Equilibria of weak acids and organic Al complexes explain activity of H+ and Al3+ in a salt extract of exchangeable cations

Two sequential extractions with unbuffered 0.1 m BaCl₂ were done to study the release of salt-exchangeable H⁺ and Al from mineral horizons of five Podzols and a Cambisol. Released Al was found to have a charge close to 3+ in all horizons and in both extractions. This finding was supported by the near-equality of the titrated exchangeable acidity (EA_T) and the sum of exchangeable acids (EA = H_e + 3Al_e, calculated from the pH and Al concentration of the extract). The ratio between EA of the second and the first extraction was over 0.50 in the Bs2 and C horizons and smaller in the other horizons. H⁺ was assumed to be in equilibrium with weak acid groups, and the modified Henderson–Hasselbach equation, pK_HH = pH ? n log (α/(1 ? α)), was used to explain pH of the extract. The degree of dissociation (α) was calculated as the ratio between effective and potential cation exchange capacity. Value of the empirical constant n was found to be near unity in most horizons. When the monoprotic acid dissociation was assumed in all horizons, pK_HH had the same value in both extractions. For Al³⁺, two equilibrium models were evaluated, describing (i) complexation reactions of Al³⁺ with soil organic matter, and (ii) equilibrium with Al(OH)₃. Apparent equilibrium constants were written as (i) pK_o = xpH ? pAl³⁺, and (ii) log Q_gibbs= log Al³⁺ ? 3log H^+. The two extractions gave an average reaction stoichiometry x close to 2 in all horizons. Results suggest that an equilibrium with organic Al complexes can be used to express dissolved Al³⁺, aluminium being apparently bound to bidentate sites. The value of log Q_gibbs was below the solubility of gibbsite (log K_gibbs = 8.04) in many horizons. In addition, log Q_gibbs of the second extraction was greater than that of the first extraction in all horizons except the C horizon. This indicates that equilibrium with Al(OH)₃ cannot explain dissolved Al³⁺ in the soils. We propose that the models of pK_HH and pK_o can be used to simulate exchangeable H⁺ and Al³⁺ in soil acidification models.     

中国亚热带地区不同发育阶段杉木林生物量、凋落物及养分流

杉木生长快、产量高、材质好,是中国亚热带地区最重要的造林树种之一,在中国南方人工林经营中占有重要地位。对8、14和24年生杉木人工林生物量、凋落物及其养分流进行的研究结果表明:杉木人工林具有很高的生物生产力和50%-70%的树干生物量积累比例。杉木是低养分归还的针叶树种,凋落量少,而且针叶凋落前养分发生一定程度的转移,凋落物养分含量低,短轮伐期连栽收获制度造成的养分损失是导致杉木人工林地力衰退的原因之一。图1表7参22。     

欧亚大陆地上森林凋落物的研究

根据一个包括471个林分的森林凋落物数据库,本文对欧亚大陆森林生态系统的凋落物产量进行了估计。结果表明:欧亚大陆森林生态系统凋落物产量为每年6.53 Pg (1 Pg = 1015g),其中二分之一发生在热带和亚热带森林,三分之一发生在寒带森林,剩余的发生在温带森林。因此,在欧亚大陆森林生态系统中,森林凋落物每年从森林植被转移大约2.94 Pg 碳到土壤亚系统。表3参18。 关键词:碳流动;欧亚大陆森林;森林凋落物     

Areal activities and stratification of hydrolytic enzymes involved in the biochemical cycles of carbon, nitrogen, sulphur and phosphorus in podsolized boreal forest soils

A novel approach allowing on-site high throughput enzyme activity measurements by fluorogenic model substrates was applied to study the functioning of enzymes involved in biochemical cycling of nutrients in boreal forest soil ecosystems. The examined enzymes comprised α-glucosidase, β-glucosidase, β-xylosidase, β-cellobiosidase, N-acetyl-glucosamidase, acetate-esterase, butyrate-esterase, phosphomonoesterase, sulphatase and aminopeptidase, whereby spatial and seasonal variation of their activity was investigated over nine seasons in 2 years. The studied sites of boreal podzolized soil of Pinus sylvestris and Picea abies forest were located in central Finland. Activity of all enzymes except sulphatase was highest in the humus layer in all seasons. Maximum sulphatase activity was located below the humus layer in the soil column. Annual activities of acetate-esterase, butyrate-esterase, β-glucosidase and phosphomonosterase calculated to in situ temperature during the year were 480-700, 690-950, 110-190 and 110-200 mol m⁻² year⁻¹, respectively. They were up to 100 fold higher than the other six measured activities. The overall turnover capacity of the enzymes was >1000 mol of ester linked carbon, >700 mols carbon from different carbohydrates, 100-200 mol of ester linked phosphate, 10-40 mol of ester linked sulphate m⁻² year⁻¹. Winter time (November-April) contributed from 7 to 32% to the annual turnover capacity indicating important enzyme activities also during a cold period of the year. Clear-cutting of the tree stand did not adversely affect enzyme activities related to the cycling of carbon, nitrogen, sulphur and phosphorus during the year. The pH optimum for hemicellulose and cellulose hydrolysing enzymes was pH 3-4 and the pH optimum of phosphomonoesterase, sulphatase, aminopeptidase and N-acetyl-glucosamidase was 4-5. This shows that the hydrolytic activities were adapted to the acid pH-values of the soils. The soil hydrolytic potential was many fold higher as compared to the actual amount of litter it received in the P. sylvestris and P. abies forests.     

Pressurized hot water extraction of Norway spruce hemicelluloses using a flow-through system

Norway spruce saw meal was extracted with pressurized hot water at 120–240°C using a flow-through system. Only small amounts of hemicelluloses were extracted at 120–160°C, but dissolution was significantly enhanced when higher extraction temperatures were applied. All hemicelluloses but only 15% of lignin were removed from wood at 220°C, and even less lignin was extracted at lower temperatures. Partial degradation of cellulose seemed to take place only at 240°C. Of the total amount of extracted hemicelluloses, 4–22% was hydrolyzed to monosaccharides. Although the average molar masses of extracted hemicelluloses decreased with increasing extraction temperature, even at 240°C the extracted carbohydrates occurred, on average, as polysaccharides. Polysaccharides with an average molar mass of 31 kDa were obtained at 170°C. The molecular-mass characteristics and yield of carbohydrates depend on the extraction temperature, which should be chosen based on the end use of the isolated hemicelluloses.     

Soil respiration after slash and stump removal in three clear-cut areas with patch scarification and mounding

We studied the soil carbon dioxide respiration (R_s) at three clear-cut mesic forest sites in south, central and north central Finland, which had been treated with different intensities of stump lifting and slash removal and then patch mounded and planted with spruce. The follow-up period after the initial calibration lasted for five consecutive years. Throughout the study the R_s remained at fairly steady levels according to the study site and soil disturbance level. Based on a split-plot test using the general linear model there were no significant differences in the R_s between the different stump and slash removal treatments at the three study sites, but unaffected and moderately affected soil surfaces had significantly higher R_s than mounds and wheel ruts. We conclude that the removal of stumps and slash have minor direct effects on R_s, but large indirect effects through soil disturbance.     

Apparent Cation – Exchange Equilibria and Aluminium Solubility in Solutions Obtained from Two Acidic Forest Soils by Centrifuge Drainage Method and Suction Lysimeters

Apparent cation–exchange equilibria and solubility of aluminium were analysed in two acidic forest soils: a Cambisol and a Cambic Podzol. Soil solution was obtained by a centrifuge drainage method from fresh soil samples and with suction lysimeters. The total positive charge of the measured cations as well as the concentrations of the cations were generally much larger in the centrifugates than in the lysimeter solutions, which implies that total charge of soil solution is larger in small pores than in large pores. Hydrogen ion in particular was concentrated in some of the centrifugates, the ratio centrifugate:lysimeter solution being over 10. The total positive charge of the measured cationsdecreased with increasing depth with both methods. Theapparent cation–exchange coefficients K _H-Ca, K _Al-Ca, and K _K-Ca had different values in the methods, and the variation in the cation exchange coefficients was larger in the lysimeter method than in the centrifuging method. The coefficient K _Mg-Ca had similar values in both methods. The results imply that mobile solution could not have cation–exchange equilibria with bulk exchangeable cations in the soils, although solution in small pores seemed to have equilibria. Solubility of Al did not follow the solubility of an Al(OH)₃ phase in the centrifugates, and the centrifugates with a H⁺ activity larger than 60 μmol were undersaturated with respect to the gibbsite. Solubility of Al was between gibbsite and amorphousAl(OH)₃ in the lysimeter solutions. Differencesbetween the centrifugates and the lysimeter solutionsin the ion concentrations and in the apparent chemicalequilibria were similar for both soils studied.     

The effects of soil and air temperature on CO2 exchange and net biomass accumulation in Norway spruce, Scots pine and silver birch seedlings

Soil temperature is proposed to affect the photosynthetic rate and carbon allocation in boreal trees through sink limitation. The aim of this study was to investigate the effect of temperature on CO(2) exchange, biomass partitioning and ectomycorrhizal (ECM) fungi of boreal tree species. We measured carbon allocation, above- and below-ground CO(2) exchange and the species composition of associated ECM fungi in the rhizosphere of Scots pine (Pinus sylvestris L.), Norway spruce (Picea abies K.) and silver birch (Betula pendula Roth) seedlings grown in soil maintained at 7-12, 12-15 and 16-22 °C. We found increased root biomass and photosynthetic rate at higher soil temperatures, but simultaneously with photosynthesis rate, higher temperature generally increased soil respiration as well as shoot, and root and rhizosphere respiration. The net CO(2) exchange and seedling biomass did not increase significantly with increasing temperature due to a concomitant increase in carbon assimilation and respiration rates. The 2-month-long growth period in different soil temperatures did not alter the ECM fungi species composition and the below-ground carbon sink strength did not seem to be directly related to ECM biomass and species composition in any of the tree species. Ectomycorrhizal species composition and number of mycorrhiza did not explain the CO(2) exchange results at different temperatures.     

Effects of site preparation on soil properties and on morphology of Pinus sylvestris and Picea abies seedlings sown at different dates

The aims of the study are to find out the effects of site preparation on soil properties and on the morphology of three-year-old Pinus sylvestris L. and Picea abies (L.) Karst. seedlings sown at different dates along a slope with variation in soil texture, water, and fertility. Based on the hypothesis that soil texture affects soil water content, water retention capacity, and nutrient content, we studied site preparation of varying intensities: exposed C horizon, mounds (broken O/E/B horizons piled over undisturbed ground), and exposed E/B horizon. Though the growing time difference between sowings was about one month, after three growing seasons, spring-sown seedlings were larger than summer-sown seedlings. P. sylvestris seedlings were largest with mounds and smallest with exposed C horizon, but site preparation did not affect the morphology of P. abies seedlings.     

Apparent cation-exchange equilibria in podzolic forest soils

The Gaines–Thomas selectivity coefficient, K, was used to express the relation between the cations in solution and the cations in exchange sites in podzolic forest soils. Soil solution was obtained by centrifuging a fresh bulked soil sample. Exchangeable cations HX, AlX, CaX, MgX and KX and effective cation-exchange capacity, CEC_e, were determined with 0.1 m BaCl₂. Apparent values of K indicated a preference of Ca²⁺ over Mg²⁺ and over Al³⁺ in O, A and B horizons (log K_Al–Ca < 0 and log K_Mg–Ca < 0), whereas log K_K–Ca and log K_H–Ca exceeded zero. The horizons were similar with respect to log K_H–Ca, and the differences in log K_Mg–Ca were small. Log K_K–Ca and log K_Al–Ca increased in the horizons in the order O < A < B. Log K_Al–Ca was not significantly correlated with the fraction AlX/CEC_e. Log K_Mg–Ca was positively correlated with the fractions HX/CEC_e and AlX/CEC_e, and negatively correlated with log (CaX/MgX). The selectivity coefficient of binary cation exchange seemed to be applicable to in situ soil solutions. However, the fraction of each cation on exchange sites should be based on the CEC_e rather than on the sum of the two cations. The latter, also, seemed to be acceptable in cases of exchangeable cations with a large relative content in soil, e.g. in Al³⁺–Ca²⁺ exchange in A and B horizons, and in H⁺–Ca²⁺ exchange in O and A horizons.