Episodic Stream Acidification Caused by Atmospheric Deposition of Sea Salts at Acadia National Park, Maine, United States

Major episodic acidifications were observed on several occasions in first-order brooks at Acadia National Park, Mount Desert Island, Maine. Short-term declines of up to 2 pH units and 130-mu-eq L-1 acid-neutralizing capacity were caused by HCl from soil solutions, rather than by H2SO4 or HNO3 from precipitation, because (1) SO4 concentrations were constant or decreased during the pH depression, (2) Cl concentrations were greatest at the time of lowest pH, and (3) Na:Cl ratios decreased from values much greater than those in precipitation (a result of chemical weathering), to values equal to or less than those in precipitation. Dilution, increases in NO3 concentrations, or increased export or organic acidity from soils were insufficient to cause the observed decreases in pH. These data represent surface water acidifications due primarily to an ion exchange "salt effect" of Na+ for H+ in soil solution, and secondarily to dilution, neither of which is a consequence of acidic deposition. The requisite conditions for a major episodic salt effect acidification include acidic soils, and either an especially salt-laden wet precipitation event, or a period of accumulation of marine salts from dry deposition, followed by wet inputs.

The Response of a Small Stream in the Lesni Potok Forested Catchment, Central Czech Republic, to a Short-Term In-Stream Acidification

Lesni Potok stream drains a forested headwater catchment in the central Czech Republic. It was artificially acidified with hydrochloric acid (HCl) for four hours to assess the role of stream substrate in acid-neutralisation and recovery. The pH was lowered from 4.7 to 3.2. Desorption of Ca and MP and desorption or solution of Al dominated acid-neutralisation; Al mobilisation was more important later. The stream substrate released 4.542 meq Ca, 1, 184 meq Mg, and 2,329 meq Al over a 45 in long and I in wide stream segment, smaller amounts of Be. Cd, Fe, and Mn were released. Adsorption of SO42- and desorption of F- occurred during the acidification phase of the experiment. The exchange reactions were rapidly reversible for Ca, Mg and SO42- but not symmetric as the substrate resorbed 1083, 790 and 0 meq Ca, Mg, and Al. respectively, in a 4-hour recovery period. Desorption of SO42- occurred during the resorption of Ca and Mg. These exchange and dissolution reactions delay acidification, diminish the pH depression and retard recovery from episodic acidification. The behaviour of the stream substrate-water interaction resembles that for soil-soil water interactions. A mathematical dynamic mass-balance based model, MASS (Modelling Acidification of Stream Sediments), was developed which simulates the adsorption and desorption of base cations during the experiment and was successfully calibrated to the experimental data.

Response of a First-Order Stream in Maine to Short-Term In-Stream Acidification

An experimental short-term acidification with HCl at a first-order stream in central Maine, USA was used to study processes controlling the changes in stream chemistry and to assess the ability of stream substrate to buffer pH. The streambed exerted a strong buffering capacity against pH change by ion exchange during the 6-hour acidification. Streambed substrates had substantial cation and anion exchange capacity in the pH range of 4.1 to 6.5. The ion exchange for cations and SO42- were rapid and reversible. The speed of release of cations from stream substrates was Na1+ > Ca2+ > Mg2+ > Aln+ > Be2+, perhaps relating to charge density of these cations. Ca2+ desorption dominated neutralisation of excess H+ for the first 2 hr. As the reservoir of exchangeable Ca diminished, desorption land possibly dissolution) of Al3+ became the dominant neutralising mechanism. The exchangeable land possibly soluble) reservoir of Al was not depleted during the 6-hour acidification. Sulphate adsorption during the acidification reduced the concentration of SO42- in stream water by as much as 20 mu eq L-1 (from 70 mu eq L-1). Desorption of SO42- and adsorption of base cat ions after the artificial acidification resulted in a prolongation of the pH depression. The streambed had the capacity to buffer stream water chemistry significantly during an acidifying event affecting the entire upstream catchment.

Animal Guts as Nonideal Chemical Reactors: Partial Mixing and Axial Variation in Absorption Kinetics

Animal guts have been idealized as axially uniform plug-flow reactors (PFRs) without significant axial mixing or as combinations in series of such PFRs with other reactor types. To relax these often unrealistic assumptions and to provide a means for relaxing others, I approximated an animal gut as a series of n continuously stirred tank reactors (CSTRs) and examined its performance as a Function of n. For the digestion problem of hydrolysis and absorption in series, I suggest as a first approximation that a tubular gut of length L and diameter D comprises n=L/D tanks in series. For n greater than or equal to 10, there is little difference between performance of the nCSTR model and an ideal PFR in the coupled tasks of hydrolysis and absorption. Relatively thinner and longer guts, characteristic of animals feeding on poorer forage, prove more efficient in both conversion and absorption by restricting axial mixing, in the same total volume, they also give a higher rate of absorption. I then asked how a fixed number of absorptive sites should be distributed among the n compartments. Absorption rate generally is maximized when absorbers are concentrated in the hindmost few compartments, but high food quality or suboptimal ingestion rates decrease the advantage of highly concentrated absorbers. This modeling approach connects gut function and structure at multiple scales and can be extended to include other nonideal reactor behaviors observed in real animals.

Kinetics and Mechanism of Oxygen Delignification

Considerable research has been conducted into the kinetics and selectivity of the oxygen delignification process to overcome limitation in its use. However most studies were performed in a batch reactor whereby the hydroxide and dissolved oxygen concentrations are changing during the reaction time in an effort to simulate tower performance in pulp mills. This makes it difficult to determine the reaction order of the different reactants in the rate expressions. Also the lignin content and cellulose degradation of the pulp are only established at the end of the experiment when the sample is removed from the batch reactor. To overcome these deficiencies, we have adopted a differential reactor system used frequently for fluid-solid rate studies (so-called Berty reactor) for measurement of oxygen delignification kinetics. In this reactor, the dissolved oxygen concentration and the alkali concentration in the feed are kept constant, and the rate of lignin removal is determined from the dissolved lignin content in the outflow stream measured by UV absorption. The mass of lignin removed is verified by analyzing the pulp at several time intervals. Experiments were performed at different temperatures, oxygen pressures and caustic concentrations. The delignification rate was found to be first order in HexA-free residual lignin content. The delignification rate reaction order in caustic concentration and oxygen pressure were determined to be 0.42 and 0.44 respectively. The activation energy was found to be 53kJ/mol. The carbohydrate degradation during oxygen delignification can be described by two contributions: one due to radicals produced by phenolic delignification, and a much smaller contribution due to alkaline hydrolysis. From the first order of the reaction and the pKa of the active lignin site, a new oxygen delignification mechanism is proposed. The number 3 carbon atom in the aromatic ring with the attached methoxyl group forms the lignin active site for oxygen adsorption and subsequent electrophic reaction to form a hydroperoxide with a pKa value similar to that of the present delignification kinetics. The uniform presence of the aromatic methoxyl groups in residual lignin further support the first order in lignin kinetics.