Effects of ethanol addition on micellar solubilization and plume migration during surfactant enhanced recovery of tetrachloroethene

Alcohol addition has been suggested for use in combination with surfactant flushing to enhance solubilization kinetics and permit density control of dense non-aqueous phase liquid (DNAPL)-laden surfactant plumes. This study examined the effects of adding ethanol (EtOH) to a 4% Tween 80 (polyoxyethylene (20) sorbitan monooleate) solution used to flush tetrachloroethene (PCE)-contaminated porous media. The influence of EtOH concentration, subsurface layering and scale on flushing solution delivery and PCE recovery was investigated through a combination of experimental and mathematical modeling studies. Results of batch experiments demonstrated that the addition of 2.5%, 5% and 10% (wt.) EtOH incrementally increased the PCE solubilization capacity and viscosity of the surfactant solution, while reducing solution density from 1.002 to 0.986 g/cm3. Effluent concentration data obtained from one-dimensional (1-D) column experiments were used to characterize rate-limited micellar solubilization of residual PCE, which was strongly dependent upon flow velocity and weakly dependent upon EtOH concentration. Two-dimensional (2-D) box studies illustrated that minor differences (0.008 g/cm3) between flushing and resident solution density can strongly influence surfactant front propagation. A two-dimensional multiphase simulator, MISER, was used to model the influence of EtOH composition on the aqueous flow field and PCE mass recovery. The ability of the numerical simulator to predict effluent concentrations and front propagation was demonstrated for both 1-D columns and 2-D boxes flushed with EtOH-amended Tween 80 solutions. Results of this study quantify the potential influence of alcohol addition on surfactant solution properties and solubilization capacity, and demonstrate the importance of considering small density variations in remedial design.     

Herbivory in the gammarid amphipod Aora typica: relationships between consumption rates, performance and abundance across ten seaweed species

This paper reveals a substantial capacity for herbivory of seaweeds in the gammarid amphipod Aora typica, adults eating seven of ten taxonomically and morphologically diverse seaweed species offered to them in a no-choice assay. The green algae Ulva spathulata and Enteromorpha intestinalis were consumed at the highest rates in both no-choice (2.3–2.5 mg blotted weight individual⁻¹ day⁻¹) and multiple-choice assays (0.5–1.3 mg blotted weight individual⁻¹ day⁻¹). Adult A. typica collected from two different species of brown seaweeds had very similar feeding preferences to each other. Juvenile A. typica grew to reproductive maturity on the green algae E. intestinalis and U. spathulata, and the brown algae Carpophyllum maschalocarpum and Ecklonia radiata. In common with previous studies on members of other amphipod families, survivorship of juvenile amphipods was positively correlated with feeding preferences of adults across seaweed species (r ²=0.43, P=0.04). However, densities of A. typica on seaweeds in the field (excluding the intertidal E. intestinalis and U. spathulata) were not significantly correlated with feeding preferences of adults (r ²=0.07, P=0.5) or survivorship of juveniles (r ²=0.17, P=0.31). This suggests that either host seaweeds are not a major dietary component of these amphipods in nature, or that the host’s value as a food source is overridden by other properties such as the degree of shelter it affords from larger consumers. This study provides the first demonstration that a member of the cosmopolitan amphipod family Aoridae is capable of consuming a diverse range of seaweeds.     

Mate competition in the velvet swimming crab Necora puber: effects of perceived resource value on male agonistic behaviour

Male velvet swimming crabs [Necora puber (L.)] were observed to engage in long and vigorous agonistic interactions to gain possession of a sexually receptive female. The role of agonistic behaviour in male mate competition in this species was examined by investigating the effect of the perceived presence of sexually receptive females on interactions between males. Exposing male crabs to water conditioned by sexually receptive females resulted in prolonged interactions, with a greater incidence of potentially injurious behaviour than interactions between control crabs, exposed only to sea water. Maleconditioned water also resulted in more offensive behaviour, but these interactions were of shorter duration and not significantly different from sea water controls. Agonistic superiority was strongly correlated with contestant relative size when males were exposed to male-conditioned water or sea water, but not when exposed to female-conditioned water. Overall, the results conformed with the general predictions of game theoretic models in relation to the influence of resource value on agonistic behaviour. Crabs were more persistent and probably incurred greater fitness costs in the perceived presence of a sexually receptive female, when interactions may have been resolved on the basis of factors more closely related to actual fighting ability than the relative body sizes of contestants.     

Deposition velocities to Sorbus aria, Acer campestre, Populus deltoides X trichocarpa 'Beaupré', Pinus nigra and X Cupressocyparis leylandii for coarse, fine and ultra-fine particles in the urban environment

Trees are effective in the capture of particles from urban air to the extent that they can significantly improve urban air quality. As a result of their aerodynamic properties conifers, with their smaller leaves and more complex shoot structures, have been shown to capture larger amounts of particle matter than broadleaved trees. This study focuses on the effects of particle size on the deposition velocity of particles (Vg) to five urban tree species (coniferous and broadleaved) measured at two field sites, one urban and polluted and a second more rural. The larger uptake to conifers is confirmed, and for broadleaves and conifers Vg values are shown to be greater for ultra-fine particles (Dp < 1.0 microm) than for fine and coarse particles. This is important since finer particles are more likely to be deposited deep in the alveoli of the human lung causing adverse health effects. The finer particle fraction is also shown to be transported further from the emission source; in this study a busy urban road. In further sets of data the aqueous soluble and insoluble fractions of the ultra-fines were separated, indicating that aqueous insoluble particles made up only a small proportion of the ultra-fines. Much of the ultra-fine fraction is present as aerosol. Chemical analysis of the aqueous soluble fractions of coarse, fine and ultra-fine particles showed the importance of nitrates, chloride and phosphates in all three size categories at the polluted and more rural location.     

Enzymatic treatment of sulfonated aromatic amines generated from reductive degradation of reactive azo dyes.

Anaerobic degradation, an effective treatment process of textile industry effluent, generates sulfonated aromatic amines, which are carcinogenic, mutagenic, and resistant to microbial degradation. These aromatic amines can be effectively removed by oxidative polymerization catalyzed by peroxidase enzyme. The amines, generated in this study from the anaerobic reduction by zero-valent iron of two reactive azo dyes (Reactive Red 2 [RR2] and Reactive Black 5 [RB5]), were successfully removed (90%) by Arthromyces ramosus peroxidase (ARP). For better understanding of the process, enzymatic treatment of two model compounds, diphenylamine (DPA) and 2-amino-8-naphthol-3,6-disulfonic acid (ANDSA), were also studied. Diphenylamine has a similar diarylamine bond as RR2. The ANDSA has a similar structure as the dye reduction products. The secondary amine bond in DPA and RR2 were oxidized by ARP. Enzymatic reaction of sulfonated aromatic amines generated soluble colored compounds, which were removed by coagulant. Optimum reaction parameters were also determined.     

LP/LIF study of the formation and consumption of mercury (I) chloride: kinetics of mercury chlorination

The laser photolysis/laser induced fluorescence (LP/LIF) technique has been applied to studies of gas-phase mercury (Hg) chlorination. Mercury (I) chloride (HgCl) was been detected via LIF at 272 nm from reactions of elemental Hg with Cl atoms generated from the 193 nm photolysis of carbon tetrachloride. While the formation of HgCl was too fast to be observed on millisecond time scales, the kinetics of the consumption of HgCl have been determined at temperatures characteristic of post-combustion conditions. Rate coefficients and Arrhenius parameters for the reaction of HgCl with Cl2, HCl and Cl atoms were determined. The reaction of HgCl with Cl2 was the fastest reaction studied, while the reaction of HgCl with HCl was the only reaction to show any measurable temperature dependence. Estimates of the rate coefficient for the reaction Hg + Cl --> HgCl were determined using a modeling approach. Comparisons of these new measurements with model predictions are discussed.     

TNT particle size distributions from detonated 155-mm howitzer rounds

To achieve sustainable range management and avoid or minimize environmental contamination, the Army needs to know the amount of explosives deposited on ranges from different munitions and how these are degraded and transported under different geological and climatic conditions. The physical form of the deposited explosives has a bearing on this problem, yet the shapes and size distributions of the explosive particles remaining after detonations are not known. We collected residues from 8 high-order and 6 low-order non-tactical detonations of TNT-filled 155-mm rounds. We found significant variation in the amount of TNT scattered from the high-order detonations, ranging from 0.00001 to 2% of the TNT in the original shell. All low-order detonations scattered percent-level amounts of TNT. We imaged thousands of TNT particles and determined the size, mass and surface-area distributions of particles collected from one high-order and one low-order detonation. For the high-order detonation, particles smaller than 1 mm contribute most of the mass and surface area of the TNT scattered. For the low-order detonation, most of the scattered TNT mass was in the form of un-heated, centimeter-sized pieces whereas most of the surface area was again from particles smaller than 1 mm. We also observed that the large pieces of TNT disintegrate readily, giving rise to many smaller particles that can quickly dissolve. We suggest picking up the large pieces of TNT before they disintegrate to become point sources of contamination.     

Oxygen-binding by haemocyanins from an ecological series of amphipod crustaceans

The oxygen-binding properties of haemocyanins (Hc) from three species of gammaridean amphipods, Gammarus locusta (L.) (subtidal), Echinogammarus pirloti (Sexton and Spooner), (intertidal, marine) and E. marinus (Leach) (intertidal, estuarine), one species of hyalid amphipod Hyale nilsonni Rathke (high intertidal, marine) and the talitrid amphipod Orchestia gammarellus (Pallas) (semi-terrestrial) have been studied. All the species were collected from the Firth of Clyde, Scotland, during the spring of 1992. The oxygen-carrying capacity of haemolymph from each species was low, although variable, and was correlated with the low concentration of Hc present. The Hc oxygen-affinity of native gammarid haemolymph was relatively high [partial pressure of oxygen required for half-saturation, P₅₀=4 to 5 torr (0.53 to 0.67 kPa)] at their respective in vivo pH values. At equivalent pH, however, Hc from G. locusta displayed a lower O₂-affinity than either Echinogammarus species. Gammarid Hcs had a large Bohr effect ( log P₅₀/ pH=-1.16 to-1.47). Resuspended Hc isolated from whole H. nilsonni showed similar O₂-binding properties to those of the gammaridean amphipods [P₅₀=6.3 torr (1.44 kPa) at pH=8.0; log P₅₀/pH=-1.20]. Comparable data for haemolymph from O. gammarellus showed that the Hc had a lower affinity for O₂ [P₅₀=14.1 torr (1.87 kPa) at in vivo pH] and exhibited a more moderate Bohr effect ( log P₅₀/ pH=-0.79). To eliminate the possibility that these differences were due to the different haemolymph constituents, each of the Hcs were pelleted and resuspended in physiological saline. The differences noted above persisted, demonstrating that they were due to inherent O₂-binding properties of the Hc molecules themselves. An increase in L-lactate resulted in an increase in Hc oxygen-affinity for both Echinogammarus species but not for O. gammarellus. This study has confirmed that there is a clear difference between Hcs from aquatic and semi-terrestrial amphipod genera. The results lend further support to the hypothesis that the move on to land by amphipod crustaceans is accompanied by a decrease in Hc oxygen-affinity, a decrease in the Bohr effect and a decrease in effector (in this case L-lactate) sensitivity.     

The burrows and physiological adaptations to a burrowing lifestyle of Natatolana borealis (Isopoda: Cirolanidae)

The isopod Natatolana borealis Lilljeborg constructs U-shaped burrows in soft mud, the bore of which closely approximates the width of the occupant. Within artificial burrows, the isopods are largely quiescent and often adopt a position close to one of the burrow openings. Conditions within burrows constructed in the laboratory are moderately hypoxic [11.7 to 14.9 kPa (88 to 112 torr)], with isopods showing discontinuous irrigation behaviour (pleopod beating). Rates of oxygen consumption (measured at 10°C) are maintained approximately constant over a wide range of oxygen partial pressure (P_{O 2}) due, in part, to a pronounced increase in pleopod beat rate. Values for the critical partial pressure of oxygen (P_c), the P_{O 2} at which can no longer be maintained independent of P_{O 2}, were 2.0 to 3.3 kPa (15 to 25 torr). N. borealis can survive lengthy periods (65 h at 5°C) of anoxia, during which there is a significant reduction in the carbohydrate concentration and an increase in the l-lactate concentration of the tissues. The oxygencarrying capacity of the haemolymph of N. borealis was low. The haemocyanin showed a relatively high oxygen affinity [P₅₀=0.39 kPa (2.99 torr) at 10°C at the in vivo pH of 7.80] and a pronounced Bohr effect (-1.22). These characteristics may be advantageous to a burrowing mode of life and also for the conditions likely to be encountered in fish carcasses into which they burrow en masse to feed.