Three Mn dioxides—birnessite, cryptomelane, and pyrolusite—were examined for their ability to deplete the concentration of As(III), a highly toxic pollutant, in solution. The depletion [oxidation of As(III) to As(V) and sorption of As(III)] of As(III) by all three Mn dioxides follows first‐order kinetics. The rate constants for the depletion of As(III) by birnessite and cryptomelane at 298 K are 0.267 and 0.189 h−1, respectively. On the other hand, the depletion rate of As(III) by pyrolusite is much slower: the rate constant at 298 K is 0.44 × 10−3 h−1. This difference in the rate of depletion is largely attributed to the crystallinity and specific surfaces of the Mn dioxides. Pyrolusite is highly ordered and has a low specific surface of 0.8 hm2/kg (7.9 m2/g); conversely, birnessite and cryptomelane are poorly crystalline and have relatively high specific surfaces of 27.7 and 34.6 hm2/kg (277 and 346 m2/g), respectively. The energies of activation for the depletion of As(III) by the Mn dioxides range from 26.0 to 32.3 kJ/mol. The reaction appears to be predominantly diffusion‐controlled. The ability of the Mn dioxides to sorb As(III) and As(V) appears to be related to the specific surface and the point‐of‐zero charge of the oxides. The data indicate that, after the systems have reached equilibrium with respect to the sorption of total As, the depletion of As(III) by the oxides is still progressing. This is apparently because of the one‐to‐one relationship between the amount of As(III) depleted and the amount of As(V) appearing in solution.

Sediments from five lakes in southern Saskatchewan, Canada, oxidize As(III) (arsenite) to As(V) (arsenate). The oxidation is not affected by flushing N2 or air through the sediment suspensions, nor does the addition of HgCl2 to the system eliminate the conversion of As(III) to As(V). The oxidation is an abiotic process with microorganisms playing a relatively minor role in this system. Because As(III) is more toxic and sorbed to a lesser extent by sediments than As(V), the suspended and bottom sediments may potentially alleviate the toxicity of As(III) through abiotic oxidation in aquatic environments.

The importance of various sediment components in the oxidation of As(III) (arsenite) to As(V) (arsenate) by freshwater lake sediments in southern Saskatchewan was examined. Treating the sediments with hydroxylamine hydrochloride or sodium acetate to remove Mn greatly decreased the oxidation of As(III). Furthermore, synthetic Mn(IV) oxide was a very effective oxidant with respect to As(liD: 216 t~g As(V)/ml was formed in solution when 1000 txg As(III)/ml was added to suspensions of 0.1 g of the oxide. These results indicate that Mn in the sediment was probably the primary electron acceptor in the oxidation of As(III). The conversion of As(III) to As(V) by naturally occurring carbonate and silicate minerals common in sediments was not evident in the system studied. Sediment particles >20 ~.m in size are the least effective in oxidizing As(III); the oxidizing ability of the 5-20-, 2-5-, and <2-/~m particle size fractions varies depending on the sediment. The concentration of As(V) in equilibrated solutions after adding increasing amounts of As(III) (as much as 100/~g/ml) to 1 g of the three sediments ranged from approximately 3.5 to 19 p.g/ml. Because As(III) is more toxic and soluble than As(V), Mn-bearing components of both the colloidal and non-colloidal fractions of the sediments may potentially detoxify any As(Ill) that may enter aquatic environments by converting it to As(V). This is very important in reducing the As contamination and in maintaining the ecological balance in aquatic environments.

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Abstract--This investigation was carried out to study the effect of different concentrations of citric acid and glycine, which are common in freshwaters, on the kinetics of the adsorption of Hg by kaolinite under various pH conditions. The data indicate that Hg adsorption by kaolinite at different concentrations of citric acid and glycine obeyed multiple first order kinetics. In the absence of the organic acids, the rate constants of the initial fast process were 46 to 75 times faster than those of the slow adsorption process in the pH range of 4.00 to 8.00. Citric acid had a significant retarding effect on both the fast and slow adsorption process at pHs of 6.0 and 8.0. It had a significant promoting effect on the fast and slow adsorption process at pH 4.00. Glycine had a pronounced enhancing effect on the rate of Hg adsorption by kaolinite during the fast process. The rise in pH of the system further increased the effect of glycine on Hg adsorption. The magnitude of the retarding/promoting effect upon the rate of Hg adsorption was evidently dependent upon the pH, structure and functionality of organic acids, and molar ratio of the organic acid/Hg. The data obtained suggest that low-molecular-weight organic acids merit close attention in studying the kinetics and mechanisms of the binding of Hg by sediment particulates and the subsequent food chain contamination.

Periphytic biomass in a downriver riffle of the Grand River in Southern Ontario, Canada was measured with concrete-block glass slide samplers from May to December 1971. Average rate of accumulation of periphyton on glass slides was 266.2 mg/m2/day ash-free weight, 120.9 mg/m2/day carbon, 20.4 mg/mz/day nitrogen, or 1.11 mg/mZ/day chlorophyll a and on concrete blocks was 590.0 mg/mZ/day ash-free weight, 202.9 mg/mZ/day carbon, 22.8 mg/m2/day nitrogen, or 2.95 mg/ mz/day chlorophyll a. The standing biomass of periphyton on glass slides varied from a maximum of 21.6 g/m2 between May 28 and July 15 to a minimum of 0.7 g/m2 in December with an average of 8.6 g/m2. The biomass on concrete blocks ranged from a high of 132.5 g/m2 in August to a low of 29.9 g/m2 in October with a mean of 66.1 g/rnZ. The well established periphyton on concrete blocks towards the end of the study period was similar to that from native rocks with respect t o biomass, carbon and nitrogen contents, and ratios of biomass t o chlorophyll a. This suggests t h a t concrete blocks are a better substrate than glass slides for measuring riverbed periphyton.By comparing biomass of periphyton on slides and on concrete blocks, the average rate of loss of periphyton from concrete blocks was estimated to be 2.9 g/m'/day, representing 63% of the mean total accumulation rate of the periphyton. The magnitude of the estimated total loss and the high standing biomass of the periphyton on concrete blocks manifest the importance of the periphyton as a source of organic matter in the river. Contents

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Particulate organic matter in a downriver riffle of the Grand River, the largest Canadian Great Lakes tributary, was studied between June 1970 and April 1972. In winter and spring, concentrations of particulate organic matter (1.0–26.2 mg/l) varied with river flow. High summer levels (3.4–12.7 mg/l) were attributable to high autochthonous primary production. Mean chlorophyll a concentration in summer (29.8 mg/m3) was nearly 15 times higher than in winter, and 8 times the spring mean level. High algal cell counts (15,000–19,000 cells/l) also occurred in summer. Autochthonous and allochthonous contributions to the total particulate organic carbon input to the river in summer were estimated by daily organic input and river flow relationships, carbon to chlorophyll a and to pheopigments ratios. The allochthonous source accounted for 21.5% of the total organic carbon while the autochthonous contributed the remaining 78.5%. The latter included living algae (23.0%), senescent plant material (30.3%) and detritus (25.2% — including microbes). The study establishes a new approach whereby the various components of particulate organic matter in river water can be indirectly partitioned and their biomass estimated by using quantitative relationships among readily obtainable parameters of river flow, standing biomass, chlorophyll a and pheopigments.