Feasibility of phosphate fertilizer to immobilize cadmium in a field

To reduce effectively cadmium (Cd) phytoextractability by phosphate fertilizer in Cd contaminated soil, fused and superphosphate (FSP) was applied at the rate of 0, 33.5 (recommendation level), 167.5, and 335 kg P ha⁻¹ for radish (Raphanus sativa L.). Unlike from what we expected, soil Cd extractability and Cd concentration in radish increased with increasing FSP application in the field. To determine the effect of FSP on Cd immobilization, FSP was mixed with the selected soil at the rate of 0, 200, 400, 800, and 1600 mg P kg⁻¹ and then incubated for 8 weeks. As observed in the field study, NH₄OAc extractable Cd concentration increased slightly with FSP addition up to 400 mg P kg⁻¹ and thereafter dramatically decreased upon increasing its application rate. Soil pH and negative charge were decreased at low level of FSP application up to 400 mg P kg⁻¹, but thereafter continually increased with increasing application level. This could be indirect evidence that net soil negative charge was increased by the specific adsorption of phosphate at the high rate of FSP application over 400 mg P kg⁻¹. The labile Cd fraction (water soluble and exchangeable + acidic fraction) increased with increasing FSP application by 400 mg P kg⁻¹ and thereafter gradually decreased with corresponding increase in unlabile fraction (oxidizable and residual fraction). Based on these results, FSP might be applied with a very high rate over 800 mg P kg⁻¹ to decrease Cd extractability in the selected field. However, this level is equivalent to 1440 kg P ha⁻¹, which is about 43 times higher than the recommendation levels for radish production and resulted in a significant increase in water soluble P concentration creating a new environmental problem. Therefore, the feasibility of FSP to reduce Cd extractability in the field is very low.     

Pentachlorophenol sorption by variable-charge soils in methanol-water mixture: pH effect at the low solvent volume fraction

Information on how cosolvents affect sorption of ionizable chemicals by soils with heterogeneous variable-charge mineral surface domains is sparse. In this study, the effect of soil-solution pH in methanol/water solutions on sorption of pentachlorophenol (PCP) by variable-charge soils with a range of hydrophilic (f Hphilic) and hydrophobic (f Hphobic) sorption domains was characterized. PCP sorption by 10 variable-charge soils was measured as a function of apparent pH (pH app) and methanol volume fraction (fc8) decreased log-linearly with increasing fc, but the slope of the relationship was less for anionic PCP. The empirical solvent-sorbent interaction term for anionic PCP (alpha i) was inversely correlated with f Hphilic (r2=0.82), which is consistent with methanol-induced increases in anion exchange. For neutral PCP, the empirical term (alpha n) was positively correlated with f Hphobic (r2=0.84), supporting methanol-induced increases in solution and sorbent hydrophobicity. Sorption of PCP by two soils with varying f Hphilic in the pH app range from 3 to 8 at fc相似文献   

Decomposition and mineralization of cefaclor by ionizing radiation: kinetics and effects of the radical scavengers

There has been recent growing interest in the presence of antibiotics in different environmental sectors. One considerable concern is the potential development of antibiotic-resistant bacteria in the environment, even at low concentrations. Cefaclor, one of the beta-lactam antibiotics, is widely used as an antibiotic. Kinetic studies were conducted to evaluate the decomposition and mineralization of cefaclor using gamma radiation. Cefaclor, 30 mg/l, was completely degraded with 1,000 Gy of gamma radiation. At a concentration of 30 mg/l, the removal efficiency, represented by the G-value, decreased with increasing accumulated radiation dose. Batch kinetic experiments with initial aqueous concentrations of 8.9, 13.3, 20.0 and 30.0mg/l showed the decomposition of cefaclor using gamma radiation followed a pseudo first-order reaction, and the dose constant increased with lower initial concentrations. At a given radiation dose, the G-values increased with higher initial cefaclor concentrations. The experimental results using methanol and thiourea as radical scavengers indicated that ()OH radicals were more closely associated with the radiolytic decomposition of cefaclor than other radicals, such as e(aq)(-) or ()H. The radical scavenger effects were tested under O(2) and N(2)O saturations for the enhancement of the TOC percentage removal efficiencies in the radiolytic decomposition of cefaclor. Under O(2) saturation, 90% TOC removal was observed with 100,000 Gy. Oxygen is well known to play a considerable role in the degradation of organic substances with effective chain reaction pathways. According to the effective radical reactions, the enhanced TOC percentage removal efficiencies might be based on the fast conversion reactions of e(aq)(-) and ()H with O(2) into oxidizing radicals, such as O(2)(-) and HO(2)(), respectively. 100% TOC removal was obtained with N(2)O gas at 20,000 Gy, as reducing radicals, such as e(aq)(-) and ()H, are scavenged by N(2)O and converted into ()OH radicals, which have strong oxidative properties. The results of this study showed that gamma irradiation was very effective for the removal of cefaclor in aqueous solution. The use of O(2) or N(2)O, with radiation, shows promise as effective radical scavengers for enhancing the TOC or COD removal efficiencies in pharmaceutical wastewaters containing antibiotics. However, the biological toxicity and interactions between various chemicals during the radiolytic treatment, as well as treatments under conditions more representative of real wastewater will require further studies.     

Comparative and combined toxicities of toluene and methyl tert-butyl ether to an Asian earthworm Perionyx excavatus

An earthworm assay was used to assess the toxicity of two main gasoline components. Ecotoxicities of toluene and methyl tert-butyl ether (MTBE) were compared for Asian earthworm Perionyx excavatus separately and in combination. Sum of toxic unit (TU) at 50% mortality for the mixture (LC50mix) was estimated from the dose (TU-based)-response relationships by the Trimmed Spearman-Karber method. Toluene was shown to be about five and two times more toxic to P. excavatus than MTBE in filter paper contact test and natural soil tests, respectively. This is primarily due to the adsorption of toluene to soil particles, leading to less bioavailability of toluene to the earthworm in soil. The combined effect of toluene and MTBE was investigated using toxic unit model, and it was found to be almost additive and synergistic responses to P. excavatus in filter paper contact test and soil tests, respectively. The combined effect of toluene and MTBE in filter paper contact test was not consistent with the results in soil toxicity tests. This phenomenon may be associated with the interaction of soil salts with pollutants. Treatment with toluene and MTBE also affected the behavior and morphology of P. excavatus. It indicates that the VOCs induce metabolic and functional damages in earthworms. Combined effects of gasoline components should be taken into account to soil risk assessment.     

Characterization of cyclohexane and hexane degradation by Rhodococcus sp. EC1

Cyclohexane is a recalcitrant compound that is more difficult to degrade than even n-alkanes or monoaromatic hydrocarbons. In this study, a cyclohexane-degrading consortium was obtained from oil-contaminated soil by an enrichment culture method. Based on a 16S rDNA polymerase chain reaction-denaturing gradient gel electrophoresis method, this consortium was identified as comprising Alpha-proteobacteria, Actinobacteria, and Gamma-proteobacteria. One of these organisms, Rhodococcus sp. EC1, was isolated and shown to have excellent cyclohexane-degrading ability. The maximum specific cyclohexane degradation rate (Vmax) for EC1 was 246 micromol g-DCW(-1) (dry cell weight)h(-1). The optimum conditions of cyclohexane degradation were 25-35 degrees C and pH 6-8. In addition to its cyclohexane degradation abilities, EC1 was also able to strongly degrade hexane, with a maximum specific hexane degradation rate of 361 micromol g-DCW(-1)h(-1). Experiments using 14C-hexane revealed that EC1 mineralized 40% of hexane into CO2 and converted 53% into biomass. Moreover, EC1 could use other hydrocarbons, including methanol, ethanol, acetone, methyl tert-butyl ether, pyrene, diesel, lubricant oil, benzene, toluene, ethylbenzene, m-xylene, p-xylene and o-xylene. These findings collectively suggest that EC1 may be a useful biological resource for removal of cyclohexane, hexane, and other recalcitrant hydrocarbons.     

Catalytic reduction of sulfur dioxide with carbon monoxide over tin dioxide for direct sulfur recovery process

SO(2) reduction by CO over SnO(2) catalyst was studied in this work. The parameters were the reaction temperature, space velocity (GHSV) and [CO]/[SO(2)] molar ratio. The optimal temperature, GHSV and [CO]/[SO(2)] molar ratio were 550 degrees C, 8000 h(-1) and 2.0, respectively. Under these conditions, the SO(2) conversion and sulfur selectivity were about 78% and 68%, respectively. The following reaction pathway involving two mechanisms was proposed in SO(2) reduction by CO over SnO(2) catalyst: in the first step involving Redox mechanism, the elemental sulfur was produced by the mobility of the lattice oxygen between SO(2) and SnO(2) surface. In the second step, COS was formed by the side reaction between elemental sulfur and CO or metal sulfide and CO. In the third step involving COS intermediate mechanism, the abundant elemental sulfur was produced by the SO(2) reduction by COS which was produced in the second step and was more effective reducing agent than CO.     

Development of human dermal epithelial cell-based bioassay for the dioxins

None of bioassays is complete for assessing biological impact in humans upon the xenobiotic exposure due to species and organ-specific responsiveness. Thus, it is speculated that the human cell-based bioassay may be more appropriate system because of its direct relevance to humans. Here, we have developed a human epidermal cell-based bioassay for the dioxins and related compounds. The AD12-SV40-immortalized human keratinocyte cell line was stably transfected with a recombinant expression vector which contains the luciferase gene under dioxin-inducible control of four DREs. The tansfectants showed a consistent dose-response of luciferase activity upon dioxin exposure even after 120 passages. The maximal half effective dose (EC50) was 200 pM with a maximum of 32-fold induction of luciferase activity at 5 nM. The minimum detection limit was 10 pM. Optimal exposure time for the assay was 24h. When cells were treated with aryl hydrocarbon receptor agonists of different toxic equivalent factor (TEF) values, the shape of the dose-response curve for each compound was parallel to that of TCDD and the maximum response was similar, indicating that this bioassay system can be applied to generate the total toxic equivalency (TEQ) estimate from the samples. When relative induction potency of luciferase activities for each compound was calculated, it was similar to WHO-TEF values within an order of magnitude. This human cell system can be used as an efficient screening tool to quantify the TEQ values of dioxin-like chemicals in the samples and may help understand the interspecies difference between humans and animals.     

Characterization of controlled-release KMnO4 (CRP) barrier system for groundwater remediation: a pilot-scale flow-tank study

Release and spreading of permanganate (MnO(4)(-)) in the well-based controlled-release potassium permanganate (KMnO(4)) barrier system (CRP system) was investigated by conducting column release tests, model simulations, soil oxidant demand (SOD) analyses, and pilot-scale flow-tank experiments. A large flow tank (L x W x D=8m x 4m x 3m) was constructed. Pilot-scale CRP pellets (OD x L=0.05 m x1.5m; n=110) were manufactured by mixing approximately 198 kg of KMnO(4) powders with paraffin wax and silica sands in cylindrical moulds. The CRP system (L x W x D=3m x 4m x 1.5m) comprising 110 delivery wells in three discrete barriers was constructed in the flow tank. Natural sands (organic carbon content=0.18%; SOD=3.7-11 g MnO(4)(-)kg(-1)) were used as porous media. Column release tests and model simulations indicated that the CRP system could continuously release MnO(4)(-) over several years, with slowly decreasing release rates of 2.5 kg d(-1) (day one), 109 g d(-1) (day 100), 58 g d(-1) (year one), 22 g d(-1) (year five), and 12 g d(-1) (year 10). Mean MnO(4)(-) concentrations within the CRP system ranged from 0.5 to 6 mg l(-1) during the 42 days of testing period. The continuously releasing MnO(4)(-) was gradually removed by SOD limiting the length of MnO(4)(-) zone in the porous media. These data suggested that the CRP system could create persistent and confined oxidation zone in the subsurface. Through development of advanced tools for describing agent transport and facilitating lateral agent spreading, the CRP system could provide new approach for long-term in situ treatment of contaminant plumes in groundwater.     

Quaternary stratigraphy, sediment characteristics and geochemistry of arsenic-contaminated alluvial aquifers in the Ganges–Brahmaputra floodplain in central Bangladesh

This study focuses on the Quaternary stratigraphy, sediment composition, mineralogy, and geochemistry of arsenic (As)-contaminated alluvial aquifers in the Ganges–Brahmaputra floodplain in the central Bangladesh. Arsenic concentrations in 85 tubewells in Manikganj area, 70 km northwest of Dhaka City, range from 0.25 µg/L to 191 µg/L with a mean concentration of 33 µg/L. Groundwater is mainly Ca–HCO₃ type with high concentrations of dissolved As, Fe, and Mn, but low level of SO₄. The uppermost aquifer occurs between 10 m and 80 m below the surface that has a mean arsenic concentration of 35 µg/L. Deeper aquifer (> 100 m depth) has a mean arsenic concentration of 18 µg/L. Sediments in the upper aquifer are mostly gray to dark-gray, whereas sediments in the deep aquifer are mostly yellowing-gray to brown. Quartz, feldspar, mica, hornblende, garnet, kyanite, tourmaline, magnetite, ilmenite are the major minerals in sediments from both aquifers. Biotite and potassium feldspar are dominant in shallow aquifer, although plagioclase feldspar and garnet are abundant in deep aquifer sediments. Sediment composition suggests a mixed provenance with sediment supplies from both orogenic belts and cratons. High arsenic concentrations in sediments are found within the upper 50 m in drilled core samples. Statistical analysis shows that As, Fe, Mn, Ca, and P are strongly correlated in sediments. Concentrations of Cd, Cu, Ni, Zn, and Bi also show strong correlations with arsenic in the Manikganj sediment cores. Authigenic goethite concretions, possibly formed by bacteria, are found in the shallow sediments, which contain arsenic of a concentration as high as 8.8 mg/kg. High arsenic concentrations in aquifers are associated with fine-grained sediments that were derived mostly from the recycled orogens and relatively rapidly deposited mainly by meandering channels during the Early to Middle Holocene rising sea-level conditions.     

Hydrochemistry of urban groundwater, Seoul, Korea: the impact of subway tunnels on groundwater quality

Hydrogeologic and hydrochemical data for subway tunnel seepage waters in Seoul (Republic of Korea) were examined to understand the effect of underground tunnels on the degradation of urban groundwater. A very large quantity of groundwater (up to 63 million m³ year^− 1) is discharged into subway tunnels with a total length of 287 km, resulting in a significant drop of the local groundwater table and the abandonment of groundwater wells. For the tunnel seepage water samples (n = 72) collected from 43 subway stations, at least one parameter among pathogenic microbes (total coliform, heterotrophic bacteria), dissolved Mn and Fe, NH₄⁺, NO₃⁻, turbidity, and color exceeded the Korean Drinking Water Standards. Locally, tunnel seepage water was enriched in dissolved Mn (avg. 0.70 mg L^− 1, max. 5.58 mg L^− 1), in addition to dissolved Fe, NH₄⁺, and pathogenic microbes, likely due to significant inflow of sewage water from broken or leaking sewer pipes.Geochemical modeling of redox reactions was conducted to simulate the characteristic hydrochemistry of subway tunnel seepage. The results show that variations in the reducing conditions occur in urban groundwater, dependent upon the amount of organic matter-rich municipal sewage contaminating the aquifer. The organic matter facilitates the reduction and dissolution of Mn- and Fe-bearing solids in aquifers and/or tunnel construction materials, resulting in the successive increase of dissolved Mn and Fe. The present study clearly demonstrates that locally significant deterioration of urban groundwater is caused by a series of interlinked hydrogeologic and hydrochemical changes induced by underground tunnels.