Modelling episodic acidification of surface waters: the state of science

Field studies of chemical changes in surface waters associated with rainfall and snowmelt events have provided evidence of episodic acidification of lakes and streams in Europe and North America. Modelling these chemical changes is particularly challenging because of the variability associated with hydrological transport and chemical transformation processes in catchments. This paper provides a review of mathematical models that have been applied to the problem of episodic acidification. Several empirical approaches, including regression models, mixing models and time series models, support a strong hydrological interpretation of episodic acidification. Regional application of several models has suggested that acidic episodes (in which the acid neutralizing capacity becomes negative) are relatively common in surface waters in several regions of the US that receive acid deposition. Results from physically based models have suggested a lack of understanding of hydrological flowpaths, hydraulic residence times and biogeochemical reactions, particularly those involving aluminum. The ability to better predict episodic chemical responses of surface waters is thus dependent upon elucidation of these and other physical and chemical processes.     

Effects of clearfelling on stream and soil water aluminium chemistry in three UK forests

Data are presented demonstrating how clearfelling has changed soil and stream water aluminium chemistry. For soil waters, a strong empirical relationship was observed between inorganic aluminium (Al(inorg)) and total inorganic anion (TIA) concentrations. Before felling, chloride and sulphate accounted for the largest proportion of the TIA concentration. After felling, in soils where nitrification was active, nitrate became increasingly important. Where this led to an increase in TIA, Al(inorg) concentrations increased. Over five years, nitrate concentrations have fallen, along with TIA, resulting in a sympathetic decline in Al(inorg). Streams draining clearfelled areas initially became more acid, although chloride and sulphate concentrations decreased. Stream water nitrate concentrations increased soon after felling and remained higher than controls for up to four years. While nitrate concentrations were high, Al(inorg) remained unchanged. Subsequently, as nitrate and TIA decreased, Al(inorg) also declined to concentrations below those in the control stream. Clearfelling upland forests will not necessarily result in immediate improvements in water quality, although long-term benefits may be seen before canopy-closure of the next crop.     

Cadmium availability to the cyanobacterium Synechocystis aquatilis in solutions containing chloride

Availability of cadmium to Synechocystis aquatilis (estimated by 109Cd sorption and cadmium toxicity-14C method) in solutions containing cadmium and complexing (KCl) or non-complexing (KNO3) salts, in the range of 0-0.5 m was investigated. Both cadmium surface adsorption and transport into the cells were lower in solutions containing cadmium chloride complexes (CdCl+, CdCl2, CdCl3-) than in those containing cadmium in the form of Cd2+. Also, cadmium toxicity in solutions of higher KCl concentrations, in which CdCl+ and CdCl2 forms predominated, was significantly limited.     

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.     

Responses of microbial populations in the rhizosphere to deposition of simulated acidic rain onto foliage and/or soil

Air pollutants or some chemicals applied to plant foliage can alter the ecology of the rhizosphere. Experiments were conducted to distinguish among possible foliage-mediated versus soil- or root-mediated effects of acid deposition on microorganism in the rhizosphere. Seedlings of a sorghum x sudangrass hybrid in pots of non-sterile soil-sand mix in a greenhouse were exposed to simulated rain solution adjusted with H2SO4 + HNO3 to pH 4.9, 4.2, 3.5 or 2.8. Solutions were applied as simulated rain to foliage and soil, foliage only (soil covered by plastic, and deionized water applied directly to the soil), or soil only (solution applied directly to the soil). Solutions were applied on 16 days during a 6-week period (1.5 cm deposition in 1 h per application). Plant shoot and root dry weights and population densities of selected types of bacteria, filamentous actinomycetes and fungi in the rhizosphere were quantified after exposures were completed. Deposition of simulated acidic rain onto foliage alone had no effect on plant biomass or microbial population densities in the rhizosphere (colony-forming units per gram of rhizosphere soil). However, plant growth was stimulated and all microbial populations in the rhizosphere increased 3- to 8-fold with increased solution acidity (relative to pH 4.9 solution) when solution penetrated the soil. Statistical analyses indicated that the acid dose-population response relationships for soil-only and foliage-and-soil applications were not different. Thus, no foliage-mediated effect of simulated acidic rain on rhizosphere ecology was detected.     

Response of the Plastic Lake catchment, Ontario, to reduced sulphur deposition

As a consequence of decreases in the emission rate of sulphur in eastern North America in the late 1970s and early 1980s, sulphate deposition in central Ontario declined by about 40%, but has remained constant for about six years. Plastic Lake, a small, dilute lake on the Precambrian shield that the authors have studied since 1979, acidified between the start of the study and about 1986, but since then has not changed. The authors also monitored the chemistry of streamwater draining the Plastic Lake catchment. Water quality of runoff from an upland site improved rapidly (pH and alkalinity increased, SO4(2-) and Al decreased), but two factors offset these improvements. A small wetland area downstream reversed most of these changes, resulting in a constant output of strong acid from the catchment. In addition, in extremely dry years (1983, 1987, 1989) there were very high concentrations of SO4(2-) in the streamwater, suggesting substantial re-oxidation of reduced S in the catchment.     

Rate-temperature responses in scyphozoan medusae and polyps

The effects of temperature on oxygen consumption and spontaneous rhythmic activity have been investigated in various stages of the life histories of 3 species of jellyfish from the Chesapeake Bay, USA. All 3 species clearly show the ability to acclimate positively to temperature change. Thermal sensitivity of metabolism in the winter medusa Cyanea capillata fulva is fairly low at temperature intervals which are experienced in nature. Polyps of the two summer medusae, Chrysaora quinquecirrha and Aurelia aurita, show reduced metabolic sensitivity at temperatures normally accompanying high developmental activity and the onset of strobilation.     

Simulation of a 100-MW solar-powered thermo-chemical air separation system combined with an oxy-fuel power plant for bio-energy with carbon capture and storage (BECCS)

The combination of concentrated solar power–chemical looping air separation (CSP-CLAS) with an oxy-fuel combustion process for carbon dioxide (CO₂) capture is a novel system to generate electricity from solar power and biomass while being able to store solar power efficiently. In this study, the computer program Advanced System for Process Engineering Plus (ASPEN Plus) was used to develop models to assess the process performance of such a process with manganese (Mn)-based oxygen carriers on alumina (Al₂O₃) support for a location in the region of Seville in Spain, using real solar beam irradiance and electricity demand data. It was shown that the utilisation of olive tree prunings (Olea europaea) as the fuel—an agricultural residue produced locally—results in negative CO₂ emissions (a net removal of CO₂ from the atmosphere). Furthermore, it was found that the process with an annual average electricity output of 18 MW would utilise 2.43% of Andalusia’s olive tree prunings, thereby capturing 260.5 k-tonnes of CO₂, annually. Drawbacks of the system are its relatively high complexity, a significant energy penalty in the CLAS process associated with the steam requirements for the loop-seal fluidisation, and the gas storage requirements. Nevertheless, the utilisation of agricultural residues is highly promising, and given the large quantities produced globally (~?4 billion tonnes/year), it is suggested that other novel processes tailored to these fuels should be investigated, under consideration of a future price on CO₂ emissions, integration potential with a likely electricity grid system, and based on the local conditions and real data.