relationship between performance changes during long-term use and changes in physicochemical properties was evaluated. The results showed that membrane performance deterioration (i.e., reduced water flux, reduced contaminant rejection, and increased fouling propensity) occurred as a result of membrane use in the desalination facility, and that the main physicochemical changes responsible for performance deterioration were reduction in PVA coating coverage and bromine uptake by polyamide. The latter was likely promoted by oxidant residual in the membrane feed water. Our findings indicate that the optimization of membrane materials and processes towards maximizing the stability of the PVA coating and ensuring complete removal of oxidants in feed waters would minimize membrane performance deterioration in water purification facilities.

Immobilization of arsenate in kaolinite by the addition of magnesium oxide: An experimental and modeling investigation.

MgO was chosen as an As(V) immobilization agent and a series of immobilization experiments was performed to obtain insights into the behavior of As(V) and MgO during leaching tests. Our experimental and modeling results demonstrated that As(V) immobilization by MgO consists of the following steps: (i) an increase in sample pH, (ii) desorption of As(V) from the samples, and (iii) the re-immobilization of As(V) by MgO/Mg(OH)2 particles. Regarding the behavior of MgO, the modeling results showed that when the MgO dosage was 25 mgMgO/4 g-drysample or less, the majority of MgO was used to increase pH, and less than 1% of MgO was used to sorb As(V), which was consistent with the result of leaching tests showing that a high level of As(V) was leached at the MgO dosages. On the other hand, when the MgO dosage was above 25 mgMgO/4 g-drysample, the percentage of MgO used for As(V) sorption increased up to 35%, and correspondingly, the As(V) leaching level decreased to below 0.01 mgAs/L at an MgO dosage of 75 mgMgO/4 g-drysample. Additionally, when the MgO dosage was 50 mgMgO/4 g-drysample or more, it was found that more than 40% of MgO remained as fresh MgO without undergoing chemical reactions.

Recovery of Cr as Cr(III) from Cr(VI)-contaminated kaolinite clay by electrokinetics coupled with a permeable reactive barrier.

Zero-valent iron (Fe(0)) and magnetite (Fe3O4) were investigated as potential reductants in an electrokinetic/permeable reactive barrier hybrid system (EK/PRB) for the recovery of Cr as Cr(III) from Cr(VI)-contaminated kaolinite. For the EK/Fe(0) PRB, regardless of the pH in the anode well, the system facilitated the reduction of Cr(VI) into Cr(III), but the recovery of the Cr(III) in the PRB was low. Conversely, the reduction of Cr(VI) occurred only in the PRB for the EK/Fe3O4 PRB. However, when the anode pH was not controlled and the soil pH values correspondingly decreased gradually from the anode side, a greater fraction of Cr(VI) sorbed onto the kaolinite; as a result, a lower amount of Cr(VI) migrated to the Fe3O4 PRB. In addition, it was found that the majority of Cr(VI) migrating to the Fe3O4 PRB retained its oxidation state without being converted into Cr(III). These two adverse effects were mitigated by maintaining the soil pH values at 6.8, but at the same time, 18% of Cr(VI) penetrated through the Fe3O4 PRB. The penetration of Cr(VI) through the Fe3O4 PRB was successfully prevented by increasing the reaction time through the introduction of a cation exchange membrane between the Fe3O4 PRB and the anode well.

A mechanistic study of arsenate removal from artificially contaminated clay soils by electrokinetic remediation.

Batch desorption experiments and bench-scale electrokinetic experiments were performed to elucidate the electrokinetic remediation mechanisms of arsenate from artificially contaminated kaolinite. The electrokinetic experiments in which a constant voltage was applied demonstrated that high soil pH favored arsenate remediation with respect to both the remediation time and electricity consumption. It was also demonstrated that applying a pulse voltage (1 h ON, 1 h OFF) significantly improved the electricity consumption efficiency when the soil pH was maintained at the initial value during the experiments; this trend was not observed when the soil pH was gradually increased from the cathode side. These electrokinetic experimental results, with the support of arsenate desorption data obtained from batch experiments, indicate that the remediation rate-limiting step varied with soil pH. When the soil pH was maintained at the initial value of 7.2 during the experiments, arsenate desorption was the remediation rate-limiting step rather than the migration of dissolved arsenate toward the anode. Conversely, when the cathode pH was not controlled and the soil pH was correspondingly increased gradually from the cathode side, the migration of hydroxyl and desorbed arsenate ions toward the anode played a more important role in the control of the overall remediation efficiency.

An electrokinetic/Fe0 permeable reactive barrier system for the treatment of nitrate-contaminated subsurface soils.

Effective nitrate removal by Fe(0) permeable reactive barriers (Fe(0) PRB) has been recognized as a challenging task because the iron corrosion product foamed on Fe(0) hinders effective electron transfer from Fe(0) to surface-bound nitrate. The objectives of this study were (i) to demonstrate the effectiveness of an electrokinetic/Fe(0) PRB system for remediating nitrate-contaminated low permeability soils using a bench-scale system and (ii) to deepen the understanding of the behavior and fate of nitrate in the system. Bench-scale laboratory experiments were designed to investigate the influence of the Fe(0) content in the permeable reactive barrier, the pH in the anode well, and the applied voltage on remediation efficiency. The experimental results showed that the major reaction product of nitrate reduction by Fe(0) was ammonium and that nitrate reduction efficiency was significantly influenced by the variables investigated in this study. Nitrate reduction efficiency was enhanced by either increasing the Fe(0) content in the Fe(0) reactive barrier or decreasing the initial anode pH. However, nitrate reduction efficiency was reduced by increasing the applied voltage from 10 V to 40 V due to the insufficient reaction time during nitrate migration through the Fe(0) PRB. For all experimental conditions, nearly all nitrate nitrogen was recovered in either anode or cathode wells as nitrate or ammonium within 100 h, demonstrating the effectiveness of the system for remediating nitrate-contaminated subsurface soils.

Origins and transport of aquatic dioxins in the Japanese watershed: soil contamination, land use, and soil runoff events.

Significant dioxins accumulations in Japanese forests and paddy fields have been observed, and surface soil runoff caused by rainfall and irrigation (i.e., soil puddling in paddy fields) results in dioxins input into the aquatic environment. An extensive investigation into the origins and transport of aquatic dioxins in the Yasu watershed, Japan was conducted considering surface soil contamination level, land use, and type of soil runoff event (i.e., irrigation runoff [IR], rainfall runoff [RR], and base flow [BF]). Combined use of the chemically activated luciferase expression (CALUX) assay together with high-resolution gas chromatography and high-resolution mass spectrometry (HRGC/HRMS) efficiently enabled this study, so that origins, transport, and dynamic movement of aquatic dioxins in the watershed were revealed. The particulate organic carbon normalized particulate-dioxins WHO-toxic equivalent (TEQ) concentration predicted by the CALUX assay (Spar) was found to be a convenient molecular marker to indicate origins of aquatic dioxins and clearly reflect surface soil contamination level, land use, and soil runoff events. Using experimental results and theoretical modeling, the annual loading amount of dioxins at the middle reach of the river was estimated to be 0.458 mg WHO-TEQ in 2004. More than 96.6% of the annual loading amount was attributed to RR and derived almost evenly from forest and paddy fields at the study location. Because the annual loading amount at the middle reach is less than 0.5% of the total dioxins accumulated in the upper basin, dioxins runoff from the Japanese watershed will continue. This study shows that the combined use of the bioassay with HRGC/HRMS can provide new insights into dioxins transport and fate in the environment.

Mass loading and partitioning of dioxins in irrigation runoff from Japanese paddy fields: combination usage of the CALUX assay with HRGC/HRMS.

Lack of understanding of dioxins mass loading into the aquatic environment motivated the quantitative investigation of dioxins runoff from paddy fields during one entire irrigation period in the Minakuchi region, Japan. Combination use of the chemically activated luciferase gene expression (CALUX) bioassay together with high resolution gas chromatography and high resolution mass spectrometry (HRGC/HRMS) enabled efficient investigation of dioxins contamination. The result shows that the congener profile in irrigation runoff is quite similar to those in paddy soil samples and that 1,3,6,8-/1,3,7,9-TeCDD and OCDD derived from pesticides (i.e., pentachlorophenol (PCP) and chloronitrophen (CNP)) are predominant congeners in irrigation runoff. Although it is not surprising that dioxins concentration was strongly dependent on the suspended solids (SS) and the particulate organic carbon (POC) concentration, the dioxins toxic equivalency (TEQ) concentration was extremely high in irrigation runoff (max: 16,380 pg/L, corresponding to 12 pg WHO-TEQ/L) due to runoff of highly contaminated paddy soils. The results imply that dioxins concentration in a river must be monitored considering soil contamination level, land use, and soil runoff events. Using experimental data and a theoretical model, the mass loading of dioxins from the paddy fields by irrigation runoff was estimated to be 1.50 x 10(-2)% of total amount of dioxins accumulated in the paddy fields. Given the results of other researches, it is implied the following: 1) large portion of paddy soils released into the river appear to be settled on the riverbed due to small water flux, and, then, washed out and transported by rainfall runoff after irrigation period, 2) rainfall runoff itself also wash out paddy soils directly from paddy fields. Combination use of the CALUX bioassay with HRGC/HRMS is demonstrated as an alternative strategy to assess dioxins contamination in the environment.

Performance characterization of nanofiltration membranes based on rigid star amphiphiles.

The objective of this study was to develop new nanofiltration (NF) membranes capable of providing significantly greater water permeability and higher rejection of water contaminants compared to state-of-the-art NF membranes. The active layer of the new NF membranes is prepared with rigid star amphiphiles (RSAs) synthesized as part of this study. Performance characterization for a first generation of RSA membranes in a bench-scale apparatus reveals that most of the new membranes provide water permeability of 1.3-3.1 times that of two commercial NF membranes with polyamide active layers while providing comparable rejection of the organic contaminant surrogate Rhodamine WT. However, the rejection of arsenious acid (H3AsO3) by most new NF membranes was found to be lower than that by the two commercial NF membranes tested. Future research efforts of this study will focus on exploring if H3AsO3 rejection could be significantly increased, without negatively affecting water permeability and organic contaminant rejection, by addition of various chemical groups to RSA hydrophobic cores and hydrophilic branches, and by RSA cross-linking.