Thermodynamic and kinetic studies on Cs+- and Sr2+-exchange in natural zeolite from Akita,Japan

Thermodynamic and kinetic studies on the adsorption of Cs⁺ and Sr²⁺ by Na-exchanged clinoptilolite-rich zeolite rock from Akita (Northern Japan) were performed for the purpose of nuclear waste treatment. The thermodynamic parameters such as selectivity coefficient, thermodynamic equilibrium constant, and standard free energy of exchange were evaluated. These values indicated that the selectivity order was determined as Cs⁺ > Na⁺ > Sr²⁺. In order to discuss the adsorption mechanism of Cs⁺ and Sr²⁺ onto Na-exchanged clinoptilolite, the effective diffusion coefficients were calculated and two kinetic models, pseudo-first-order and pseudo-second-order kinetic model, were tested. For all systems studied, chemisorption seems significant in the rate-controlling step, and the pseudo-second-order kinetic model provided the best correlation of the experimental data.     

Composition of green turtle feeding aggregations along the Japanese archipelago: implications for changes in composition with current flow

In order to develop effective conservation strategies for endangered migratory species, the link between feeding and breeding grounds needs to be clarified. In this study, the genetic compositions of consecutive Japanese feeding aggregations of green turtles (Chelonia mydas) along the Kuroshio Current were examined by mixed-stock analyses of mitochondrial DNA control-region sequences. The results indicated that the southern feeding aggregation around Yaeyama (24.3°N, 124.0°E) was sourced from various Pacific rookeries in the Yaeyama, Ogasawara, Western Pacific, and Indian Oceans and Southeast Asia. Among northern feeding aggregations, the Ginoza (26.5°N, 128.0°E) aggregation was also sourced from the Western Pacific Ocean, but the Nomaike (31.4°N, 130.1°E), Muroto (33.2°N, 134.2°E), and Kanto (35.6°N, 140.5°E) aggregations were contributed mostly by the closer Ogasawara rookeries. The reduced contribution from tropical Pacific rookeries to northern feeding aggregations and the significant correlation between genetic differentiation and geographical distance matrices of feeding aggregations indicated that most hatchlings from these regions transported by the Kuroshio Current settle in upstream feeding grounds along the Japanese archipelago, implying that current flow influences the composition of feeding aggregations. Differences in the composition of relatively close neritic feeding aggregations have important conservation implications, for which both regional and multinational conservation strategies are needed.     

Influence of oxalic acid formed on the degradation of phenol by Fenton reagent

The objective of this work is to examine the influence of oxalic acid formed on the degradation of phenol by Fenton reagent. Oxalic acid formed at initial stage within 30 min significantly suppresses the reduction of ferric ion, thus terminating degradation reaction. The yield of oxalic acid is dependent on the amount of ferrous ion dosed since the minimal amount of oxalic acid is formed after the degradation reaction terminates. Mineralization of phenol by Fenton reagent stagnates after 120 min under the conditions used in this study. The reason why the mineralization stagnated can be assumed to be following two mechanisms other than the depletion of H₂O₂. In the case where a small amount of ferrous ions is dosed, the reduction of ferric ions is minimal by oxalic acid formed. In the case where a large amount of ferrous ions is dosed, the amount of degradable organic compounds is insufficient owing to preferential conversion to oxalic acid. The mineralization can be enhanced by the intermittent dosing of ferrous ions, which facilitates the suppression of oxalic acid formation during the degradation by Fenton reagent.     

Eco-balance analysis of land use combinations to minimize environmental impacts and maximize farm income in northern Japan

Relationships among global warming potential (GWP), farmland surplus nitrogen (FSN) and income for major land uses in the Ikushunbetsu watershed were compared using the eco-balance method. An empirical model was created for carbon dioxide, methane and nitrous oxide for both uplands and paddy rice using monitoring data from 22 fields. The greenhouse gas emissions were converted into GWP, whereas yield and FSN were obtained from interviews with farmers and a literature survey. Land use distribution was obtained by ground surveys in 2002, 2005 and 2007. The analysis showed that paddy rice and soybeans were characterized by a high GWP, low FSN and high income, whereas onions and vegetables had a high FSN but low GWP and moderate income. Wheat showed a negative GWP in some years, and abandoned areas always exhibited negative values. The total GWPs for the region were 14,184, 11,085 and 8,337 Mg CO₂ year⁻¹ for 2002, 2005 and 2007, respectively. The contribution of paddy rice to GWP was highest, ranging from 40 to 75%. To find optimal land use combinations that provide higher incomes and lower GWPs and FSNs than at present, all possible land use combinations were analyzed by changing the land use proportion from 0 to 100% at an interval of 10%. The number of land use combinations meeting the requirements in the three investigated years was 205. Abandoned area, which had the smallest environmental load, was included in every land use combination, indicating that land uses with low environmental impacts should be maintained at a certain proportion to mitigate the environmental load accompanying land uses with high production.     

Application of crosswell seismic tomography using difference analysis with data normalization to monitor CO2 flooding in an aquifer

A pilot-scale experiment for carbon dioxide (CO₂) sequestration was undertaken at the Nagaoka test field in Japan. Time-lapse crosswell seismic tomography was conducted to detect and monitor the movement of CO₂ injected into an aquifer. We applied difference analysis with data normalization (DADN) to the time-lapse data to eliminate false images that were apparent in a conventionally processed difference section. Conventional difference analysis calculates travel-time delays after inversion, whereas the DADN method calculates them from raw travel-time records before inversion. Thus, fewer errors are generated with the DADN method compared to a conventional inversion analysis. We applied the DADN method to time-lapse tomography data recorded before and after the injection of CO₂ and computed the velocity variation in a subsurface section, which clearly showed the distribution of CO₂ flooding within a high permeability zone in the aquifer and showed no CO₂ leakage into the caprock. Our results also show the maximum velocity decrease as a result of CO₂ injection was about 9%, which is close to the results obtained in laboratory experiments. Finally, numerical simulations were inverted to test the effectiveness of the conventional and DADN methods in dealing with noise. These tests showed that the DADN method effectively reduces unique coherent noise for particular receiver and source combinations. We concluded that the DADN method provides useful data for monitoring the flow of CO₂ sequestered in underground aquifers.     

Restoration of cadmium-contaminated paddy soils by washing with ferric chloride: Cd extraction mechanism and bench-scale verification

The ability of FeCl3 to extract Cd from three paddy soils was compared with that of various irons, manganese, and zinc salts to elucidate the extraction mechanism. Manganese, zinc and iron salts (including FeCl3) extracted 4-41%, 8-44% and 24-66% of total Cd, respectively. This difference reflected the pH of the extraction solution, indicating that the primary mechanism of Cd extraction by FeCl3 is proton release coupled with hydroxide generation, as iron hydroxides are insoluble. Washing with FeCl3 led to the formation of Cd-chloride complexes, enhancing Cd extraction from the soils. FeCl3 effectively extracted Cd from all of the three soils compared to HCl that is a conventional washing chemical, when the concentrations of the two washing chemicals were between 15 and 60mM(c) (at above extraction pH 2.4), while the corresponding extraction pH of FeCl3 was slightly higher than HCl. As HCl is the strong acid of complete dissociation, if excess amount of HCl was added to soil, it is possible to give the dissolution of clay minerals in soils. In contrast, proton release from FeCl3 is controlled by the chemical equilibrium of hydroxide formation. While soil fertility properties were affected by a bench-scale soil washing with 45mM(c) FeCl3, adverse effects were not crucial and could be corrected. The bench-scale test confirmed the effectiveness of FeCl3 for removal of soil Cd. The washing had no negative effect on rice yield and lowered the Cd concentration of rice grain and rice straw in a pot experiment.     

Gaseous nitrous acid (HONO) and nitrogen oxides (NOx) emission from gasoline and diesel vehicles under real-world driving test cycles

Reactive nitrogen species emission from the exhausts of gasoline and diesel vehicles, including nitrogen oxides (NO_x) and nitrous acid (HONO), contributes as a significant source of photochemical oxidant precursors in the ambient air. Multiple laboratory and on-road exhaust measurements have been performed to estimate the NO_x emission factors from various vehicles and their contribution to atmospheric pollution. Meanwhile, HONO emission from vehicle exhaust has been under-measured despite the fact that HONO can contribute up to 60% of the total hydroxyl budget during daytime and its formation pathway is not fully understood. A profound traffic-induced HONO to NO_x ratio of 0.8%, established by Kurtenbach et al. since 2001, has been widely applied in various simulation studies and possibly linked to under-estimation of HONO mixing ratios and OH radical budget in the morning. The HONO/NO_x ratios from direct traffic emission have become debatable when it lacks measurements for direct HONO emission from vehicles upon the fast-changing emission reduction technology. Several recent studies have reported updated values for this ratio. This study has reported the measurement of HONO and NO_x emission as well as the estimation of exhaust-induced HONO/NO_x ratios from gasoline and diesel vehicles using different chassis dynamometer tests under various real-world driving cycles. For the tested gasoline vehicle, which was equipped with three-way catalyst after-treatment device, HONO/NO_x ratios ranged from 0 to 0.95 % with very low average HONO concentrations. For the tested diesel vehicle equipped with diesel particulate active reduction device, HONO/NO_x ratios varied from 0.16 to 1.00 %. The HONO/NO_x ratios in diesel exhaust were inversely proportional to the average speeds of the tested vehicles.

Implications: Photolysis of HONO is a dominant source of morning OH radicals. Conventional traffic-induced HONO/NO_x ratio of 0.8% has possibly linked to underestimation of the total HONO budget and consequently underestimation of OH radical budget. The recently reported HONO/NO_x ratio of ~1.6% was used to stimulate HONO emission, which resulted in increased HONO concentrations during morning peak hours and its impact of 14% OH increment in the morning. However, the results were still lower than the measured concentrations. More studies should be conducted to establish an updated traffic-induced HONO/NO_x ratio.     

Online measurements of low-volatile organic chlorine for dioxin monitoring at municipal waste incinerators

In this study, an automatic sampling device and an analysis device have been developed for the measurement of low-volatile organic chlorine (LVOCl) in flue gas. The concentrations of dioxins (polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and dioxin-like polychlorinated biphenyls) have been estimated by online measurements of LVOCl at a municipal solid waste incinerator (MSWI) using these devices. The LVOCl concentration at the outlet of the selective catalyst reactor (SCR) of the MSWI increased momentarily up to 95 μg Cl m⁻³ during the startup period of the MSWI; subsequently, it gradually decreased to less than 1.0 μg Cl m⁻³ after 50 h from the start of waste feeding. The concentration of toxic equivalent quantity (TEQ)-Dioxins at the SCR outlet had a linear positive relationship with the LVOCl concentrations. Moreover, the level of TEQ-Dioxins concentration can be estimated by using this relationship with LVOCl. From our results, since the LVOCl concentrations in a flue gas can thus be automatically analyzed every hour by online measurements, the operators of an MSWI would be able to monitor approximate TEQ-Dioxin emissions on a daily basis.     

Phosphorus recovery from secondary effluent and side-stream liquid in a sewage treatment plant using zirconium-loaded saponified orange waste

Zirconium was loaded onto orange waste, a cheap and available agricultural waste in Japan, to investigate the feasibility of its utilization for phosphorus recovery from secondary effluent and side-stream liquid, which contain 5.9 and 68.2 mg/dm³ phosphorus, respectively. The phosphorus removal from side-stream liquid by using zirconium-loaded saponified orange waste (Zr-SOW) gel increased with an increasing solid/liquid ratio, and it was found that Zr-SOW gel showed better performance than zirconium ferrite. The prepared adsorbent was effective for phosphorus removal and exhibited a reasonably high adsorption capacity, twice than that of zirconium ferrite. The secondary effluent was treated in a column packed with Zr-SOW gel, and an dynamic adsorption capacity of 1.3 mol-P/kg was attained. The adsorbed phosphorus from the column was successfully eluted as a concentrated form by using a small amount of 0.2 M NaOH. Throughout the elution process, zirconium was not leaked from the adsorption gel.     

Leaching of heavy metals by citric acid from fly ash generated in municipal waste incineration plants

The leaching behavior of heavy metals from municipal waste incineration (MWI) fly ash was investigated in this study. The leaching process includes two steps, i.e., fly ash was firstly washed with water, and then subjected to citric acid leaching. The main parameters of the washing process such as liquid/solid ratio, washing time, and number of washing were tested. The optimum conditions for water washing were found as follows: washing time 5–10 min, liquid/solid ratio 10:1 (ml:g), and number of washing was twice; under these conditions, 86% Na, 70% K, 12% Ca, 1.2% Al, and 0.5% Pb were removed from the fly ash in the prewashing. From the results of screening tests of leaching lixiviants, citric acid was found to be the most effective leaching agent, taking account of its environmentally benign characteristics. Optimum metal extraction can be achieved with citric acid under the following conditions: pH 3.0, liquid/solid ratio 40 (ml:g), citric acid concentration 0.10 mol/dm³, contact time 20 min at room temperature.