Taku Fujiwara

Modeling of sulfonamide antibiotic removal by TiO(2)/high-silica zeolite HSZ-385 composite.

TiO(2)/high-silica zeolite composite synthesized by a sol-gel method was applied for the removal of sulfamethazine (SMT) antibiotic from water, and simple models including both adsorption and photocatalytic decomposition were developed. In this study, two types of models were constructed: a synergistic model that included the interaction between the zeolite and TiO(2) in the composite, and an individual model, which did not include the interaction. We obtained rate constants for adsorption, desorption and photocatalytic decomposition experimentally, and compared them with the results calculated using the synergistic and individual models. The individual model predicted that ca. 55% of SMT would be removed from the system after 6h of treatment; however, our experiments showed that 80% of the SMT was removed, suggesting the existence of another reaction pathway. Therefore, a synergistic model was constructed, in which, part of the SMT was adsorbed onto the zeolite within the composite, desorbed from the zeolite and migrated to the TiO(2), and was then photocatalytically decomposed. Experiments were carried out with varying amounts of the TiO2-zeolite composite, and the synergistic model was validated. We estimated that 10% of the desorbed SMT was photocatalytically decomposed without being released into the water. When TiO(2)-zeolite composite concentrations were 0.04, 0.12 and 0.20g/L, and the treatment time was 6h, the proportions of the total decomposition of SMT that occurred via this synergistic reaction pathway were calculated as 52.2%, 58.6% and 66.7%, respectively. In other words, over half of the SMT was decomposed through the synergistic reaction, which played a very significant role in the overall removal of SMT (the remainder of the SMT was decomposed through simple photocatalysis on the TiO(2)).

Nitrous oxide emission mechanisms during intermittently aerated composting of cattle manure.

To investigate the mechanisms of nitrous oxide (N₂O) emission during intermittent aeration in the composting process, a laboratory scale experiment with continuous measurement of N₂O emission was conducted with cattle manure. A low oxygen mode (2.5% oxygen in the inlet for 1 day), anaerobic mode (0.13% oxygen for 0.25 day), and aerated mode (20.5% oxygen for 2 days) were sequentially set up three times after 22 days of continuous aeration to replicate intermittent aeration. The total N₂O emission was 0.26-0.35 mmol, 0.27-0.32 mmol, and 0.14-0.23 mmol during the low oxygen, anaerobic, and aerated modes, respectively. Denitrification was indicated as the main N₂O emission pathway in the anaerobic and low-oxygen modes, while nitrification was indicated as the main pathway in the aerated mode and under continuous aeration. Results from this study suggest that nitrification is an important pathway for N₂O emission as well as denitrification.

Photocatalytic decomposition of crotamiton over aqueous TiO2 suspensions: Determination of intermediates and the reaction pathway

The photocatalytic degradation of crotamiton in aqueous solution using TiO(2) was investigated. To investigate the effect of initial pH, the photodegradation behaviors of three types of pharmaceuticals were compared (crotamiton, clofibric acid, sulfamethoxazole). The degradation rates of crotamiton in the pH range 3-9 were nearly equal, but those of clofibric acid and sulfamethoxazole were affected by pH. At pH>6.5, TiO(2) particles, clofibric acid and sulfamethoxazole had negative charge, therefore, the repulsive force between TiO(2) particles and anionic pharmaceuticals occurred and a low reaction rate at high pH was observed. The effect of UV intensity and TiO(2) concentration on photodegradation efficiency was also investigated. Linear and logarithmical relationships between UV intensity, TiO(2) concentration and the reaction rate constant were confirmed. Furthermore, the structures of photodegradation intermediates formed concomitantly with the disappearance of crotamiton were estimated. Seven intermediates were characterized by LC/MS/MS analyses, and it was assumed that the photocatalytic degradation of crotamiton was initiated by the attack of electrophilic hydroxyl radicals on aromatic rings and alkyl chains.

Photocatalytic decomposition behavior and reaction pathway of sulfamethazine antibiotic using TiO2.

The photocatalytic degradation of sulfanethazine (SMT), one of the sulfonamide antibiotics, in aqueous solution by TiO2 was investigated. The time courses of SMT concentration, the amount of non-purgeable organic carbon, and the concentrations of ions such as SO4(2-), NH4(+), and NO3(-) formed during the photocatalytic reaction were measured and the structures of seven intermediates formed with the disappearance of SMT were also estimated by LC/MS/MS analyses. In addition to that of SMT, the decomposition behaviors of model compounds sulfanilic acid (SA) and 4-amino-2, 6-dimethylpyrimidine (ADMP) were investigated using the TiO2/UV system. The observed photocatalytic degradation behaviors of SMT, SA, and ADMP gave new insight into the degradation pathway of SMT. Especially, the formation of p-aminophenol during SMT decomposition, which until now has not been reported in previous studies concerning the photocatalytic decomposition of SMT and other sulfonamide antibiotics. These results indicate the existence of a novel photocatalytic degradation pathway for sulfonamides. The direct substitution of the sulfonamide group with a hydroxyl group is suggested.

Nutrient recovery from biomass cultivated as catch crop for removing accumulated fertilizer in farm soil

As a result of long-term continuous use of fertilizers in farm land, a large amount of nutrients accumulate in the soil, increasing the risk of eutrophication or nitrate pollution of groundwater. For rehabilitating the farm soil and recovering nutrients such as nitrogen, phosphorus and potassium, a new system has been developed by our research group. This paper discusses the methodology of extracting nutrients from biomass in order to recover phosphorus and other nutrients in crystal form. Around 80% or higher extraction rates were achieved for phosphorus and potassium by soaking the powdered tissue in distilled water or 1% NaOH solution for 24 h. The extracted phosphorus and potassium act as a potential resource for recycled fertilizer or other industrial materials.

Comparison of simultaneous and separate processes: saccharification and thermophilic L-lactate fermentation of catch crop and aquatic plant biomass.

Catch crop candidates (corn, guinea grass) for recovering nutrients from farm soil and aquatic plants (water caltrop, water hyacinth) were utilized to produce l-lactic acid. The efficiencies of pre-treatment methods for enzymatic saccharification and l-lactate production of two fermentation processes, thermophilic simultaneous saccharification and fermentation (SSF), as well as separate saccharification and fermentation, were compared. Conditions were set at 55°C and pH 5.5 for non-sterile fermentation. Alkaline/peroxide pre-treatment proved the most effective for saccharification in pre-treated corn, guinea grass, water caltrop and water hyacinth with glucose yields of 0.23, 0.20, 0.11 and 0.14 g/g-dry native biomass (24-hour incubation period), respectively. Examination of the two types of thermophilic l-lactate fermentation employed following alkaline/peroxide pre-treatment and saccharification demonstrated that the l-lactate yield obtained using SSF (0.15 g/g in the case of corn) was lower than that obtained using separate saccharification and fermentation (0.28 g/g in the case of corn). The lower yield obtained from SSF is likely to have resulted from the saccharification conditions used in the present study, as the possibility of cellulase deactivation during SSF by thermophilic l-lactate producing bacteria existed. A cellulase that retains high activity levels under non-sterile conditions and a l-lactate producer without cellulose hydrolysis activity would be required in order for SSF to serve as an effective method of l-lactate production.

Adsorptive removal of sulfonamide antibiotics in livestock urine using the high-silica zeolite HSZ-385

The adsorptive removal of seven sulfonamide antibiotics using the high-silica zeolite HSZ-385 from distilled water, synthetic urine and real porcine urine was investigated. The pH greatly affected the adsorption efficiency, and the amounts of all sulfonamide antibiotics adsorbed on HSZ-385 decreased at alkaline conditions compared with that at neutral conditions. During storage, the pH and ammonium-ion concentration increased with urea hydrolysis for porcine urine. We clarified that the adsorption efficiency of sulfonamides in synthetic urine was equivalent to that in distilled water, suggesting that adsorption behavior was not affected by coexistent ions. HSZ-385 could adsorb sulfonamide antibiotics in real porcine urine even though the non-purgeable organic carbon concentration of porcine urine was 4-7 g/L and was two orders of magnitude higher than those of sulfonamides (10 mg/L each). Moreover, the adsorption of sulfonamides reached equilibrium within 15 min, suggesting that HSZ-385 is a promising adsorbent for removing sulfonamides from porcine urine.

Emission and control of N2O and composition of ash derived from cattle manure combustion using a pilot-scale fluidized bed incinerator

This study investigates the emission of nitrous oxide (N2O) and discusses the reduction of N2O emissions during the 24-h combustion of cattle manure using a pilot-scale fluidized bed incinerator under various experimental conditions. The results of these experiments were then validated against previously reported data. In addition, the characteristics of cattle manure incineration ash and their changes under different combustion conditions were estimated. In incineration experiments with composted cattle manure, N2O concentrations using multi-stage combustion were 75% lower than the concentrations resulting from normal combustion without additional auxiliary fuel, since N2O could be decomposed in the high-temperature zone formed by the inlet of the secondary combustion air. The N2O emission factor under normal combustion conditions (800°C) was 6.0% g-N2O-N/g-N. This result is similar to the values found in previous studies at the same temperature. The N2O emission factor was decreased to 1.6% g-N2O-N/g-N using a multi-stage combustion procedure. The current Japanese N2O emission factor of 0.1% g-N2O-N/g-N is an underestimate for some conditions and should be uniquely specified for each condition. Finally, cattle manure ash contains ample fertilizer elements, little Fe, Al and Zn, but abundant Cl. Therefore if Cl could be removed by some kind of pretreatment, cattle manure ash could be used as a favourable fertilizer.

Seasonal changes in the performance of a catch crop for mitigating diffuse agricultural pollution

An in situ technology for mitigating diffuse agricultural pollution using catch crops was developed for simultaneously preventing nitrate groundwater pollution, reducing nitrous oxide (N2O) gas emissions, and removing salts from the topsoil. Seasonal changes in the performance of a catch crop were investigated using lysimeters in a full-scale greenhouse experiment with 50 d cultivation of dent corn. Catch crop cultivation significantly reduced the leached mineral nitrogen by 89-91% in summer, 87-89% in spring, and 61-82% in winter, and it also significantly reduced the N2O emission by 68-84% in summer. The amounts of nitrogen uptake by the catch crop were remarkably higher than those of leached nitrogen and N2O emission in each season. Catch crop cultivation is a promising technology for mitigating diffuse agricultural pollution.

Characteristics of Nutrient Salt Uptake Associated with Water Use of Corn as a Catch Crop at Different Plant Densities in a Greenhouse

Abstract Dent corn, as a catch crop used for salt removal, was cultivated at different densities, i.e ., 7.3 (low density), 59.7 (normal density), and 119.5 plants m −2 (high density), during a 50 d fallow period after cultivation of a commercial crop in a greenhouse, to analyze the characteristics of nutrient salt (N, K, Mg, and Ca) uptake by roots and to study the effect of plant density on the characteristics associated with crop water use. Leaf area index for the high and normal density treatments reached extremely high values of 24.3 and 14.9, respectively. These values induced higher transpiration rates that were estimated using the Penman-Monteith model with the incorporation of specific parameters for crop and greenhouse conditions. The total N, K, Mg, and Ca contents in the crop canopy at harvest were 26.8, 13.0, 1.0, and 1.7 g m −2 , respectively, under the high density treatment. The dynamics of salt uptake rates for high, normal, and low density treatments were evaluated by assessing weekly changes in salt content, and were subsequently compared against the transpiration rate. A positive linear relationship was obtained between these 2 parameters for all 3 density treatments and all tested salts. Hence, higher transpiration rates caused higher salt uptake rates through water absorption. On the other hand, salt uptake efficiency per unit water use by cultivation was lower in the low density treatment. Therefore, management procedures with dense planting that induce higher transpiration rates and lower evaporation rate are extremely important for the effective cultivation of corn catch crops.