Integration of traditional and innovative characterization techniques for flux-based assessment of Dense Non-aqueous Phase Liquid (DNAPL) sites

Key attributes of the source zone and the expanding dissolved plume at a trichloroethene (TCE) site in Australia were evaluated using trends in groundwater monitoring data along with data from on-line volatile organic compound (VOC) samplers and passive flux meters (PFMs) deployed in selected wells. These data indicate that: (1) residual TCE source mass in the saturated zone, estimated using two innovative techniques, is small ( 10 kg), which is also reflected in small source mass discharge ( 3 g/day); (2) the plume is disconnecting, based on TCE concentration contours and TCE fluxes in wells along a longitudinal transect; (3) there is minimal biodegradation, based on TCE mass discharge of  6 g/day at a plume control plane  175 m from source, which is also consistent with aerobic geochemical conditions observed in the plume; and (4) residual TCE in the vadose zone provides episodic inputs of TCE mass to the plume during infiltration/recharge events. TCE flux data also suggest that the small residual TCE source mass is present in the low-permeability zones, thus making source treatment difficult. Our analysis, based on a synthesis of the archived data and new data, suggests that source treatment is unwarranted, and that containment of the large TCE plume ( 1.2 km long,  0.3 km wide; 17 m deep;  2000–2500 kg TCE mass) or institutional controls, along with a long-term flux monitoring program, might be necessary. The flux-based site management approach outlined in this paper provides a novel way of looking beyond the complexities of groundwater contamination in heterogeneous domains, to make intelligent and informed site decisions based on strategic measurement of the appropriate metrics.     

Second trimester diagnosis of Neu Laxova syndrome

This is the first report of a prenatally diagnosed case of Neu Laxova syndrome (NLS) from India. This also includes a case of NLS in monochorionic diamniotic twins and two more cases in which we were able to detect most of the features of NLS as early as 19 to 20 weeks by routine antenatal ultrasonography. Severe intrauterine growth retardation (IUGR), microcephaly, central nervous system (CNS) abnormality, joint contractures, and abnormal facies are the major diagnostic features observed in prenatal ultrasonography. Risk factors such as consanguinity and history of intrauterine death or stillbirth in siblings have been noted in all the cases, but none of the three families that were reported had previously had an affected fetus. The spectrum of skin manifestations and frequency of occurrence of major clinical features of the syndrome have been discussed. Review of the literature on NLS and possibility of detecting the syndrome in the second trimester is discussed. Copyright © 2002 John Wiley & Sons, Ltd.     

Heterogeneous oxidation by ozone of naphthalene adsorbed at the air-water interface of micron-size water droplets

The mass transfer of naphthalene vapor to water droplets in air was studied in the presence of ozone (O3) in the gas phase. A falling droplet reactor with water droplets of diameters 55, 91, and 182 microm was used for the study. O3 reacted with naphthalene at the air-water interface, thereby decreasing the mass transfer resistance and increasing the rate of uptake of naphthalene into the droplet. A Langmuir-Hinshelwood reaction mechanism at the air-water interface satisfactorily described the surface reaction. The first-order surface reaction rate constant, ks, increased with decreasing droplet size. Three organic intermediates were identified in the aqueous phase as a result of ozonation of naphthalene at the surface of the droplet indicating both peroxidic and nonperoxidic routes for ozonation. The presence of an organic carbon surrogate (fulvic acid) increased both the partition constant of naphthalene and the surface reaction rate of O3. The heterogeneous oxidation of naphthalene by O3 on the droplet was 15 times faster than the homogeneous oxidation by O3 in the bulk air phase, whereas it was only 0.08 times the homogeneous gas-phase oxidation by hydroxyl radicals under atmospheric conditions.     

An improved product-process for cleaner chrome tanning in leather processing

Severe restrictions imposed by the pollution control authorities on the disposal of chromium, total dissolved solids and chlorides in tannery effluents have forced the tanners to look for low-waste, high exhaust chrome tanning salts. An improved chrome syntan with more than 90% uptake of chrome has been developed. The new product serves both as tanning and retanning agent and can be applied directly to delimed pelts thus eliminating the conventional pickling stage in the leather processing. This modified process helps to reduce the chemical oxygen demand (COD), total dissolved solids (TDS) and chlorides in the spent tan liquor by 51, 81 and 99%, respectively. The product offers full, soft leathers having shrinkage temperature comparable to conventional chrome tanned skins. Since the developed product is highly reactive, it saves time and reduces the water requirement when compared to the conventional chrome tanning method. Thus the novel product/process developed not only has advantages in reducing pollution loads but also seems to be techno-economically viable.     

Characterization of airborne particles at a high-btu coal-gasification pilot plant

Airborne particles in fugitive emissions have been measured at a slagging fixed-bed coal-gasification pilot plant using lignite. Sampling was conducted during shutdown operations and opening of the gasifier following an aborted startup. Aerosol collected with a Sierra high-volume impactor was subjected to analysis by gas chromatography, mass spectrometry, and scanning electron microscopy; aerosol collected with an Andersen low-volume impactor was subjected to flameless atomic absorption analysis. The data show that the bulk of the trace organic material is associated with small particles: these data are similar to data on ambient air reported in the literature. Particle morphologies resemble those of fly ash from coal combustion, including smooth spheres, vesicular spheres, and crystalline material. Trace element size distributions are bimodal and resemble data for ambient air. Pb-containing particles are generally submicron, while particles containing Al, Fe, and other crustal species are mostly of supermicron size. Aluminum-based aerosol enrichment factors calculated from the lignite composition show that the composition of the aerosol resembles that of the coal, with the exception of modest enrichments of Mg, Na, As, and Pb in the submicron size range. Aerosol enrichment factors based on the earth's crustal composition are somewhat greater than those based on coal composition for several elements, suggesting potential errors in using crustal enrichment data to investigate chemical fractionation during aerosol formation.     

Characterization of airborne trace metal and trace organic species from coal gasification

Fugitive emissions from a slagging fixed-bed coal-gasification pilot plant were analyzed by flameless atomic absorption spectrophotometry, gas chromatography, and mass spectrometry for trace metal and trace organic species. Analysis of the size distributions of airborne particulate matter inside the plant showed an abundance of large metal-containing particles; outdoor distributions in the vicinity of the plant resembled the indoor distributions, suggesting the importance of the gasifier in influencing ambient air quality. This conclusion was further supported by identification of similar organic compounds inside and outside the plant. Trace element enrichment factors based on the earth's crustal composition were greater than those based on the composition of the lignite used in the gasifier, showing the importance of characterizing the proper source material when inverstigating chemical fraction during aerosol formation. Enrichments in the present study were much greater than those found in previous sampling during aborted start-up and cleaning procedures, where normal operating temperatures had not yet been reached. Both studies showed evidence of enrichment factors which decreased with increasing particle size. Although much of the airborne mass was associated with large particles having low respirability, the high concentrations of some metals indoors suggests that further assessment of potential occupational exposures is warranted.     

A comparative study on the toxic effects of textile dye wastewaters (untreated and treated) on mortality and RBC of a freshwater fish Gambusia affinis (Baird and Gerard)

Comparative toxicological studies of textile dye wastewater (untreated and treated) on a freshwater fish, Gambusia affinis, revealed a marked reduction in mortality and cytotoxic effects on RBCs, measured as reduction in their counts and percent changes in their shape (poikilocytosis) and variation in their size (anisocytosis)}, after subjecting them to both physicochemical and biological treatments. On comparing the data of mortality and the cytotoxic effects on RBCs, we found poikilocytosis is a better indicator for toxicity measurement of both untreated as well as treated wastewater, especially at their lowest concentrations where percent mortality was found to be either nil or lowerer than the percentage of poikilocytic RBCs. Although percent reduction in RBC counts and changes in their size (anisocytosis) indicated toxic effects of wastewaters, but EC5o values for RBC counts were usually higher than those for poikilocytosis and mortality, and non-calculable for anisocytosis suggesting their lesser sensitivity to pollutants. In view of these findings, we recommend monitoring of toxic effects of wastewaters during fish bioassay on both mortality and variation in RBC shape.     

Organophosphorous compounds and oxidative stress: a review

Organophosphorous compounds (OP) have largely been used as pesticides globally. These chemicals induce oxidative stress as a possible mechanism of action, which has been a focus of toxicological research for the last decade. This review evaluated the presence of oxidative stress, balance between total antioxidant capacity, and oxygen free radicals associated with OP compound exposure. Oxidative stress induced by OP leads to disturbances in function of different organs and tissues. Evidence indicates that stimulation of free radical production, induction of lipid peroxidation, and disturbance of the total antioxidant capacity are mechanisms of toxicity induced by most OP. Thus, use of antioxidants may be beneficial in treatment of OP poisoning, which remains to be elucidated with further clinical trials.     

Assessing combined toxic effects of tetracycline and P25 titanium dioxide nanoparticles using Allium cepa bioassay

• UVA pre-irradiation to TiO₂ NPs enhanced its toxicity toward plant A. cepa. • UVA TiO₂ NPs increased intracellular ROS, resulting in more cell damage. • Cell death enhanced cell permeability and increased uptake of NPs. • Being highly toxic (EC₅₀ = 0.097 µmol/L), TC did not increase ROS generation. • Even at a low dose, TC enhanced the toxic potential of TiO₂ NPs significantly. Usage of titanium dioxide nanoparticles (TiO₂ NPs) and tetracycline (TC) has increased significantly in the present era. This leads to their release and accumulation in the environment. Both the compounds, individually, can have adverse toxic effects on the plants. Their binary mixtures can increase this degree of damage. The present study aimed to evaluate the toxicity of both the contaminants in individual and binary mixtures in Allium cepa. Further, the toxicity of TiO₂ NPs upon UVA pre-irradiation was also measured. Results showed that UVA pre-irradiated NPs (UVA-TiO₂ NPs) had a significant decrease in cell viability than their non-irradiated counterparts (NI-TiO₂), denoting an increase in photocatalytic activity upon UVA pre-irradiation. Very low concentrations of TC (EC₁₀ = 0.016 µmol/L) mixed with TiO₂ NPs significantly increased the toxicity for both UVA-TiO₂ and NI-TiO₂ NPs. Intracellular ROS generation was significantly high for UVA-TiO₂ NPs. However, TC did not have any effects on ROS production. Both the compounds exhibited genotoxic potential in A. cepa. Different chromosomal abnormalities like anaphase bridges, telophase bridges, laggard chromosomes, binucleate cells, etc. were observed. The binary mixture of UVA-TiO₂ NPs and TC showed the highest chromosomal aberrations (64.0%±1.26%) than the mixture with NI-TiO₂ or the individual contaminants. This decreased significantly after recovery (46.8%±1.92%), denoting the self-repair processes. This study proved that UVA-TiO₂ NPs were more toxic and could be enhanced further when mixed with a sub-lethal concentration of TC. This work will help to assess the risk of both compounds in the environment.     

AUTOMATED WEB GIS BASED HYDROGRAPH ANALYSIS TOOL,WHAT1

The separation of the base flow component from a varying streamflow hydrograph is called “hydrograph analysis.” In this study, two digital filter based separation modules, the BFLOW and Eckhardt filters, were incorporated into the Web based Hydrograph Analysis Tool (WHAT) system. A statistical component was also developed to provide fundamental information for flow frequency analysis and time series analysis. The Web Geographic Information System (GIS) version of the WHAT system accesses and uses U.S. Geological Survey (USGS) daily streamflow data from the USGS web server. The results from the Eckhardt filter method were compared with the results from the BFLOW filter method that was previously validated, since measured base flow data were not available for this study. Following validation, the two digital filter methods in the WHAT system were run for 50 Indiana gaging stations. The Nash‐Sutcliffe coefficient values comparing the results of the two digital filter methods were over 0.91 for all 50 gaging stations, suggesting the filtered base flow using the Eckhardt filter method will typically match measured base flow. Manual separation of base flow from streamflow can lead to inconsistency in the results, while the WHAT system provides consistent results in less than a minute. Although base flow separation algorithms in the WHAT system cannot consider reservoir release and snowmelt that can affect stream hydrographs, the Web based WHAT system provides an efficient tool for hydrologic model calibration and validation. The base flow information from the WHAT system can also play an important role for sustainable ground water and surface water exploitation, including irrigation and industrial uses, and estimation of pollutant loading from both base flow and direct runoff. Thus, best management practices can be appropriately applied to reduce and intercept pollutant leaching if base flow contributes significant amounts of pollutants to the stream. This Web GIS based system also demonstrates how remote, distributed resources can be shared through the Internet using Web programming.