Trace metals in interstitial waters from sandstones: acidic inputs to shallow groundwaters

There is some evidence from southern Britain that shallow groundwaters in non-carbonate lithologies may be affected by acidic deposition. To investigate this, interstitial water profiles down to 12 m have been obtained from unsaturated sands or semi-consolidated sandstones from the Folkestone Beds (Lower Greensand) of Surrey and the Sherwood Sandstone of the West Midlands. The pH of the interstitial waters generally increased with depth and reflected an increase in the base saturation of the exchange complex. Beneath the highly acidic surface soil horizons (pH 3.0-3.5), interstitial waters with a pH of 4.0-4.5 were found down to depths of several metres. The pH progressively increased to around pH 5.5 because of base cation desorption and the weathering of silicate minerals. High concentrations of aluminium (10-20 mg litre(-1)) and other metals (Fe, Mn, Cu, Ni, Co, Zn, Be) were found in the interstitial water in the upper unsaturated zone. Most metal concentrations were strongly pH-dependent but also reflected the geochemical characteristics of the parent sands or sandstones. H+ and trace element concentrations were slightly higher beneath areas of afforestation than beneath heathland. The downward fluxes of solutes have been estimated using rainfall-derived chloride as a non-reactive solute. The profiles retain a record of 10-20 years input allowing the past inputs from SO4 and other species to be estimated using solute/chloride ratios. Cation exchange sites are probably depleted over a period of decades and there can be a significant decrease in the unsaturated zone pH as a result of increased or sustained acidic deposition. The shallow groundwater environment (0-15 m) in non-carbonate terrains is therefore a sensitive environment where high metal concentrations may be generated and may ultimately lead to water quality problems in shallow water supplies.     

‘Emulsion locks’ for the containment of hydrocarbons during surfactant flushing

Reversible double water in oil in water (W/O/W) emulsions were developed to contain subsurface hydrocarbon spills during their remediation using surfactant flushing. Double emulsions were prepared by emulsifying CaCl₂ solutions in canola oil, and subsequently by emulsifying the W/O emulsions in aqueous sodium alginate solutions. The formation of double emulsions was confirmed with confocal and optical microscopy. The double emulsions reversed and gelled when mixed with the surfactants sodium dodecyl sulfate (SDS) and cocamidopropyl betaine (CPB). Gels can act as ‘emulsion locks’ to prevent spreading of the hydrocarbon plume from the areas treated with surfactant flushing, as shown in sand column tests. Shear rheology was used to quantify the viscoelastic moduli increase (gelation) upon mixing the double emulsion with SDS and CPB. SDS was more effective than CPB in gelling the double emulsions. CPB and SDS could adsorb at the interface between water and model hydrocarbons (toluene and motor oil), lowering the interfacial tension and rigidifying the interface (as shown with a Langmuir trough). Bottle tests and optical microscopy showed that SDS and CPB produced W/O and O/W emulsions, with either toluene or motor oil and water. The emulsification of motor oil and toluene in water with SDS and CPB facilitated their flow through sand columns and their recovery. Toluene recovery from sand columns was quantitated using Gas-Chromatography Mass-Spectroscopy (GC-MS). The data show that SDS and CPB can be used both for surfactant flushing and to trigger the gelation of ‘emulsion locks’. Ethanol also gelled the emulsions at 100 mL/L.     

Removal and desorption of chromium in synthetic effluent by a mixed culture in a bioreactor with a magnetic field

Two chromium removal experiments were performed in bioreactors with and without a magnetic field under the same conditions.The release of the chromium present in the biomass was tested in two experiments one with the initial pH of the medium and one with pH 4.0.The objective was to remove Cr(Ⅵ) and total Cr from the effluent,this was carried out by placing biological treatments of synthetic effluent contaminated with 100 mg/L of Cr(Ⅵ) in a bioreactor with neodymium magnets that applied a magnetic field(intensity85.4 mT) to the mixed culture.The removal of Cr(Ⅵ) was approximately 100.0% for the bioreactor with a magnetic field and 93,3% for the bioreactor without a magnetic field for9 hr of recirculation of the synthetic effluent by the bioreactor.The removal of total Cr was61.6% and 48.4%,with and without a magnetic field,respectively;for 24 hr.The desorption of Cr(VI) in the synthetic effluent was 0.05 mg/L,which is below the limit established by Brazilian legislation(0.1 mg/L) for the discharge of effluent containing Cr(Ⅵ) into bodies of water.The results obtained for the removal of chromium in synthetic effluent suggested that there was no significant influence on the viable cell count of the mixed culture.The desorption of Cr(Ⅵ) in synthetic effluent after bioadsorption of chromium by the mixed culture in the process of removal of chromium in bioreactors with and without a magnetic field was not significant in either of the experiments with different initial pHs.     

Utilization of a fumigated sediment by two benthic deposit-feeders:Abra alba (Mollusca: Bivalvia) andEupolymnia nebulosa (Annelida: Polychaeta)

The present study tested the utilization of dead microbial biomass by two benthic deposit-feeders:Abra alba (Wood) (Mollusca: Bivalvia) andEupolymnia nebulosa (Montagu) (Annelida: Polychaeta). Clams were collected in the Canet lagoon during spring 1989. Worms were collected in the Port-Vendres harbour during spring 1989. The¹⁴C-labelled (glutamic acid, 24 h) sediment used during the study was sterilized with 1% chloroform, washed with sterile seawater, and dried (60°C; 48 h). This sterilisation procedure, called fumigation is the least harmful to the sediment (Novitsky 1986). Both clams and worms were incubated in the presence of the fumigated sediment for 5, 10, 20, and 50 h. At the end of each experiment we recorded the radioactivity in four compartments: (1) sediment, (2) dissolved organic matter (DOM), (3) CO₂, and (4) animals. The radioactivity of the sediment was subdivided into five fractions: (i) soluble in 2N HCl, (ii) soluble in hot 5% trichloroacetic acid (TCA), (iii) soluble in 1N NaOH, (iv) soluble in hot 6N HCl, (v) residual (after combustion in a Leco carbon analyser). In the first set of experiments, after 20 h of incubation, 5.4 and 4.7% of the total radioactivity was taken up by clams and worms, respectively. However, a model revealed that this uptake could have been correlated with the release of radiolabelled DOM (33% of total radioactivity during the first 5 h). In order to test this assumption, we used the same protocol with three additional washes of the fumigated sediment. This resulted in a significantly lower uptake by the clams (1.9% of the total radioactivity byt = 50 h), whereas the worms exhibited an uptake similar to that in the initial experiment (5.1% of total radioactivity byt = 50 h). These results underline the importance of considering interactions with DOM when applying radiotracer techniques to the study of benthic food chains. The average ingestion rates of fumigated sediment byA. alba andE. nebulosa were 5.2 10^–2 mg sediment dry wt mg^–1 clam h^–1 and 3.5 10^–2 mg sediment dry wt mg^–1 worm h^–1, respectively, which is comparable to previous data reported for other deposit-feeding bivalves and polychaetes feeding on natural sediment or detritus. The low radioactivity recorded for CO₂ together with the similarity of the changes in the partitioning of the radioactivity within the sediment between control experiments and experiments carried out in the presence of clams or worms suggest low assimilation efficiencies. Therefore, the present study supports the fact that dead microbial biomass does not constitute an important food source for benthic deposit-feeders.     

Yield and grain quality of spring wheat (Triticum aestivum L., cv. Drabant) exposed to different concentrations of ozone in open-top chambers

Spring wheat (Triticum aestivum L., cv. Drabant) was exposed to different concentrations of ozone in open-top chambers for two growing seasons, 1987 and 1988, at a site located in south-west Sweden. The chambers were placed in a field of commercially grown spring wheat. The treatments were charcoal-filtered air (CF), non-filtered air (NF) and non-filtered air plus extra ozone (NF(+)). In 1988, one additional ozone concentration (NF(++)) was used. Grain yield was affected by the ozone concentration of the air. Air filtration resulted in an increase in grain yield of about 7% in both years, compared to NF. The addition of ozone (NF(+), NF(++)) reduced grain yield and increased the content of crude protein of the grain in both years. Filtration of the air had no significant effect on the content of crude protein, compared to NF. The results showed a strong positive chamber effect on grain yield in the cold and wet summer of 1987. In 1988, there was no net chamber effect on grain yield. The relative differences between the CF, NF and NF(+) treatments with respect to grain yield were of the same magnitude in the two years, despite the very different weather conditions.     

Plastic pellets, tar, and megalitter on Beirut beaches, 1977-1988

In the spring of 1988, five beaches along the coast of Beirut were surveyed for the presence of plastic pellets, tar, and megalitter--a follow-up to the studies conducted on the coast of Lebanon in 1977 for plastic pellet and tar occurrence, and in 1978 for containers and other megalitter on Beirut beaches. Plastic pellets were more abundant than they were in 1977 on three beaches and less so on two. Tar, however, seemed to occur much more abundantly on all five beaches. Megalitter, chiefly plastic but also paper, metal, and glass, had increased greatly compared with that seen 10 years ago. As in 1977, the unrestricted waste disposal practices of the plastic manufacturers, plus the possible loss of cargo from ships loading and unloading raw materials, are the most likely sources of plastic pellets. The abundance of tar is not surprising, considering that the Mediterranean Sea is tar-polluted and that two oil terminals occur on Lebanon's coast. Further, local gas stations frequently dump oil and grease onto the beaches, and numerous fires have occurred at coastal refineries over the past 10-15 years. All of these factors are likely to contribute to the presence of tar on the beaches. The main source of the vast quantities of megalitter on the beaches is undoubtedly the Lebanese people themselves, due to numerous population shifts and the lack of order and regulatory enforcement as a result of the civil chaos in the country. In addition, the ships docking or waiting for days, and sometimes weeks, to get into the Lebanese ports probably affect the abundance of megalitter (and tar) on the beaches.