Abiotic reductive dechlorination of chlorinated ethylenes by iron-bearing phyllosilicates

Abiotic reductive dechlorination of chlorinated ethylenes (tetrachloroethylene (PCE), trichloroethylene (TCE), cis-dichloroethylene (c-DCE), and vinylchloride (VC)) by iron-bearing phyllosilicates (biotite, vermiculite, and montmorillonite) was characterized to obtain better understanding of the behavior of these contaminants in systems undergoing remediation by natural attenuation and redox manipulation. Batch experiments were conducted to evaluate dechlorination kinetics and some experiments were conducted with addition of Fe(II) to simulate impact of microbial iron reduction. A modified Langmuir-Hinshelwood kinetic model adequately described reductive dechlorination kinetics of target organics by the iron-bearing phyllosilicates. The rate constants stayed between 0.08 (+/-10.4%) and 0.401 (+/-8.1%) day(-1) and the specific initial reductive capacity of iron-bearing phyllosilicates for chlorinated ethylenes stayed between 0.177 (+/-6.1%) and 1.06 (+/-7.1%) microM g(-1). The rate constants for the reductive dechlorination of TCE at reactive biotite surface increased as pH (5.5-8.5) and concentration of sorbed Fe(II) (0-0.15 mM g(-1)) increased. The appropriateness of the model is supported by the fact that the rate constants were independent of solid concentration (0.0085-0.17 g g(-1)) and initial TCE concentration (0.15-0.60 mM). Biotite had the greatest rate constant among the phyllosilicates both with and without Fe(II) addition. The rate constants were increased by a factor of 1.4-2.5 by Fe(II) addition. Between 1.8% and 36% of chlorinated ethylenes removed were partitioned to the phyllosilicates. Chloride was produced as a product of degradation and no chlorinated intermediates were observed throughout the experiment.     

Effect of formaldehyde on biofilm activity and morphology in an ultracompact biofilm reactor for carbonaceous wastewater treatment.

The effects of formaldehyde on biofilm morphology and biomass activity were investigated in an ultracompact biofilm reactor (UCBR) for carbonaceous wastewater treatment. The wastewater contained a fixed amount of glucose (with a chemical oxygen demand concentration of 600 mg/L) and an increasing concentration of formaldehyde (ranging from 21.4 to 271.1 mg/L). An influent formaldehyde concentration higher than 75 mg/L could facilitate filamentous growth (on biofilm) control and lead to a higher biofilm density, which is desirable as it enhanced the UCBR performance stability. However, at an influent formaldehyde concentration higher than 214.4 mg/L, biomass production was inhibited and deteriorations of biofilm morphology and biomass activity were observed. This study showed that it was desirable to maintain an influent formaldehyde concentration lower than 202.2 mg/L, as this concentration could achieve a good biofilm morphology while not inhibiting its microbial activity.     

Effect of experimental factors on nitrobenzaldehyde photoisomerization

The objective of this study was to compare the effect of various experimental factors on the photoisomerization of nitrobenzaldehyde. The experimental factors included light source, light energy, exposure time, light path distance and the concentration of nitrobenzaldehyde. The results showed that the photoisomerization of nitrobenzaldehyde increased with increasing light exposure. Different light sources and light path distances demonstrated significant impact on the reaction rate constants and half-lives of nitrobenzaldehyde. Although the light energy of UV photoreactor was 47% lower than that of xenon photoreactor, quantum yield and UV/VIS absorption pattern confirmed the finding that the effect of ultraviolet photoreactor on nitrobenzaldehyde was similar to that of xenon photoreactor with the light path of 17 cm. It was caused by the shorter wavelength of UV photoreactor mainly on 254 nn. The product of nitrobenzaldehyde photoisomerization, nitrosobenzoic acid, was detected from samples after 5 or 10 min exposure of three light sources. The concentrations of nitrosobenzoic acid increased with the increasing of exposure time up to 20 or 60 min.     

Uncertainties in current estimates of emissions of ammonia in the United Kingdom

Estimates of the emissions of ammonia have previously concentrated on animal husbandry sources from agricultural systems. Animal husbandry sources still constitute the major fraction of emissions of ammonia, but we have also considered the potential magnitude of other 'minor' sources, which may include coal combustion, waste incineration, road vehicles, sewage treatment plants, fertiliser manufacture and application, vegetation senescence and crop emissions, domestic pets, and human sources. Where possible, a provisional estimate of UK emissions from each of these sources is given. It is concluded that the potential magnitude of emissions from these 'minor' sources may make a significant contribution to the total emissions of ammonia to the atmosphere. On the basis of the available data, and the application of a range of emission factors to the UK situation, an additional annual emission potential lying in the range of approximately 80-140 ktonne year(-1) over and above that from animal husbandry has been calculated. The uncertainties in the emission estimates and instances in which a better resolution of sources is required are discussed. The emission factors used for animals in various inventories are reviewed and applied to the main UK agricultural animal populations. By using this approach, estimates of emissions from these sources range between 113 and 647 ktonne year(-1), which illustrates the uncertainties involved. It is suggested that our knowledge of the sources of ammonia, and their distribution, is far from complete.     

Transformation and adsorption of Fenamiphos, f. sulfoxide and f. sulfone in molokai soil and simulated movement with irrigation

The ban of commonly used soil fumigants, DBCP and EDB, for control of nematodes in pineapple fields has prompted investigations into a non-fumigant nematicide, fenamiphos (Nemacur^®). The transformation and adsorption in soil of fenamiphos and its transformation products, f. sulfoxide and f. sulfone were studied in the laboratory. Fenamiphos adsorption on soil exceeded that of f. sulfoxide and f. sulfone. F. sulfoxide, however, was the most persistent. A one-dimensional simulation model was used to assess the impact of transformation and adsorption on the mobility and distribution of fenamiphos and f. sulfoxide in soil. Simulated results showed that fenamiphos stayed in the topsoil and transformed rapidly to f. sulfoxide. Because of the persistence and mobility of f. sulfoxide, this metabolite leached rapidly and significant amounts remained in the soil. This suggests that for times exceeding three weeks, f. sulfoxide may be the dominant compound providing nematode control in drip-irrigated pineapple.     

An automated overlying water-renewal system for sediment toxicity studies

An automated water-renewal toxicity test system is described for exposing benthic invertebrates to whole sediments. The system will intermittently deliver laboratory or on-site water for overlying water replacement in sediment exposures. A range of cycle rates can be used to produce different volume additions of overlying water per day to exposure chambers. The system can be used with six different treatments and eight replicates per treatment producing 48 exposure chambers. Three formulated sediments with variable organic carbon (1.5%, 7.5%) and sand (14%, 63%) content were prepared to test the system exposing amphipods, Hyalella azteca and midges, Chironomus tentans in 10 day whole sediment tests. Intermittent water flow was used with a 90 min cycle time to create two volume additions of laboratory water per 24 h in exposure chambers (180 ml sediment, 320 ml water). Overlying water quality conditions, and survival and growth of both species were consistent and within acceptable limits for the testing requirements of the U.S. EPA guidelines for sediments with freshwater invertebrates.     

Plant uptake and translocation of air-borne chlordane and comparison with the soil-to-plant route

In order to assess fully the impact of persistent organic pollutants (POPs) on human health, pollutant exchange at the interface between terrestrial plants, in particular food crops, and other environmental compartments must be thoroughly understood. In this regard, transfers of multicomponent and chiral pollutants are particularly informative. In the present study, zucchini (Cucurbita pepo L.) was planted in containerized, uncontaminated soil under both greenhouse and field conditions and exposed to air-borne chlordane contamination at 14.0 and 0.20 ng/m(3) (average, greenhouses), and 2.2 ng/m(3) (average, field). Chiral gas chromatography interfaced to an ion trap mass spectrometer was used to determine the chiral (trans-chlordane, TC, and cis-chlordane, CC) and achiral (trans-nonachlor, TN) chlordane components in vegetation, air, and soil compartments. The chlordane components of interest were detected in all vegetation tissues examined--root, stem, leaves, and fruits. When compared with the data from a soil-to-plant uptake study, the compositional profile of the chlordane components, i.e. the component fractions of TC, CC, and TN, in plant tissues, showed significantly different patterns between the air-to-plant and soil-to-plant pathways. Changes in the enantiomer fractions of TC and CC in plant tissues relative to the source, i.e. air or soil, although observed, were not markedly different between the two routes. This report provides the first comprehensive comparison between two distinct plant uptake routes for POPs and their subsequent translocation within plant tissues.     

Intercomparison of reactive transport models applied to UO2 oxidative dissolution and uranium migration

Oxidative dissolution of uranium dioxide (UO₂) and the subsequent migration of uranium in a subsurface environment and an underground waste disposal have been simulated with reactive transport models. In these systems, hydrogeological and chemical processes are closely entangled and their interdependency has been analyzed in detail, notably with respect to redox reactions, kinetics of mineralogical evolution and hydrodynamic migration of species of interest.Different codes, where among CASTEM, CHEMTRAP and HYTEC, have been used as an intercomparison and verification exercise. Although the agreement between codes is satisfactory, it is shown that the discretization method of the transport equation (i.e. finite elements (FE) versus mixed-hybrid FE and finite differences) and the sequential coupling scheme may lead to systematic discrepancies.     

Water-soluble aerosol and visibility degradation in Hong Kong during autumn and early winter, 1998.

During the October-December 1998 period, 30 daily samples of size-separated airborne respirable suspended particulates (RSP) were collected at the quasi-rural Kadoorie Agricultural Research Centre (KARC) in central New Territories (NT), Hong Kong, Special Administrative Region (SAR). Results of analysis indicate that sulphate is the predominant water-soluble species, and that sulphate, nitrate and ammonium together contribute to most of the total water-soluble fine aerosol mass. An interesting result obtained through principal component analysis (PCA) following varimax rotation of the bivariate correlation matrix for water-soluble species is that the first component (PCl) is made up exclusively of SO4 and NH4 ions. The stoichiometric ratio and correlation coefficient between the two ions suggest that ammoniated sulphate compounds are the probable species responsible for the PCI. Further, the use of a linear multivariate visibility model which accommodates the effect of relative humidity (RH) shows that SO4 and NH4 are the only anions important in visibility degradation. It is found that SO4 in aerosol at the KARC can be used to predict the visual range (or extinction coefficient) recorded from Kings Park, Kowloon, approximately 10 km away. This result suggests that SO4 (and possibly NH4) is, generally, likely to be of regional rather than of local origin. Further observations suggest that the model is most applicable to a moderate visual range, 10 km < R(v) < or = 20 km under a rather broad range of ambient relative humidity, 40% < RH < or = 80. However, this inference does not preclude the contributions to visibility degradation--mostly by absorption--by some of the water-insoluble aerosol constituents, including carbon, or the pollutant gas, NO2.     

Biodegradation of 2,4,6-trichlorophenol in the presence of primary substrate by immobilized pure culture bacteria

In this study, pure strains that are capable of utilizing 2,4,6-trichlorophenol have been isolated from the mixed culture grown on substrates containing chlorophenolic compounds. Studies have been carried out on the capability of these isolated pure strains in suspended and immobilized forms to decompose 2,4,6-trichlorophenol. Additionally, the influence of primary substrates (e.g., phenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2,4-dichlorophenol) on the decomposition of 2,4,6-trichlorophenol by the isolated pure strains grown in immobilized form is also investigated. The results are: Through bacterial isolation and identification, three pure strains have been obtained: Pseudomonas spp. strain 01, Pseudomonas spp. strain 02 and Agrobacterium spp. Whether in suspended or immobilized forms, all strains have poor removal efficiencies of 2,4,6-trichlorophenol. However, addition of 200 mg/l phenol will enable the immobilized Pseudomonas spp. strain 01, and Pseudomonas spp. strain 02 to achieve 65% and 48% removal of 2,4,6-trichlorophenol, respectively. Addition of phenol will assist the immobilized Pseudomonas spp. strain 02 in achieving removal of 2,4,6-trichlorophenol but the removal efficiency is not good if the phenol concentration is too low. The optimum phenol concentration should be between 200 and 400 mg/l.