Gas-phase reaction of CCl2F2 (CFC-12) with methane

Gas-phase reaction of CFC-12 (CCl2F2) with methane was carried out in a plug flow reactor over the temperature range of 873-1123 K. The major organic halocarbons formed during the reaction were C2F4, C2H2F2, CHClF2, CH3Cl, C3H2F6 and CCl3F. The formation of all products except C2H2F2 decreased with temperature, while the selectivity to C2H2F2 (difluoroethylene) increased with temperature and reached approximately 80% at 1123 K. Under these reaction conditions, methane acts as hydrogen and carbon source, resulting in the formation of an unsaturated C2 hydrofluorocarbon from two C1 precursors.     

Rainwater chemistry at the summit and southern flank of the Itatiaia massif, Southeastern Brazil

Wet deposition and related rainwater chemistry were studied at the Itatiaia massif, on which is settled the Itatiaia National Park (INP). Samples were simultaneously collected on a weekly basis over 12 months, using automated wet and dry samplers, at the INP-Headquarters (INP-Hq; altitude=820 m) and the Itatiaia Plateau (It-Pt; altitude=2460 m). Conductivity, pH, Na(+), K(+), Mg(2+), Ca(2+), NH(4)(+), Cl(-), NO(3)(-) and SO(4)(2-) were determined in 36 rainwater samples. Volume-weighted mean (VWM) pH was lower at the INP-Hq (4.9) than at the It-Pt (5.3). Very strong correlation between Cl(-) and Na(+) was found for the INP-Hq (r=0.99). At the Itatiaia massif, SO(4)(2-), NO(3)(-), and NH(4)(+) comprised together about 60% of the total inorganic ions and appear to exert the major control on rainwater pH.     

2-Chlorobenzoate biodegradation by recombinant Burkholderia cepacia under hypoxic conditions in a membrane bioreactor.

The feasibility of applying bacterial hemoglobin technology to degrade 2-chlorobenzoate (2-CBA) through co-metabolism under hypoxic conditions in a membrane bioreactor (MBR) process has been studied in the laboratory. 2-chlorobenzoate removal and chloride release rates in the MBR system varied from 99 to 78% and 98 to 73%, respectively, depending on the operation conditions. Chemical oxygen demand (COD) removal efficiencies were more than 90% at food-to-microorganism ratios ranging from 0.32 to 0.62 g/g/d, and the observed yield was 0.13 to 0.20 g biomass/g COD. The bacterial cell-floc size-distribution analysis showed that there is a significant change in bacterial floc size due to high shear stress during operation of the MBR. To characterize growth kinetics of Burkholderia cepacia strain dinitrotoluene, a mathematical model that describes co-metabolic oxidation of 2-CBA in an MBR has been developed.     

Temporal changes in kerosene content and composition in field soil as a result of leaching

A field experiment was designed to determine the combined effect of leaching and natural attenuation on the redistribution dynamics of kerosene--a volatile petroleum hydrocarbon mixture (VPHM)--and of its selected individual components in the soil subsurface. Variables included the composition of contaminant spilled, the soil water content before contamination and the leaching pattern. Temporal changes in the residual kerosene concentration and composition in the soil subsurface of the experimental field during 39 days and leaching by 500 mm of irrigation water were determined to a depth of 100 cm. The main processes controlling contaminant attenuation were volatilization and redistribution with depth. Soil hydration status was found to affect the attenuation, redistribution and composition of VPHM in the porous media. An initial relative increase of n-alkanes in the subsurface compared with the total VPHM in the first leaching period was a result of the volatilization of low vapor pressure compounds. The redistribution of individual components in the soil profile during leaching was in accordance with their physico-chemical properties.     

The Danish incinerator dioxin study. Part 1

During the last two years an extensive series of dioxin measurements has been conducted on Danish municipal and hospital solid waste incinerators. The study was directed toward finding the total annual dioxin emissions from MSWI in Denmark, now estimated to be 3 kg. of dioxines and furanes. This sum is equivalent to 50 g. of 2,3,7,8-TCDD according to the Nordic Equivalents. Measurements were carried out according to a statistical design following a plan of pre-randomized sampling. This procedure allowed causal interpretation of the correlations found between the dioxin emissions and certain operating parameters. The statistical model obtained describes the emissions by variations between incinerators, by variation in time, and by changes in the load, the excess air and the HCl concentration in the flue gas.     

Mobility of Zn, Cd and Pb in soils as affected by poultry litter extract--I. Leaching in soil columns

Application of poultry litter to cropland may increase metal mobility, because the soluble organic ligands in poultry litter can form water-soluble complexes with metals. In this study, one uncontaminated soil and two metal-contaminated soils were sampled. A portion of the uncontaminated soil was amended with Zn, Pb, and Cd at rates of 400, 200, and 8 mg kg(-1), respectively. Packed soil columns were leached with H2O, EDTA, CaCl2, and poultry litter extract (PLE) solutions separately. No leaching of Zn, Cd, and Pb with the PLE was found in the uncontaminated soil. The retention of PLE-borne Zn indicated the potential for Zn accumulation in the soil. A large portion of the metals was leached from the metal-amended soil, and EDTA solubilized more Zn, Cd, and Pb than CaCl2 and PLE. In the metal-contaminated soils, the leaching of Zn and Cd with PLE was consistently larger than that for CaCl2, indicating that these metals were mobilized by organic ligands. The PLE did not mobilize Pb in these soils. The utilization of poultry litter in metal-contaminated soils might accelerate the movement of Zn and Cd in soil profiles.     

The oldest known tracks of web-footed birds from the Lower Cretaceous of South Korea

 We describe the oldest tracks of web-footed birds from the Early Cretaceous in South Korea. The tracks are characterized by a wide divarication angle and a long reversed hallux. The web is semipalmate and restricted to the proximal portion of the three forward digits. The tracks from the Early Cretaceous in South Korea are smaller than those of the Late Cretaceous, therefore confirming the trend of size increasing in the early evolution of birds as shown by skeletal fossils. The discovery of web-footed tracks with abundant non-web-footed tracks indicates that there was a considerable diversification of shore birds as early as the Early Cretaceous. Received: 4 November 1999 / Accepted in revised form: 28 February 2000     

‘False-negative’ and ‘false-positive’ prenatal cytogenetic results due to ‘true’ mosaicism

A 37-year-old gravida was referred for CVS because of advanced maternal age. A trisomy 21 was present in all cells after short-term incubation (direct processing (DP)) and long-term culture. According to our policy, a retap was offered for confirmation of the result during the legally required 3-day waiting period between communication of the result and termination of pregnancy. Unexpectedly all cells after DP showed a normal male chromosome complement. Further investigations revealed mosaicism in trophoblast tissue and a normal karyotype in amniotic fluid cells and fetal blood (50 mitoses each). The parents elected to continue the pregnancy after extensive ultrasound examinations did not show suspicious findings. After the birth of a healthy child, cell cultures from ten different placental sites confirmed mosaicism. Four out of 100 mitoses from a lymphocyte culture showed an additional chromosome 21. The child had no dysmorphic features and the development was normal at the age of 10 weeks. This case demonstrates the restricted validity of prenatal cytogenetic analysis in the presence of true fetal mosaicism. It also stresses the benefit of our policy to offer a retap in cases with abnormal cytogenetic results prior to termination of pregnancy which is considered unnecessary by many cytogeneticists.     

Distribution and Fractionation of Heavy Metals in Solid Waste from Selected Sites in the Industrial Belt of Delhi, India

Solid waste samples were collected from five small-scale industrial sites in the National Capital Territory (NCT) of Delhi. These industrial sites represent the regional spread of the industrial belt in the NCT of Delhi. Solid waste samples were digested using aqua-regia and HF in air tight teflon bombs for the quantitative analysis of heavy metals (Hg, Pb, Cd, Mn, Fe, Ni, Cu and Zn) by GBC model 902 atomic absorption spectrophotometer. Hg was analysed using hydrid generator attachment. Beside this sequential extraction was used to fractionate five heavy metals (Pb, Ni, Cd, Cu and Zn) into six operationally defined phases, viz. water soluble, exchangeable, carbonate-bound, Fe-Mn oxides, organic-bound and residual fractions to ascertain the relative mobility of these metals. The result obtained showed metal concentration to be in the range of Hg 0.42-2.3; Pb 23-530; Cd 014-224; Mn 494-19 964; Fe 35 684-233 119; Ni 192-1534; Cu 3065-10 144 and Zn 116-23 321 (all units in mg kg(-1)) in all the industrial areas studied. The fractionated toxic metals like Pb, Ni and Cd were observed to be in the range of 25-35, 15-50 and 40-50%, respectively, in mobile or bio-available fractions of solid waste. As this waste is often disposed-off by the roadsides, low lying areas, abandoned quarries or in landfill sites which are often not properly planned, thus posing potential risk to ground and surface water quality to millions of people living downstream.     

Numerical integration of chemical ODE problems arising in air pollution models

The numerical treatment of a regional air pollution model (such models are, as a rule, described mathematically by systems of partial differential equations) leads to the solution of very large computational problems. The chemical submodel of an air pollution model is normally the most timeconsuming part of the computational work. The application of appropriate discretization and splitting procedures reduces the chemical submodel to a large number of relatively small ODE systems (one such system per gridpoint). In the process of searching for efficient numerical algorithms for the chemical submodels one can carry out experiments by using only one such ODE system in order to facilitate the work. This approach has been used in connection with a particular chemical scheme, the condensed CBM IV scheme, which is used in several large air pollution models. Six integration algorithms have been tested on a set of typical scenarios (consisting of different starting concentrations and/or of different values of the emissions). The advantages and the disadvantages of the algorithms tested are discussed. The final decision about the most efficient algorithm, among the algorithms tested, should be made after a second series of experiments. The coupling of the chemical process with the transport of air pollution (on, at least, a twodimensional domain) together with the application of highspeed computers has to be studied in the second series of experiments, which will be performed in a subsequent paper.