Surfactant enhanced recovery of tetrachloroethylene from a porous medium containing low permeability lenses. 2. Numerical simulation

A numerical model of surfactant enhanced solubilization was developed and applied to the simulation of nonaqueous phase liquid recovery in two-dimensional heterogeneous laboratory sand tank systems. Model parameters were derived from independent, small-scale, batch and column experiments. These parameters included viscosity, density, solubilization capacity, surfactant sorption, interfacial tension, permeability, capillary retention functions, and interphase mass transfer correlations. Model predictive capability was assessed for the evaluation of the micellar solubilization of tetrachloroethylene (PCE) in the two-dimensional systems. Predicted effluent concentrations and mass recovery agreed reasonably well with measured values. Accurate prediction of enhanced solubilization behavior in the sand tanks was found to require the incorporation of pore-scale, system-dependent, interphase mass transfer limitations, including an explicit representation of specific interfacial contact area. Predicted effluent concentrations and mass recovery were also found to depend strongly upon the initial NAPL entrapment configuration. Numerical results collectively indicate that enhanced solubilization processes in heterogeneous, laboratory sand tank systems can be successfully simulated using independently measured soil parameters and column-measured mass transfer coefficients, provided that permeability and NAPL distributions are accurately known. This implies that the accuracy of model predictions at the field scale will be constrained by our ability to quantify soil heterogeneity and NAPL distribution.     

Kinetics of OH radical reactions with dibenzo-p-dioxin and selected chlorinated dibenzo-p-dioxins

The pulsed laser photolysis/pulsed laser-induced fluorescence (PLP/PLIF) technique has been applied to obtain rate coefficients for OH + dioxin (DD) (k1), OH + 2-chlorodibenzo-p-dioxin (2-CDD) (k2), OH + 2,3-dichlorodibenzo-p-dioxin (2,3-DCDD) (k3), OH + 2,7-dichlorodibenzo-p-dioxin (2,7-DCDD) (k4), OH + 2,8-dichlorodibenzo-p-dioxin (2,8-DCDD) (k5), OH + 1,2,3,4-tetrachlorodibenzo-p-dioxin (1,2,3,4-TCDD) (k6), and OH + octachlorodibenzo-p-dioxin (OCDD) (k7) over an extended range of temperature. The atmospheric pressure (740 +/- 10 Torr) rate measurements are characterized by the following Arrhenius parameters (in units of cm3 molecule(-1) s(-1), error limits are 1 omega): k1(326-907 K) = (1.70+/-0.22) x 10(-12)exp(979+/-55)/T, k2(346-905 K) = (2.79+/-0.27) x 10(-12)exp(784+/-54)/T, k3(400-927 K) = 10(-12)exp(742+/-67)/T, k4(390-769 K) = (1.10+/-0.10) x 10(-12)exp(569+/-53)/T, k5(379-931 K) = (1.02+/-0.10) x 10(-12)exp(580+/-68)/T, k6(409-936 K) = (1.66+/-0.38) x 10(-12)exp(713+/-114)/T, k7(514-928 K) = (3.18+/-0.54) x 10(-12)exp(-667+/-115)/T. The overall uncertainty in the measurements, taking into account systematic errors dominated by uncertainty in the substrate reactor concentration, range from a factor of 2 for DD, 2-CDD, 2,3-DCDD, 2,7-DCDD, and 2,8-DCDD to +/- a factor of 4 for 1,2,3,4-TCDD and OCDD. Negative activation energies characteristic of an OH addition mechanism were observed for k1-k6. k7 exhibited a positive activation energy. Cl substitution was found to reduce OH reactivity, as observed in prior studies at lower temperatures. At elevated temperatures (500 K < T < 500 K), there was no experimental evidence for a change in reaction mechanism from OH addition to H abstraction. Theoretical calculations suggest that H abstraction will dominate OH reactivity for most if not all dioxins (excluding OCDD) at combustion temperatures (>1000 K). For OCDD, the dominant reaction mechanism at all temperatures is OH addition followed by Cl elimination.     

Formation and inhibition of chloroaromatic micropollutants formed in incineration processes

The formation pathways for chlorinated aliphatic and chlorinated aromatic compounds in technical incineration processes are reviewed. It is shown that acetylene is converted to chloroaromatic compounds including PCDD/F in a special flow reactor by catalytic activity of CuCl2 in the temperature regime of a post-combustion zone of technical incinerators. Mechanistic pathways begin with chlorination of acetylene. Dichloroacetylene is further condensed to C-4 and C-6 units. Hexachlorobenzene is the dominant aromatic compound and a likely precursor to chlorinated phenols and PCDD/F. Two specific mechanisms of formation of chlorinated aromatic compounds including PCDD/F have been advanced. Both mechanisms begin with the formation of dichloroacetylene from flame pyrolysis products like acetylene. Condensation of dichloroacetylene is mediated by copper species via metallacyclic intermediates and/or a catalytic cycle involving copper stabilized trichlorovinyl radicals. The final pathways of conversion of chlorinated benzenes to PCDD/F via chlorophenols are under active investigation.     

Particulate matter in California: part 1--Intercomparison of several PM2.5, PM10-2.5, and PM10 monitoring networks

It will be many years before the recently deployed network of fine particulate matter with an aerodynamic diameter less than 2.5 microm (PM2.5) Federal Reference Method (FRM) samplers produces information on nonattainment areas, trends, and source impacts. However, data on PM2.5 and its major constituents have been routinely collected in California for the past 20 years. The California Air Resources Board operated as many as 20 dichotomous (dichot) samplers for PM2.5 and coarse PM (PM10-2.5). The California Acid Deposition Monitoring Program (CADMP) collected 12-h-average PM2.5 and PM10 from 1988 to 1995 at ten urban and rural sites and 24-h-average PM2.5 at five urban sites since 1995. Beginning in 1994, the Children's Health Study collected 2-week averages of PM2.5 in 12 communities in southern California using the Two-Week Sampler (TWS). Comparisons of collocated samples establish relationships between the dichot, CADMP, and TWS samplers and the 82-site network of PM2.5 FRM samplers deployed since 1999 in California. PM mass data from the different monitoring programs have modest to high correlation to FRM mass data, fairly small systematic biases and negative proportional biases ranging from 7 to 22%. If the biases are taken into account, all of the programs should be considered comparable with the FRM program. Thus, historical data can be used to develop long-term PM trends in California.     

Patterns of growth,energy utilization and reproduction in some meso- and bathypelagic fishes off Southern California

We have studied growth, energy use and reproduction in 4 mesopelagic fishes and 5 bathypelagic fishes living off Southern California (USA). All of the mesopelagic species underwent diurnal vertical migrations, while none of the bathypelagic species did so. The life histories of these pelagic fishes were compared among themselves and with epipelagic sardines and anchovies studied by others. The epipelagic species had the highest growth rates (estimated from otoliths, expressed in standard length or kilocalories), the mesopelagic species had the lowest growth rates and the bathypelagic species had intermediate growth rates. The relatively rapid growth rates of the bathypelagic fishes were achieved by high relative growth efficiencies made possible by low metabolic rates. Of the species studied, the lifespans of the epipelagic and bathypelagic species ranged from 4 to 8 yr and the lifespans of mesopelagic species from 5 to 8 yr. Data on egg diameters suggest that the mesopelagic species first reproduce in their 3rd yr, while the bathypelagic species do so in their last year. Epipelagic fishes generally have a large size, rapid growth, long life and early, repeated reproduction. Mesopelagic fishes are characterized by small size, slow growth, long life and early, repeated reproduction. Bathypelagic fishes generally have large size, rapid growth, somewhat shorter lives and late reproduction, which is possible a single event. The latter pattern is evidently feasible only in a rather stable environment where juvenile survivorship would always display relatively low variability. Many unusual characteristics of deep-living animals have possibly been selected by factors peculiar to the environment; however, such characteristics are just as likely to have been selected by factors equally present in many other environments, but not expressed there due to masking selective forces. In particular, we have in mind the darkness, stability and homogeneity of the bathypelagic realm as phenomena which represent the effective absence of many selective forces.The first two authors contributed equally and their names are listed in alphabetical order     

Uptake and release of phosphorus by phytoplankton in the Chesapeake Bay estuary,USA

The phytoplankton uptake and release rates for inorganic phosphate, dissolved organic phosphate and polyphosphate were estimated during 5 cruises on the Chesapeake Bay over a 9-month period. Phosphorus in all pools turned over in several minutes to 100 h, and each soluble pool appeared to contain fractions which were metabolically useful to the phytoplankton. Maximal uptake rates (V _m ) for orthophosphate ranged from 0.02 to 2.95 μg-at P (1.h)^-1 with half saturation constants (K _s ) between 0.09 and 1.72 μg-at P l^-1. At low soluble reactive phosphorus concentrations, the uptake rate of trace ³²P orthophosphate was initially rapid, but declined after 15 to 60 min incubation. The data suggest that the initial uptake phase was dominated by exchange of ³²PO₄ ^≡ for ³¹PO₄ ^≡ in the membrane transport systems whereas the subsequent phase represented the net incorporation of orthophosphate into phytoplankton cells.     

Significance of Atmospheric Ozone as a Phytotoxicant

Since the recognition of ozone as a major phytotoxicant in crop plants in 1957, ozone type symptoms have been observed in a wide range of vegetation. These observations include leafy vegetables, field, forage, and textile crops, also shrubs, broad-leafed ornamental, fruit and forest trees, and various conifers. Fumigation experiments at various institutions have confirmed the etiological relation of ozone in many of these observations. Such visible injuries fail to provide a reliable index to the damaging impact of ozone on the numerous plants affected. Hidden injury or damage by ozone at sub-necrotic levels has been reported and experimentally established in a number of crop plants. Evidence is available which indicats that citrus varieties are so affected, and that much of the citrus decline in Southern California may be ozone induced. Photochemically induced ozone may prove to be the most persistent, if not the most difficult, of atmospheric phytotoxicants to control. Ozone type injury has been reported from eighteen different states, and from Canada to Japan.     

Isotopes for improved management of nitrate pollution in aqueous resources: review of surface water field studies

Background  

Environmental agencies have to take measures to either reduce discharges and emissions of nitrate or to remediate nitrate-polluted water bodies where the nitrate concentrations exceed threshold values. Isotope data can support the identification of nitrate pollution sources and natural attenuation processes of nitrate.     

Strong links between metal contamination, habitat modification and estuarine larval fish distributions

Changes to larval fish assemblages may have far reaching ecological impacts. Correlations between habitat modification, contamination and marine larval fish communities have rarely been assessed in situ. We investigated links between the large-scale distribution of stressors and larval fish assemblages in estuarine environments. Larval fish communities were sampled using a benthic sled within the inner and outer zones of three heavily modified and three relatively unmodified estuaries. Larval abundances were significantly greater in modified estuaries, and there were trends towards greater diversity in these systems. Differences in larval community composition were strongly related to sediment metal levels and reduced seagrass cover. The differences observed were driven by two abundant species, Paedogobius kimurai and Ambassis jacksoniensis, which occurred in large numbers almost exclusively in highly contaminated and pristine locations respectively. These findings suggest that contamination and habitat alteration manifest in substantial differences in the composition of estuarine larval fish assemblages.