Solubility of a proto-imogolite sol in oxalate solutions

The amounts of aluminium liberated from a proto-imogolite (P-I) sol by 1–3 mM oxalate at pH 4·8–7·1 are found to be in excellent agreement with those calculated on the basis of the solubility product of the P-I sol, and the stability constants for aluminium oxalate complexes established earlier. Calculated solubility curves are presented for proto-imogolite sols in the presence of 10^?3, 10^?4 and 10^?5 M total oxalate over the pH range 4–8, and also for the case where oxalate concentrations are controlled by solid calcium oxalate in the presence of 0·05, 0·5 and 5 mM calcium ion. We conclude that the presence of a proto-imogolite allophane in podzol B horizons of pH 5·0 requires oxalate concentrations less than 10^?5 M. For fertile agricultural soils with typical calcium concentrations (approximately 5 mM) in the soil solution, aluminium oxalate concentrations would be limited by calcium oxalate solubility to less than 10^?6 M in the presence of proto-imogolite allophane at pH values exceeding 5·5. In leached podzolic soils calcium concentrations are generally less than 0·05 mM, and would not limit the formation of aluminium oxalate complexes.     

Kinetic parameters of the rhodanese reaction in soils

Studies to determine the kinetic parameters of the rhodanese-catalyzed reaction in soils showed that the K_m values of thiosulfate and cyanide for this enzyme are similar to those for the same enzyme isolated from other biological systems. Application of the three linear transformations of the Michaelis-Menten equation indicated that the apparent K_m constants of thiosulfate and cyanide varied among the soils used, but the results obtained by the three plots were similar. By using the Lineweaver-Burk plot. the K_m values of S₂O₃^?2 and CN^? for rhodanese activity in five soils ranged from 1.20 to 10.3 (av 5.46) and from 2.48 to 10.20 (av 5.81) mM, respectively. The V_max values ranged from 511 to 1431 (av 759) nmoles SCN^? produced · g^?1 soil · h^?1. The activation energy values ranged from 21.6 to 34.0 (av 28.0) kJ · mole^?1, and the average Q₁₀ for temperatures ranging from 10 to 60 C ranged from 1.25 to 1.45 (overall average. 1.37).     

Kinetics of cadmium uptake by green algae

The kinetics of cadmium uptake by Selenastrum capricornutum Printz was studied at 21 °C and 0 °C and at four different concentrations of free cadmium (10^?9, 10^?8, 10^?7 and 10^?3 M). The free cadmium concentrations in the medium were kept constant through buffering by a chelating agent (NTA). Initial uptake occurred within 10 min at both temperatures, indicating a fast process. At 21 °C, the cadmium uptake increased during the experimental sampling times from 0.12 to 50 h, whereas at 0 °C, the cadmium uptake remained constant after the first sampling time. Apparently, two different processes were involved in cadmium uptake, a first fast, probably passive process and a second slower, possibly physiological process. The cadmium uptake processes are described with a generalized metalligand complex formation model. The experimental dissociation constants for the fast (K _R,F ) and the slow process (K _R,S ) were reproducible for different experiments and they were both in the order of 5 10^?6 mol L^?1. For the slow process, the uptake- and release rate constants (k₁ and k₂) were quantified; for two experiments, the mean value for k_i was 111±28 L mol^?1 h^?1 and the mean value for k ₂ was (5.1±1.8) 10^?4 h^?1. These values were calculated using the fitted value of the cadmium uptake in the fast process.     

Comparison of the influence of tannic acid and selected low-molecular-weight organic acids on precipitation products of aluminum

The crystallization and surface properties of hydrolytic reaction products of Al precipitated in the presence of 1.0 · 10^?6M and 1.0 · 10^?4M tannic acid from systems at the initial Al concentrations of 1.1 · 10^?4M and 1.1 · 10^?3M and OH/Al molar ratios of 2.0 or 3.0 were examined.X-ray diffraction analyses show that the structural distortion within the hydrolytic precipitation products of Al increases with the molar ratio of tannic acid to Al. The non-crystalline to poorly ordered hydrolytic precipitation products of Al, including pseudoboehmite, are formed in the presence of tannic acid and are shown by transmission electron micrographs to be fine, shapeless and hollow colloids which are deformed and aggregated. In contrast to low molecular weight organic acids (p-hydroxybenzoic, aspartic, malic, and citric acids), the influence of tannic acid on the surface reactivities of the precipitation products of Al cannot be solely explained on the basis of its chemical affinity towards Al. In addition to complexation, the physical adsorption of the tannic acid initially present at 1.0 · 10^?6M apparently promotes structural distortion in the precipitation products and thereby increases the specific surface and the formation of active sites for surface charge development and for phosphate and Ca retention to an extent even greater than that observed with the more strongly complexing malic acid. On the other hand, when the concentration of tannic acid is increased to 1.0 · 10^?4M, the physical adsorption of the tannic acid, while enhancing Ca retention through its ability to ionize and provide negative charges, hampers phosphate retention by masking some of the active sites.     

Simultane Bestimmung von N-Transformationsraten in Bodensäulen unter Verwendung von 15-N: Stickstoffmodell für eine Terra fusca-Rendzina

Simultaneous determination of nitrogen transformation rates in soil columns using 15-N: N-Model of a Terra fusca-Rendzina soil Rates of ammonification, nitrification, immobilization, and denitrification were determined in undisturbed columns of a Terra fusca Rendzina soil. A steady input of 15-N labelled ammoniumsulfate with the irrigation water created a steady state of the turnover processes in the soil resulting in a constant output of 15-N-nitrate. In this state the rate constants (8°C) were K₁ = 0.64 for the netto-N-nitrification, K₂ = 0.11 for the netto-N-denitrification, and K₃ = 0.25 for the netto-N-immobilization. 64% of the nitrate was leached, 25% immobilized in organic matter, and 11% denitrified. Relating these rate constants to the turnover of the soil nitrogen one can calculate the mean annual rates for the different processes of a forest soil, using the mean annual temperature. For the Göttinger Wald situation (T = 6.9°C) the following rates were calculated; Ammonification = 183 kg N·ha^?1·a^?1, immobilization = 44 kg N·ha^?1·a^?1, netto N-denitrification = 19 kg N·ha^?1·a^?1, and netto-N-mineralization = 120 kg N·ha^?1·a^?1.     

Proprietes des diphenol oxydases extraites des sols

Properties of diphenol oxidases extracted from salts. Salmine and SP-Sephadex C-25 were used to separate the enzyme system associated with humic materials in the neutral extracts of fresh soils (NAFS Extract). Electrophoresis on polyacrylamide gel shows that this preparation is heterogeneous. The elementary analysis of the soil enzyme is C 43·13%; N 5·09%; H 7·21%; O 44·58%. Chromatographic analyses indicate that the soil enzyme contains 53 per cent amino acids, 36 per cent sugars and amino sugars and 10 per cent ammonium and inorganic materials. The soil enzyme has a maximum absorption at 270–280 nm. The soil enzyme degrades the following substrates at the relative rate mentioned in parentheses : d-catechin (298);p-cresol (251); catechol (156); dl-DOPA (100);p-phenylene diamine (59);p-quinol (20) in terms of rate of oxygen absorption. This enzymatic preparation has the properties of an o- and p-diphenol oxidase. The rate of decarboxylation was measured using a radiorespirometer. The following relative values are dl-DOPA-l-¹⁴C (100); dl-tyrosine-l-¹⁴C (35) ; dl-tyrptophan-1-¹⁴C (7); dl-phenylalanine-l-¹⁴C (2). The dl-DOPA-2-¹⁴C was partially degraded to ¹⁴CO₂. The O₂ absorbed and CO₂ (carboxyl) evolved in case of dl-DOPA was in the ratio of 1·8 at 37°C. The activation energy on dl-DOPA was 3·1 and 7·9 kcal/mole/°C for oxygen absorption and decarboxylation respectively. The enzymatic activity on dl-DOPA-l-¹⁴C was optimum in air and inhibited in a N₂ atmosphere. Decarboxylation on dl-DOPA-l-¹⁴C followed the Michaelis-Menten law, from which we found that K_m = 8·3 × 10^?4M for decarboxylation. The oxidative decarboxylation was inhibited by H₂O₂ (74%); KCN (75%); ascorbate (92%); BAL (97%);DIECA(90%).Melanogenesis of dl-DOPA followed first order kinetics. The maximum absorption at 305 nm during melanogenesis shows the formation of dopachrome.     

The role of organic acids in the soil solution chemistry of a podzolized soil

The soil solution chemistry of a podzolized soil in the north of Sweden was monitored for four years using percolation lysimeters. Weak organic acids were a major constituent of the soil solution and are important because of their ability to form complexes with aluminium. Dissolved organics leached from the mor layer enhance the weathering rate in the eluvial horizon by forming complexes with aluminium, especially during the autumn when the leaching of dissolved organics was greatest. The weak organic acids were titrated and their pK_a values were evaluated. Aluminium was speciated with an ion-exchange method and by applying equilibrium calculations. Formation constants for the organic aluminium complexes were calculated to be log K_Along=5.42±0.32 m ^?1 (n=13) in spring and summer and log K_Alorg=4.87±0.14 m ^?1 (n=6) in autumn. Equilibria of Al³⁺ with solid phases were also examined using solubility constants. Percolation lysimeters below undisturbed and cut-off mor layers were compared.     

Complexation of Cu2+ and Pb2+ by peat and humic acid

The binding of metal to humic substances is problematical. The approaches for studying metal binding to organic matter are briefly reviewed. Ion-selective electrodes (Cu²⁺ and Pb²⁺) were used to measure metal complexation by a whole peat and an extracted humic acid (HA) fraction. Scatchard plots and calculation of incremental formation constants were used to obtain values for the binding constants for the metals onto both peat and HA. Both the peat and the humic acid had a larger maximum binding capacity for Pb²⁺ than for Cu²⁺ (e.g. at pH = 5 HA gave 0·188 mmol Cu²⁺ g^?1 and 0·564 mmol Pb²⁺ g^?1: peat gave 0·111 mmol Cu²⁺ g^?1 and 0·391 mmol Pb²⁺ g^?1). Overall, the humic acid had a larger metal binding capacity, suggesting that extraction caused conformational or chemical changes. The binding constants (K₁) for Cu²⁺ increased with increasing pH in both peat and humic acid, and were larger in the peat at any given pH (e.g. at pH = 5 HA gave log K₁= 2·63, and peat gave log K¹= 4·47 for Cu²⁺). The values for Pb²⁺ showed little change with pH or between peat and humic acid (e.g. at pH = 5 HA gave log K¹= 3·03 and peat gave log K¹= 3·00 for Pb²⁺). In the peat, Cu²⁺ may be more able to bind in a 2:1 stoichiometric arrangement, resulting in greater stability but smaller binding capacity, whereas Pb²⁺ binds predominantly in a 1:1 arrangement, with more metal being bound less strongly. Whole peat is considered to be more appropriate than an extracted humic acid fraction for the study of heavy metal binding in organic soils, as this is the material with which metals introduced into an organic soil would interact under natural conditions.     

Kinetics of the reaction between the hydroxyl radical and organic matter standards from the International Humic Substance Society

Purpose

The objective of this study was to evaluate the effect of the physicochemical properties of five dissolved organic matter (DOM) isolates on their reactivity with the hydroxyl radical (HO·) in water.

Materials and methods

Five DOM isolates were purchased from the International Humic Substance Society (IHSS). Weight average molecular weight (M _W) of these samples was quantified using size exclusion chromatography based on polyethylene glycols as reference standards. Functional group and elemental composition of the DOM samples were available from the IHSS website. Room temperature rate constants were measured using electron pulse radiolysis.

Results and discussion

Five IHSS standards were examined in this study: two soil organic and three aquatic organic matters. The composition varied from samples that had primarily aliphatic carbon (Pony Lake fulvic acid) to mostly aromatic carbon moieties (Elliot Soil humic acid). The M _W values of the five samples ranged from 2,400 to 4,100 Da, with an average value of 3,060 Da. Second-order reaction rate constants between DOM and HO· (k _DOM-HO·) were measured using thiocyanate competition kinetics, giving values ranging from 1.21 to 10.36?×?10⁸ M_C ^?1?s^?1. The k _DOM-HO· values were not found to correlate with either M _W or the aliphatic-aromatic carbon ratio, which is consistent with previous reports looking at natural organic matter (NOM), but is different to reports on size-fractionated (ultrafiltration through 15–1 kDa membranes) effluent organic matter (EfOM). We attribute this difference to the larger molecular weight distributions in size-fractionated EfOM compared to NOM.

Conclusions

The k _DOM-HO· values in this study ranged over a factor of 10, suggesting that hydroxyl radical reactivity does depend on the sample composition; however, no major correlation was found between the measured reactivity and bulk physicochemical properties of DOM.     

Reduction of Cr(VI) by soil humic acids

The rate of hexavalent chromium reduction by a soil humic acid (SHA) was investigated in aqueous solutions where concentrations of Cr(VI), H⁺, and SHA were independently varied. Rate experiments were done with a large excess of SHA over Cr(VI). Rates of reduction depend strongly on [H⁺], increasing with decreasing pH. Typical Cr(VI)-SHA reactions display a nonlinear reduction of Cr(VI) with time that cannot be modelled with simple first- or second-order rate equations. An empirical rate equation is developed for Cr(VI)-soil humic acid reactions over a range of experimental conditions. The model is in part based on a reactive continuum concept developed for soil fulvic acids. The rate equation describing Cr(VI) reduction by SHA is: R= -(k₀+k[H⁺]^1/2)[HCrO₄^?]^1/2X_e^?1, where k₀ is (8·3 ± 1·2) × 10^?12, s^?1k is (2·04 ± 0·05) × 10^?9 l^1/2 mol^?1/2 s^?1, and X_e is the equivalent fraction of SHA oxidized. The rate equation adequately models Cr(VI) reduction in an experiment with [Cr(VI)]₀ four times greater than the maximum concentration used in its derivation. Cr(VI) reduction at pH 3 by two other SHAs can also be modelled using the rate equation. The difference between the rate coefficients for the humic acid and the fulvic acid from the same soil was greater than the difference in the rate coefficients for humic acids from different soils.     

Die Rolle der mikrobiellen Biomasse und des mineralisch fixierten Ammoniums bei den Stickstoff-Transformationen in niedersächsischen Löß-Ackerböden unter Winter-Weizen. II. Umsetzung von 15N-markiertem Stickstoff

Significance of microbial biomass and mineral fixed ammonium with respect to the nitrogen transformations in loess soils of Niedersachsen during the growing season of winter wheat. II. ¹⁵N-turnover Field experiments 1988/89 on a fallow plot of the southern Niedersachsen loess area with straw application (δ 10 t · ha^?1, homogeneously incorporated by hand) yielded an increase in microbial biomass-N (N_mic) by 60 kg N · ha^?1 · 30 cm^?1 until March 1989 and further 40 kg N · ha^?1, till May which was almost completely remobilized until harvest. For a cropped plot (with winter wheat and 10 t · ha^?1 straw incorporation), N immobilization was of similar magnitude. Up to 18% of the applied ¹⁵N-fertilizer (185 kgN · ha^?1) were microbially immobilized. In contrast to 1988/89, no significant mass change of N_mic occurred in 1991 due to straw application (δ 10t · ha^?1). Variations in the amount of N_mic were nearly independent on the treatment (crop, with 140 kg fertilizer-N · ha^?1 or without N-fertilizer, respectively; fallow plot without fertilizer-N) within a range of 225-400 kg N · ha^?1 · 30 cm^?1. Directly after N-application (each 70 kg N · ha^?1 in March and in May), up to 100% of the fertilizer-N were assimilated by the microbes. Subsequently, remobilization of the immobilized nitrogen occurred within 2 (in March) or 6 weeks (in May), respectively. Simultaneously, organic soil-N was mineralized after each N-application and minerally fixed for us biggest part. Between March and June, the fixed NH₄+ decreased by about 112 kg · ha^?1 · 30 cm^?1.     

The destruction of quartz, amorphous silica minerals, and feldspars in model experiments and in soils: Possible mechanisms, rates, and diagnostics (the analysis of literature)

The dissolution of quartz and amorphous SiO₂ proceeds via the adsorption of water molecules on the surface of these minerals with the further formation of four silanol groups around the silicon atom and the detachment of the molecules of orthosilicic acid from the surface. The rates of quartz dissolution at pH 7 and 3 constitute 10^?15.72 and 10^?16.12 mol/m² s, respectively. They increase by three orders of magnitude upon the rise in pH from 7 to 10; they also increase in the solutions of strong electrolytes and in the presence of the anions of polybasic organic acids. The dissolution of feldspars begins from the release of alkali metals and calcium from the surface of crystal lattices of these minerals into the solution in the course of the cation exchange reaction. This is a fast process, and it does not control the rate of the feldspar dissolution that depends on the concentrations of protonated (in the acid medium) and deprotonated (in the alkaline medium) complexes with participation of the surface Si-O-Si and Al-O-Si groups of the mineral lattices. The rate of dissolution of K-Na feldspars decreases from n × 10^?11 to n × 10^?12 mol/m² s upon the rise in pH from 3 to 5; it also increases in the plagioclase series with an increase in the portion of anorthite molecules and in the presence of the anions of polybasic organic acids in the solution. The rate of dissolution of feldspars in the model experiments is by 1–3 orders of magnitude higher than that obtained by different methods for native soils. This may be related to the adequacy of determination of the specific surface and its changes with time in native soils.     

Nitrogenase (C2H2) Activity in Roots of Non-Cultivated and Cereal Plants: Influence of Nitrogen Fertilizer on Populations and Activity of Nitrogen-Fixing Bacteria

Root samples of 11 non-cultivated monocotyledonous and 7 dicotyledonous species taken during a wet summer had low mean nitrogenase activities of 10.2 and 7.1 nmol C₂H₄·g^?1 DW·h^?1 after preincubation at pO₂ 0.02, respectively. Maxima of 139–169 nmol·g^?1·h^?1 were observed with Agrostis vulgaris and Agropyron repens on a sandy soil poor in C_org. Three of 6 early, but none of 4 late fodder maize cultivars had a very low activity up to 0.5 nmol·g^?1h^?1. Oat, rye and wheat roots from plots with organic or mineral N fertilizers had activities between 1.3 and 7.3 nmol·g^?1h^?1 at flowering, which were not correlated with their Azospirillum populations (10²-10⁷·g^?1 after preincubation). Winter wheat and barley roots given 0, 40, 80 and 120 kg. ha^?1 NH₄NO₃-N in 0–3 applications had mean activities of 0.08, 4.06, 0.09 and 0.08 nmol or 1.77, 2.67, 0.36 and 0.23 nmol C₂H₄g^?1·h^?1 after flowering, respectively. An appreciable part of this activity could be removed by root washing. In preincubated rhizosphere soil of wheat and barley populations of N₂-fixing, facultative anaerobic Klebsiella and Enterobacter spp. were 10–100 times higher than those of Azospirillum sp., both being higher in O N than in 80 kg N·ha^?1 trials.     

Extraction and speciation analysis of roxarsone and its metabolites from soils with different physicochemical properties

Purpose

The application of roxarsone (ROX), an arsenic-containing compound, as a feed additive in the animal production industry results in elevated soil levels of ROX and its metabolites, namely, monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenate (As(V)), and arsenite (As(III)). This study was conducted to study the extraction and speciation analysis of ROX-related arsenicals in soils with different physicochemical properties and the possible effects of soil properties on the extraction of ROX and its metabolites.

Materials and methods

Analytical method based on high-performance liquid chromatography (HPLC)-inductively coupled plasma–mass spectrometry (ICP-MS) was employed to determine the concentrations of As(III), DMA, MMA, As(V), and ROX extracted by different extraction solvents from different soils spiked by arsenicals. Validity of the developed method was assessed by the recovery efficiencies of arsenic species in soil-dissolved matter solutions containing 20 μg As?·?L^?1 of each arsenic species. Effects of soil properties on the extraction of ROX and its metabolites were analyzed by Pearson’s correlation.

Results and discussion

Arsenic species were separated using gradient elution of water and 20 mmol?·?L^?1 (NH₄)₂HPO₄ + 20 mmol?·?L^?1 NH₄NO₃ + 5 % methanol (v/v) within 27 min. The linear ranges of all arsenicals were 0–200 μg As?·?L^?1 with R ²?>?0.9996. The developed method provided lower limits of detection for As(III), DMA, MMA, As(V), and ROX (0.80, 0.58, 0.35, 0.24, and 1.52 μg As?·?L^?1, respectively) and excellent recoveries (92.52–102.2 %) for all five species. Arsenic speciation was not altered by 0.1 mol?·?L^?1 NaH₂PO₄ + 0.1 mol?·?L^?1 H₃PO₄ (9:1, v/v), which offered better average extraction efficiencies for As(III), As(V), DMA, MMA, and ROX (32.49, 92.50, 78.24, 77.64, and 84.54 %, respectively). Extraction performance of arsenicals was influenced by soil properties, including pH, cation exchange capacity (CEC), total Fe, and amorphous Fe.

Conclusions

ROX and its metabolites from soils could be satisfactorily separated by the developed method for the studied arsenicals. To extract arsenic species from soils, 0.1 mol?·?L^?1 NaH₂PO₄ + 0.1 mol?·?L^?1 H₃PO₄ (9:1, v/v) was recommended. Extraction efficiencies of arsenicals were influenced more by solvent composition than soil physicochemical properties. The present study provides a valuable tool and useful information for determining the concentrations of ROX and its metabolites in contaminated soils.

     

Ozone Formation Potentials of Volatile Organic Compounds and Ozone Sensitivity to Their Emission in the Megacity of São Paulo, Brazil

In the present study, a three-dimensional Eulerian photochemical model was employed to estimate the impact that organic compounds have on tropospheric ozone formation in the Metropolitan Area of São Paulo (MASP). In the year 2000, base case simulations were conducted in two periods: August 22–24 and March 13–15. Based on the pollutant concentrations calculated by the model, the correlation coefficient relative to observations for ozone ranged from 0.91 to 0.93 in both periods. In the simulations employed to evaluate the ozone potential of individual VOCs, as well as the sensitivity of ozone to the VOC/NO _x emission ratio, the variation in anthropogenic emissions was estimated at 15% (according to tests performed previously variations of 15% were stable). Although there were significant differences between the two periods, ozone concentrations were found to be much more sensitive to VOCs than to NO _x in both periods and throughout the study domain. In addition, considering their individual rates of emission from vehicles, the species/classes that were most important for ozone formation were as follows: aromatics with a kOH?>?2?×?10⁴ ppm^?1 min^?1; olefins with a kOH?<?7?×?10⁴ ppm^?1 min^?1; olefins with a kOH?>?7?×?10⁴ ppm^?1 min^?1; ethene; and formaldehyde, which are the principal species related to the production, transport, storage and combustion of fossil fuels.     

Phosphorus Efficiency of Buckwheat (Fagopyrum esculentum)

The ability of buckwheat (Fagopyrum esculentum) roots to acquire phosphorus (P) was characterized by investigating P uptake, morphological features, and chemical changes in the rhizosphere. Over a range of nutrient solution P concentrations (5–500 μmol · L^?1), maximum shoot growth was achieved with a P supply between 5 and 100 μmol · L^?1. Root weight and root length, as well as length and frequency of root hairs, were higher at low P levels. Root surface and the root surface/shoot dry weight ratio reached high values. Though P uptake rates were only moderate (0.15 pmol · cm^?1 root · sec^?1), shoot P concentrations were high (1.8% of dry weight with 100 μM P) predominantly being inorganic (80%). Phosphorus efficiency was characterized by a high specific absorption rate (810 mmol P · kg^?1 root dry wt · d^?1) rather than by an efficient utilization for dry weight production. Root exudates of low-P plants had lower pH values than exudates of high-P plants and increased the solubility of FePO₄ and MnO₂ to a greater extent. Amounts of exuded organic acids and phenolics were low and could not account for the observed solubilization of FePO₄ and MnO₂. Enhanced hydrolysis of glucose-6-phosphate by exudates from low-P plants was due to an increased “soluble” acid phosphatase activity, and root surface phosphatase activity was also slightly enhanced with P deficiency. In the rhizosphere soil of buckwheat, some depletion of organic P forms was observed, and in pot trials with quartz sand, buckwheat utilized glucose- 6-phosphate as a P source at the same rate as inorganic P.     

Sawdust: Cost Effective Scavenger for the Removal of Chromium(III) Ions from Aqueous Solutions

Cr(III) ions sorption onto sawdust of spruce (Picea smithiana) has been studied thoroughly using radiotracer technique. Maximum sorption (94%) of Cr(III) ions (8.98×10^?5 M) onto sorbent surface is achieved from deionized water in 20 min agitation time using 200 mg of sawdust. The sorption data followed the Freundlich, Dubinin-Radushkevich (D-R) and Langmuir isotherms. Freundlich constants l/n = 0.86 ± 0.07 and C _e = 85.0 ± 25.8 mmole g^?1 have been estimated. Sorption capacity, X _m = 0.82± 0.3 mmole g^?1, β = ?0.00356± 0.00017 kJ² mole^?2 and energy, E = 11.9± 0.3 kJ mole^?1 have been evaluated using D-R isotherm. The Langmuir constants Q = 5.8± 0.2 μmole g^?1 and b = (7.4± 0.5)×10⁴ dm³ mole^?1 have been calculated. The variation of sorption with temperature yields thermodynamic parameters Δ H = ?11.6± 0.3 kJ mole^?1, Δ S = ?16.2± 0.9 J mole^?1 K^?1 and Δ G = ?6.8± 0.3 kJ mole^?1 at 298 K. The negative value of enthalpy and free energy reflect the exothermic and spontaneous nature of sorption respectively. Among the anions studied oxalate, citrate, carbonate and borate have reduced the sorption. The cations Y(III), Ce(II) and Ca(II) suppressed sorption. The sawdust column can be used to separate Cr(III) ion from Cs(I), I(I),Tc (VII) and Se (IV).     

Photochemical Formation of OH Radicals in Dew Formed on the Pine Needles at Mt. Gokurakuji

Photochemical formation rates and sources of the hydroxyl (OH) radical were determined in dew water formed on the surface of Japanese red pine (Pinus densiflora) needles of declining (NO₂ polluted area) and healthy pine stands at Mt. Gokurakuji located west of Hiroshima city in western Japan. The measured OH radical photoformation rates in dew water (n=10), which were normalized to the rate at midday on May 1 at 34°N, ranged from 0.67 to 5.18 µM h^?1 (1M=1mol L^?1). The mean value (2.69 µM h^?1) was higher than that in dew water collected on a Teflon board and higher than the mean value in rain water published previously. Of the total OH radical formation rate observed in dew water on the pine needles, 16.4 % was estimated to originate from N (III) (NO₂ ^? and HNO₂) and 24.6 % was estimated to originate from NO₃ ^?. There were other sources of OH radical photochemical formation in dew water on the pine needles besides photolysis of NO₂ ^? and NO₃ ^?.     

The Odd–Even Behaviour of Dicarboxylic Acids Solubility in the Atmospheric Aerosols

The solubility and the enthalpy of dicarboxylic acids have been determined in water at intervals between 278.5 and 543.5 K. At 298.15 K, the values derived were: Δ_sol H _m (m?=?1.33 mol kg^?1)?=?29.80 kJ mol^?1for oxalic acid; Δ_sol H _m (m?=?16.03 mol kg^?1)?=?12.82 kJ mol^?1 for malonic acid; Δ_sol H _m (m?=?0.75 mol kg^?1)?=?28.20 kJ mol^?1 for succinic acid; Δ_sol H _m (m?=?8.77 mol kg^?1)?=?48.01 kJ mol^?1 and Δ_sol H _m (m?=?0.17 mol kg^?1)?=?40.30 kJ mol^?1 for glutaric and adipic acid respectively. The solubility value exhibits a prominent odd–even effect with respect to terms with even number of carbon atoms with the odd carbon numbers showing much higher solubility. Observations made in the atmospheres suggest that this odd–even effect may have implications for the relative abundance of these acids in aerosols.