Kinetics of radiocesium released from contaminated soil by fertilizer solutions

(137)Cs is one of the major artificial radionuclides found in environments; but the mechanisms behind fertilizer-induced (137)Cs desorption from soil remain unknown. This study aimed to investigate the kinetics and mechanisms underlying the various cations and anions that cause Cs release from soil under acidic conditions. NH(4)H(2)PO(4) (1M), 0.5M (NH(4))(2)SO(4), 1M NH(4)Cl, 1M KCl or 1M NaCl solutions were added to (137)Cs-contaminated soil. The power function model well described the short term (137)Cs desorption with the solutions. The rate coefficients for (137)Cs release from soil in NH(4)H(2)PO(4), (NH(4))(2)SO(4), NH(4)Cl, and KCl solutions were 7.7, 7.3, 6.8, and 6.1 times higher than the rate observed in a NaCl solution, respectively. The NH(4)H(2)PO(4) and (NH(4))(2)SO(4) solutions induced significantly greater (137)Cs release from the contaminated soil than the NH(4)Cl, KCl and NaCl solutions. After four times repeated extractions with the fertilizer solutions, the total amount of (137)Cs extracted by (NH(4))(2)SO(4) and NH(4)Cl solutions reached equilibrium, while that extracted using an NH(4)H(2)PO(4) solution continued to increase. The combined effect of phosphate and protons was the major mechanism behind (137)Cs release from contaminated soils, when an NH(4)H(2)PO(4) solution was used.     

Removal of humic acid using TiO2 photocatalytic process--fractionation and molecular weight characterisation studies

The photocatalytic removal of humic acid (HA) using TiO₂ under UVA irradiation was examined by monitoring changes in the UV₂₅₄ absorbance, dissolved organic carbon (DOC) concentration, apparent molecular weight distribution, and trihalomethane formation potentials (THMFPs) over treatment time. A resin fractionation technique in which the samples were fractionated into four components: very hydrophobic acids (VHA), slightly hydrophobic acids, hydrophilic charged (CHA) and hydrophilic neutral (NEU) was also employed to elucidate the changes in the chemical nature of the HA components during treatment. The UVA/TiO₂ process was found to be effective in removing more than 80% DOC and 90% UV₂₅₄ absorbance. The THMFPs of samples were decreased to below 20 μg l⁻¹ after treatments, which demonstrate the potential to meet increasingly stringent regulatory level of trihalomethanes in water. Resin fractionation analysis showed that the VHA fraction was decreased considerably as a result of photocatalytic treatments, forming CHA intermediates which were further degraded with increased irradiation time. The NEU fraction, which comprised of non-UV-absorbing low molecular weight compounds, was found to be the most persistent component.     

Constituents of volatile organic compounds of evaporating essential oil

Essential oils containing aromatic compounds can affect air quality when used indoors. Five typical and popular essential oils—rose, lemon, rosemary, tea tree and lavender—were investigated in terms of composition, thermal characteristics, volatile organic compound (VOC) constituents, and emission factors. The activation energy was 6.3–8.6 kcal mol^?1, the reaction order was in the range of 0.6–0.8, and the frequency factor was 0.01–0.24 min^?1. Toluene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, n-undecane, p-diethylbenzene and m-diethylbenzene were the predominant VOCs of evaporating gas of essential oils at 40 °C. In addition, n-undecane, p-diethylbenzene, 1,2,4-trimethylbenzene, m-diethylbenzene, and 1,2,3-trimethylbenzene revealed high emission factors during the thermogravimetric (TG) analysis procedures. The sequence of the emission factors of 52 VOCs (137–173 mg g^?1) was rose ≈ rosemary > tea tree ≈ lemon ≈ lavender. The VOC group fraction of the emission factor of aromatics was 62–78%, paraffins were 21–37% and olefins were less than 1.5% during the TG process. Some unhealthy VOCs such as benzene and toluene were measured at low temperature; they reveal the potential effect on indoor air quality and human health.     

Cesium and strontium sorption by selected tropical and subtropical soils around nuclear facilities

The dynamics of Cs and Sr sorption by soils, especially in the subtropics and tropics, as influenced by soil components are not fully understood. The rates and capacities of Cs and Sr sorption by selected subtropical and tropical soils in Taiwan were investigated to facilitate our understanding of the transformation and dynamics of Cs and Sr in soils developed under highly weathering intensity. The Langmuir isotherms and kinetic rates of Cs and Sr sorption on the Ap1 and Bt1 horizons of the Long-Tan (Lt) and the A and Bt1 horizons of the Kuan-Shan (Kt), Mao-Lin (Tml) and Chi-Lo (Cl) soils were selected for this study. Air-dried soil (<2 mm) samples were reacted with of 7.5 × 10⁻⁵ to 1.88 × 10⁻³ M of CsCl (pH 4.0) or 1.14 × 10⁻⁴ to 2.85 × 10⁻³ M of SrCl₂ (pH 4.0) solutions at 25 °C. The sorption maximum capacity (q_m) of Cs by the Ap1 and Bt1 horizons of the Lt soil (62.24 and 70.70 mmol Cs kg⁻¹ soil) were significantly (p < 0.05) higher than those by the A and Bt1 horizons of the Kt and Cl soils (26.46 and 27.49 mmol Cs kg⁻¹ soil in Kt soil and 34.83 and 29.96 mmol Cs kg⁻¹ soil in Cl soil, respectively), however, the sorption maximum capacity values of the Lt and Tml soils did not show significant differences. The amounts of pyrophosphate extractable Fe (Fe_p) were correlated significantly with the Cs and Sr sorption capacities (for Cs sorption, r² = 0.97, p < 1.0 × 10⁻⁴; for Sr sorption, r² = 0.82, p < 2.0 × 10⁻³). The partition coefficient of radiocesium sorbed on soil showed the following order: Cl soil ? Kt soil > Tml soil > Lt soil. It was due to clay minerals. The second-order kinetic model was applied to the Cs and Sr sorption data. The rate constant of Cs or Sr sorption on the four soils was substantiality increased with increasing temperature. This is attributable to the availability of more energy for bond breaking and bond formation brought about by the higher temperatures. The rate constant of Cs sorption at 308 K was 1.39-2.09 times higher than that at 278 K in the four soils. The activation energy of Cs and Sr sorbed by the four soils ranged from 7.2 to 16.7 kJ mol⁻¹ and from 15.2 to 22.4 kJ mol⁻¹, respectively. Therefore, the limiting step of the Cs⁺ or Sr²⁺ sorption on the soils was diffusion-controlled processes. The reactive components, which are significantly correlated with the Langmuir sorption maxima of Cs and Sr by these soils, substantially influenced their kinetic rates of Cs and Sr sorption. The data indicate that among components of the subtropical and tropical soils studied, short-range ordered sesquioxides especially Al- and Fe-oxides complexed with organics play important roles in influencing their capacity and dynamics of Cs and Sr sorption.     

Microbial dechlorination of 2,4,6‐trichlorophenol in anaerobic sewage sludge

Abstract

The dechlorination of 2,4,6‐trichlorophenol (TCP) in municipal sewage sludge with a chlorophenol (CP)‐adapted consortium was investigated. Results show that dechlorination rates differed according to the source of the sludge samples used in the batch experiments. No significant differences in 2,4,6‐TCP dechlorination were observed following treatment with inoculum at densities ranging from 10% to 50% (V/V), but a significant delay was noted at 5% (V/V) density. Overall, results show that the higher the 2,4,6‐TCP concentration, the slower the dechlorination rate. The addition of acetate, lactate, pyruvate, vitamin B₁₂ or manganese dioxide did not results in a significant change in 2,4,6‐TCP dechlorination. Data collected from a bioreactor experiment revealed that pH 7.0 and a total solid concentration of 10 g/L were optimal for dechlorination. Dechlorination rates decreased significantly at higher agitation speeds. 2,4,6‐TCP dechlorination was enhanced under methanogenic conditions, but it was inhibited under denitrifying and sulfate‐reducing conditions.     

Seasonal Source-Receptor Relationships in a Petrochemical Industrial District over Northern Taiwan

Abstract

This study investigated the relationships between meteorological data, pollution sources, and receptors over northern Taiwan. During the intensive sampling period in summer 1992, the weather was controlled predominantly by a Pacific subtropical high and by Typhoon Mark. During the other intensive sampling period in winter 1993, while a cold frontal system approached Taiwan, the northeasterly winds prevailed most of the time. The local circulation such as land-sea breeze only developed under weak synoptic environment. Particle concentrations and element composition in winter were higher than in summer. This can be attributed to the high convection of air mass, which leads to the vertical dispersion of pollutants in summer. In addition to the subtropical high pressure, typhoons are frequently accompanied with high-wind speeds and unstable weather conditions that also dilute and eliminate the pollutants. In winter, the prevailing northeasterlies might carry pollutants from Midland China. Furthermore, the anticyclone system develops a stagnant condition that easily leads to pollutant accumulation. In this case, the wind direction affected the source contribution of the receptor and the PM₁₀ displays a higher correlation with coarse and fine particulate than meteorological parameters in summer. In addition, the mixing height shows a high correlation with PM₁₀ in winter.     

Emission factor of exhaust gas constituents during the pyrolysis of zinc chloride immersed biosolid

Pyrolysis enables ZnCl₂ immersed biosolid to be reused, but some hazardous air pollutants are emitted during this process. Physical characteristics of biosolid adsorbents were investigated in this work. In addition, the constituents of pyrolytic exhaust were determined to evaluate the exhaust characteristics. Results indicated that the pyrolytic temperature was higher than 500 °C, the specific surface area was >900 m²/g, and the total pore volume was as much as 0.8 cm³/g at 600 °C. For non-ZnCl₂ immersed biosolid pyrolytic exhaust, VOC emission factors increased from 0.677 to 3.170 mg-VOCs/g-biosolid with the pyrolytic temperature increase from 400 to 700 °C, and chlorinated VOCs and oxygenated VOCs were the dominant fraction of VOC groups. VOC emission factors increased about three to seven times, ranging from 1.813 to 21.448 mg/g for pyrolytic temperatures at 400–700 °C, corresponding to the mass ratio of ZnCl₂ and biosolid ranging from 0.25–2.5.     

Probabilistic risk assessment for personal exposure to carcinogenic polycyclic aromatic hydrocarbons in Taiwanese temples

To assess how the human exposure to airborne carcinogenic polycyclic aromatic hydrocarbons (PAHs) during working in or visiting a typical Taiwanese temple, we present a probabilistic risk model, appraised with reported empirical data. Two approaches are applied, one based on animal-derived benzo[a]pyrene (B[a]P) toxic equivalents (B[a]P(eq)) of individual PAHs and one is assumed that the potency of PAH mixtures is linked to their B[a]P level. The model integrates probabilistic exposure profiles of total-PAH and particle-bound PAH levels inside a temple from a published exploratory study with probabilistic incremental lifetime cancer risk (ILCR) models taking into account inhalation and dermal contact pathways, to quantitatively estimate the exposure risks for three age groups of adult, adolescent, and child. Risk analysis indicates that 90% probability inhalation ILCRs for three age groups have orders of magnitude around 10(-7)--10(-6); whereas for the dermal contact ILCRs ranging from 10(-5) to 10(-4), indicating high potential cancer risk. All 90% probabilities of B[a]P- and B[a]P(eq)-based total ILCRs are larger than 10(-6), indicating unacceptable probability distributions for three age groups. Sensitivity analysis indicates that to increase the accuracy of the results efforts should focus on a better definition of probability distributions for inhalation cancer slope factor, inhalation rates, and particle-bound PAH-to-skin adherence factor. We estimate risk-based visiting frequency advice for adult, adolescent, and child to a temple ranging from 5 to 7, 17 to 23, and 48 to 65 year(-1), respectively, based on an average 3h residence time.     

Linking valve closure behavior and sodium transport mechanism in freshwater clam Corbicula fluminea in response to copper

Sediment geochemical technique was employed to assess how the sediment records reflect the environmental changes of Jiaozhou Bay, a semi-enclosed bay adjacent to Qingdao, China. In the past hundred years, Jiaozhou Bay has been greatly impacted by human interventions. A dated core sediment by 210Pb chronology was analyzed for trace metals including Li, Cd, Cr, Pb, Cu, Ni, Co, Zn together with C, N, P and BSi. Based on the research, the development of Jiaozhou Bay environment in the past hundred years can be divided into three stages: (1) before the 1980s characterized by relatively low sedimentation rate, weak heavy metal pollution and scarce eutrophication; (2) from the 1980s to 2000, accelerating in the 1990s, during which high sedimentation rates, polluted by heavy metals and the frequent occurrence of red tide; (3) after 2000, the period of the improvement of environment, the whole system has been meliorated including the heavy metal pollution and hypernutrification.     

Applying mass transfer models for controlling organic compounds in ozonation process

Mass transfer plays a significant role in the ozonation process. The prediction models associated with the volumetric overall mass transfer coefficient (K_La) and initial fractional ozone absorption (FOA₀) during the ozonation process were developed through the use of dimensional analysis. It was found that the volumetric overall mass transfer coefficient is the function of diffusivity, agitation speed, and gas flow rate, and the parameters in the K_La equation are determined. Application of the prediction models for K_La and FOA₀ would yield information to choose the most practically feasible operating parameters. The removability of total organic carbon (TOC) can be estimated based on the mass balance relationship and kinetic expression of TOC oxidation, during continuous laboratory ozonation of humic acid solution. The reaction rate constant averaged 0.0291 L/mg·min. The developed model in combination with the mass transfer and reaction kinetics can be used successfully in forecasting the most efficient agitation speed to control the formation of organic compounds. Also, the critical value of ozone partial pressure to achieve the highest TOC removability can be determined through the use of the above developed model.