High immobilization of soil cesium using ball milling with nano-metallic Ca/CaO/NaH2PO4: implications for the remediation of radioactive soils

This report shows that cesium can be immobilized in soils with an efficiency of 96.4% by ball milling with nano-metallic Ca/PO₄. In Japan, the major concern on ¹³⁷Cs deposition and soil contamination due to the emission from the Fukushima Daiichi nuclear power plant showed up after a massive quake on March 11, 2011. The accident rated 7, the highest possible on the international nuclear event scale, released 160 petabecquerels (PBq) of iodine ¹³¹I and 15 PBq of ¹³⁷Cs according to the Japanese Nuclear and Industrial Safety Agency. Both ¹³⁷Cs and ¹³¹I radioactive nuclides are increasing cancer risk. Nonetheless, ¹³⁷Cs, with a half-life of about 30 years compared with 8 days for ¹³¹I, is a major threat for agriculture and stock farming and, in turn, human life for decades. Therefore, in Japan, the ¹³⁷Cs fixation and immobilization in contaminated soil is the most important problem, which should be solved by suitable technologies. Ball milling treatment is a promising treatment for the remediation of cesium-contaminated soil in dry conditions. Here, we studied the effect, factors and mechanisms of soil Cs immobilization by ball milling with the addition of nano-metallic Ca/CaO/NaH₂PO₄, termed “nano-metallic Ca/PO₄.” We used scanning electron microscopy combined with electron dispersive spectroscopy (SEM/EDS) and X-ray diffraction. Results show that immobilization efficiency increases from 56.4% in the absence of treatment to 89.9, 91.5, and 97.7 when the soil is ball-milled for 30, 60 and 120 min, respectively. The addition of nano-metallic Ca/PO₄ increased the immobilization efficiency to about 96.4% and decreased the ball milling time. SEM/EDS analysis allows us to observe that the amount of Cs decreased on soil particle surface. Use of nano-metallic Ca/PO₄ over a short milling time also decreases Cs leaching. Therefore, ball milling with nano-metallic Ca/PO₄ treatment may be potentially applicable for the remediation of radioactive Cs-contaminated soil in dry conditions.     

Zinc oxide nanoparticles as efficient catalyst for the synthesis of novel di-spiroindolizidine bisoxindoles in aqueous medium

Environmental Chemistry Letters - Developing environmentally benign synthetic protocols such as reaction in water is a major challenge. However, many of the known methods carried out in an...     

Allometric models for the estimation of above- and below-ground biomass of Jatropha curcas L. in semi-arid regions of Southern India

Jatropha curcas L. (Jatropha) is an important multipurpose tree valued for oil. In India, plans are underway to bring substantial area under this crop for meeting the biofuel requirements of the country. A study was conducted to develop allometric relationships in Jatropha to predict various biomass-related components (above ground and below ground) using easily measurable attributes, viz. collar diameter, tree height, number of branches, crown diameter, and crown depth. Further, it was aimed to establish the reliability of these relationships using an independent dataset obtained from varied management situations. Destructive sampling was carried out during the rainy season of 2011, when Jatropha plants were eight years old. Highly significant allometric relationships (F-values significant at 1% level) were obtained while predicting various biomass components (above, below, and total) using easily measurable attributes with R² values ranging from 0.89 to 0.98. Of all the predictors, collar diameter exhibited a highly significant relationship with total dry biomass per plant (R² = 0.97). The allometric relationships developed were validated with an independent dataset. The allometric relationships developed would serve as valuable tools for estimating total dry biomass production and carbon sequestration with reasonable accuracy in Jatropha systems, as they are proposed to be taken up in substantial area in the years to come.     

The significance of trisomy 7 mosaicism in chorionic villus cultures

Two cases of mosaic trisomy 7 confined to the cultured cells and not found in direct preparation were detected from 200 consecutive first-trimester chorionic villus samples (CVS) analysed. The mosaicism was similar in the two cases, but the pregnancy outcome was different. In both cases, the direct metaphases from the CVS were 46, XY. Culture metaphases were mos46,XY/47,XY, + 7; the trisomy 7 was seen in 34 per cent of cells from case 1 and 53 per cent from case 2. A sonogram at 15¹/₂ weeks revealed fetal death in utero in case 1, and the patient declined amniocentesis. The fetal tissue failed to grow in culture, but the placental cultured cells were 47,XY, + 7 in 28 (100 per cent) cells analysed. In the second case, all the amniotic fluid cells were 46,XY and the pregnancy resulted in a normal male with a 46,XY karyotype in the cord blood and foreskin fibroblast cultures. The term placenta was mosaic with 13/163 (8 per cent) trisomy 7 cells. Extensive cytogenetic studies on the placenta for the first time confirmed trisomy 7 mosaicism confined to the villus cultures.     

Stable chlorine intramolecular kinetic isotope effects from the abiotic dehydrochlorination of DDT

INTENTION, GOAL, SCOPE, BACKGROUND: Identifying different sources and following reaction pathways of chlorinated organic contaminants in the environment can be challenging, especially when only their concentrations are available. Compound-specific stable chlorine measurements of some contaminants have recently been shown to provide additional information and an increased understanding of their biogeochemistry. These studies, however, have been generally limited to volatile molecules. OBJECTIVE: Here, the stable chlorine isotope ratios of the semi-volatile pesticide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) were investigated. Specifically, the intramolecular stable chlorine isotopic compositions of DDT and the kinetic isotope effect (KIE) for the abiotic dehydrochlorination of DDT to 2,2-bis(p-chlorophenyl)-1,1-dichloroethene (DDE) were determined. METHODS: Selective chemical oxidation of DDT to dichlorobenzophenone (DCBP) and analysis of each compound was used to calculate the stable chlorine isotope ratios of the alkyl and aromatic chlorines in DDT. To determine the KIE for dehydrochlorination, DDT was reacted in a basic solution to yield DDE at 52 degrees C, 60 degrees C, and 72 degrees C for 3, 5, and 5 days, respectively. RESULTS AND DISCUSSION: Significant intramolecular stable chlorine isotopic differences were observed in one sample of DDT where the alkyl and aromatic delta 37Cl values were -5.76 +/- 0.45 and -2.21 +/- 0.24%@1000, respectively. Dehydrochlorination of DDT to DDE in basic solutions at 52, 60, and 70 degrees C resulted in a substantial intramolecular KIE where the alkyl chlorines of DDE shifted by approximately 3%@1000 relative to the alkyl chlorines in DDT. However, no temperature dependence was observed. The KIE, calculated by an iterative program, was 1.009. CONCLUSIONS: Intramolecular differences in the stable chlorine isotope ratios were observed in DDT and this is the first such finding. Dehydrochlorination of DDT yields a measurable and distinct intramolecular stable chlorine KIE. RECOMMENDATION AND OUTLOOK: The results of this study demonstrate the existence of significant intramolecular differences in chlorinated organic compounds. Many other chlorinated semi-volatile and volatile organic contaminants are synthesized from multiple sources of chlorine, and we recommend that similar studies be performed on many such molecules in order to attain a clear understanding of their intramolecular chlorine isotopic differences. The existence of a measurable KIE for the dehydrochlorination of DDT to DDE shows the potential strength of using isotopic measurements to investigate the biogeochemistry of these important compounds. For example, the isotopically depleted aqueous chloride produced by dehydrochlorination of DDT to DDE may be a useful tracer of these reactions in freshwater environments.     

Variations in bottom sediment nutrient and metal concentrations in the Genesee River watershed,New York

Variations in nutrient and metal concentrations of fluvial sediment may be due to varying combinations of natural and man-made factors: basin geology, surface erosion, riverbank erosion, industrial or other cultural contamination, the presence of minerals rich in trace elements (e.g. chromite), sediment ion-exchange capacity, sediment organic content, and the presence of metallic oxides. The data reported here were obtained in a study in New York State of sediment transport from the Genesee River watershed to Lake Ontario (6,500 km²; 2,400 sq.mi.). One hundred bottom sediment samples collected over a period of a year were chemically analyzed for aluminium, chromium, copper, iron, manganese, nickel, lead, zinc, total carbon, total organic carbon, total nitrogen, and phosphorus. The metal concentrations (arithmetic means ±S.D., in μg/g) were: Al, 6,660±2,620; Cr, 14±9; Cu, 18±7; Fe, 15,060±7,312; Mn, 424±212; Ni, 23±13; Pb, 40±67; and Zn, 69±37. For the major nutrients the results (mean ±1 S.D. in %) were: total carbon, 2.06 ± 1.68; total organic carbon, 1.37 ± 1.28; total nitrogen, 0.105 ± 0.098; and phosphorus, 0.0560 ± 0.014.     

Environmental Monitoring of Benzene and Alkylated Benzene from Vehicular Emissions

The volatile organic pollutants from direct vehicular exhaust were trapped with activated charcoal, desorbed with carbon disulphide and analysed by GC/MS with tert-butyl benzene as an internal standard. A comparative study was made from the exhaust of 1000 cc, 1300 cc, 1600 cc cars, pickup, lorry(diesel), 125 cc and 70 cc motorbikes. The level of pollutants emitted were in the following order, motorbike(petrol) car(petrol) pickup(petrol) lorry(diesel). The range of highest emission (125 cc motorbike) to the lowest emission (lorry(diesel)) was of the order of 102 for benzene, 6×102 for ethyl benzene, 5×102 for toluene and 3×102 for xylenes. Among cars, those fitted with catalytic convertors emitted a lower level of benzene (2 to 3 times) when compared with those without catalytic convertors. Similar studies on the air in air-conditioned buses, non air-conditioned buses and three metres from the edge of the road shows that they have the same pollutant level. The level of these pollutant as compared to those from direct car exhaust are of the order of 102 times less for benzene, xylene and toluene and 103 times less for ethylbenzene. The levels of benzene, toluene, ethylbenzene and xylenes by the road side and in the buses were found to be lower than the exposure limits of ACGIH, OSHA and EH40.     

A numerical model for drying of spherical object in an indirect type solar dryer and estimating the drying time at different moisture level and air temperature

A numerical model for simultaneous heat and mass transfer was developed for solar drying of spherical objects and the object considered is green peas. Solar collector outlet temperature is assumed as drying chamber temperature and justified through energy balance equations. Assumptions are imposed on heat and mass transfer governing equations without losing the physics of the problem. Discretization is performed by finite difference method with implicit scheme. To generalize, the governing equation and boundary conditions are non-dimensionalized. The set of finite difference equations was solved by Tridiagonal Matrix Algorithm and a computer code in MATLAB was developed to solve them. The drying curves showed two stages of drying, initial, and secondary drying stage. At all drying temperatures and drying time, the center moisture was maximum and it was minimum at the boundary. A percentage of 85.67 surface moisture content and 25.33% center moisture was eliminated in the first 1 hr at 348 K. The product should be dried up to 7.45, 4.74, and 3.74 hr at air drying temperatures of 318, 333, and 348 K respectively, to maintain 10% of the product’s initial moisture content. The result is compared with the experimental result from literature and they are found to be in good agreement.     

Influence of nanoscale zero-valent iron on hydraulic conductivity of a residual clayey soil and modeling of the filtration parameter

Environmental Science and Pollution Research - Contaminated clay soils pose problems to public health and the environment in several parts of the world. Very little is known about the transport of...